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LITHIUM

BATTERIES
Science and Technology
Gholam-Abbas Nazri
Gianfranco Pistoia
[Eds.)

Stabilization of Layered Oxide Cathode

LiNi02 Structure
LITHIUM BATTERIES
Science and Technology
LITHIUM BATTERIES
Science and Technology

Edited by

Gholam-Abbas Nazri
General Motors Research & Development Center
Warren, Michigan, U.S.A.

Gianfranco Pistoia
Consultant Rome,
Italy

Springer
Editors
Gholam-Abbas Nazri Gianfranco Pistoia
General Motors R&D and Planning Center Via G. Scalia, 10
MC 480-102-RCEL 00136 Rome
30500 Mound Road Italy
Warren, MI 48090-9055
USA

ISBN: 978-1-4020-7628-2 (hardcover)


ISBN: 978-0-387-92674-2 (softcover) e-ISBN: 978-0-387-92675-9

Library of Congress Control Number: 2008941279

© Springer Science+Business Media, LLC 2003, First softcover printing 2009


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Contributors XV
xvii

damentals

erials Aspects: An Overview


anthiram
l.l. Introduction 3
1.2. Basic Concepts of Rechargeable Lithium Batteries 3
1.3. Cells with Insertion Compounds as Both Anode and Cathode 8
1.4. Layered Oxide Cathodes 11
1.4.1. Layered LiCo02 12
1.4.2. Layered LiNi02 19
1.4.3. Other Layered Oxides 24
1.5. Spinel Oxide Cathodes 25
1.5.1. Spinel Manganese Oxides 26
1.5.2. Other Spinel Oxides 30
1.6. Oxide Cathodes with Polyanions 32
1.7. Other Oxide Cathodes 33
1.8. Anode hosts 35
1.9. Conclusions 36
References 37

Role of Electronic Properties in the Electrochemical Behavior of


ercalation Compounds from a First Principles Vantage Point
Vander Ven and G. Ceder
2.1. Introduction 42
2.2. General Electronic Structure of Octahedral Transition Metal Ions 45
2.3. First Principles Method 48
2.3.1. The Local Density Approximation (LDA) 54
2.3.2. The Generalized Gradient Approximation (GGA) 54
2.3.3. Spin Polarization 55
2.3.4. Caveas About Approximations to DFf 55
2.3.5. Different Numerical Schemes 57
2.4. Electronic Structure of LixCo02 58
2.4.1. Covalent Bonding in LixCo02 58
2.4.2. Experimental Evidence for Shift in Covalency 62
2.4.3. The Role of Covalency in Determining Thermodynamic,
Kinetic and Structural Properties of LixCo02 64
2.5. Electronic Properties in LiNi02: the 180° Interaction 67
2.6. Layered to Spinel Transformation in LixMn02 71
2.6.1.The Crystallography and Thermodynamics of the Layered
to Spinel Phase Transformation 71
2.6.2. A Two Stage Transformation Mechanism 73
2.6.3. Suppressing the Layered to Spinel Transformation 78
2.7.Conclusions 79
References 80
Contents

thesis of Battery Materials


. Whittingham 85
3.1. Introduction 86
3.2. The Synthesis and Manufacture of Titanium Disulfide
3.3. Synthesis of Alkali Ion Intercalates by Insertion into the Host 88
Lattice (and the Reverse) 90
3.4. High Temperature Synthesis of Layered Oxides 93
3.5. Hydrothermal and Solvothermal Synthesis of Cathode Materials 95
3.6. Ion Exchange Methodes for Lithium Manganese Oxides Synthesis
3.7. Stabilization of Layered LiMn02 and the Mixed Metal Oxides 97
Li(Ni,Mn,Co)02
3.8. Addition of Carbon Conductive Diluents Post-Synthesis and 99
in-situ: LiFeP04 102
3.9. Synthesis of Anode Materials 103
3.10. Mechanochemistry and Mechanical Grinding 105
References

ode Materials

es and Composite Anodes: An Overview


Nazar and 0. Crosnier
4.1. Introduction: Lithium Metal and Carbon Based Materials 112
4. I.I. Issue of Safety, A Brief History 113
4.1.2. Carbonaceous Materials 114
4.1.3. Looking to the Future 115
4.2. Compounds and Composites of Sn, Sb and AI 116
4.2.1. Intermetallics Composites and Binary Phases Comprised of 117
Sn, Sb and AI
4.2.2. Silicides 127
4.3. Metal Oxides 129
4.3.1. Transition Metal Oxides Where Insertion Governs the
Process 130
4.3.2. Transition Metal Oxides Where Reduction of Metal Oxide
to Metallic or Semi-metal Occurs 130
4.3.3. Mixed Transition Metal Oxides- Where Both Reduction and 132
and alloying are Responsible for Li Capacity
4.4. Nitrides and Phosphides 132
4.4. I. Nitrides 132
4.4.2. Phosphides 134
4.5. Conclusions 138
References 139

onaceous and Graphitic Anodes


inter, K.-C. Moeller and J. 0. Besenhard
5.1. Carbons in Ion Transfer Batteries 144
5.2. History of Lithiated Carbons 146
5.3. Electrochemical Li Storage in Carbon 148
5.3.1. Carbonaceous Host Materials and Their Properties 148
5.3.2. Electrochemical Li Storage in Graphitic Carbons 153
5.3.3. Electrochemical Li Storage in Non-Graphitic Carbons 160
5.4. Reactions of Lithiated Carbons with the Electrolyte 167
ts 5.4.1.
Interph
ase
Formation- Metallic Li Anode vs. LixC 6 Anode and Oxide vii
Cathode
5.4.2. Unsolvated and Solvated Lithium Intercalation
5.5. What is Special About Lithiated Carbons?
References 168
171
hite-Electrolyte Interface in Lithium-Ion Batteries 179
azri, B.Yebka, and G.-A. Nazri 180
6.1. Introduction
6.2. Experimental Set Up to Evaluate Surface Reactions of Graphite
Anodes
6.2.1. Graphite Types 195
6.2.2. A General Procedure to Fabricate Carbon Anodes and
their Evaluation 198
6.3. Graphite Cycling and Film Formation 198
6.3.1. Gas Generation on Graphites
6.3.2. Infrared Spectroscopy of SEI Layer on Graphite Anodes 200
6.3.3. Thermal Analysis of SEI Layer on Graphite Anodes 203
6.4. Conclusions 207
References 208
216
Key Role of Nanoparticles in Reactivity of 3d Metal Oxides Towards Li 217
Tarascon, S. Grugeon, S. Laruelie, D. Larcher and P. Poizot 218
7.1. Introduction 220
7.2. Experimental 221
7.3. Results and Discussion 222
7.3.1. Reactivity of 3d Metal Oxides Towards Li 222
7.3.2. Rationalization and Potential Applications 226
7.3.3. Practical Application Considerations 234
7.3.4. Acting on Reaction Paths Through Particle Size 236
7.4. Conclusions 244
References 245

de and Silicide Negative Electrodes


Amatucci and N. Pereira
8.1. Introduction 247
8.2. The Nitrides 248
8.2.1. The Ternary Nitrides 248
8.2.2. The Binary Nitrides 254
8.2.3. Summary- Nitrides 258
8.3. Silicides 259
8.3.1. Introduction 259
8.3.2. Ternary Li-Si-M Systems at Elevated Temperature 260
8.3.3. Silicides at Ambient Temperature 262
8.3.4. Summary- Silicides 267
References 268

s and Intermetallic Anodes


Huggins
9.I. Introduction 270
9.2. Alloys as an Alternative to Pure Lithium 271
Contents

9.2.1. Lithium- Carbon Alloys 271


9.3. Principles Determining the Potentials and Capacities of Alloy
Electrodes Under Equilibrium Conditions 272
9.3.1. Relations Between Phase Diagrams, the Composition
Dependence of the Potential, and the Capacity of
Electrodes 273
9.3.2. An Example, The Lithium-Antimony System 275
9.3.3. Relation Between the Potentials and Thermodynamic
Data 278
9.3.4. Temperature Dependence of the Equilibrium Potential 279
9.3.5. Experiments at Ambient Temperature 283
9.4. Liquid Binary Alloys 283
9.5. Mixed-Conductor Matrix Electrodes 286
9.6. Decrepitation 290
9.7. Formation of Amorphous Products at Ambient Temperature 293
9.8. Summary 294
References 295

rent Issues of Metallic Lithium Anode


shikawa and M. Morita
I 0.1. Intrinsic Advantages and Drawbacks of Metallic Lithium Anode 297
10.2. Historical Aspects in Rechargeable Metallic Lithium Batteries 298
10.3. Recent Trends in the Development of Batteries with aLi Anode 300
10.4. Optimization of the Lithium Anode Interface 300
I 0.4.1. Fundamentals 300
10.4.2. Effect of Additives 303
10.5. Physical Factors Affecting the Lithium Interface 303
10.6 Recent Advances in the Research on Metallic Lithium Anode 304
References 311

athode Materials
nds in Cathode Materials for Rechargeable Batteries
Pasquali, S. Passerini and G. Pistoia
11.1. Introduction 315
11.2. Methods of Synthesis 317
11.3. Effect of Particle Size and Morphology on Cathode Behavior 321
11.4. Natural vs. Artificial Cathodic Films 324
11.5. Specific Cathode Materials 327
11.5.1. LiNi02 and LiCo02 327
11.5.2. Manganese Spinels 335
11.5.3. Layered LixMn02 and Similar Cathodes 341
11.5.4. 3 V Cathodes 344
11.5.5. A Special Case: LiFeP04 347
11.5.6. Sulphur and Organic or Inorganic Sulphides 350
11.5.7. High Voltage Materials 351
11.6. Concluding Remarks 352
References 353

el Cathode Materials for Lithium-Ion Batteries


ia and M. Yoshio
ts ix

12.1. Introduction 361

12.2. LiMn204 and Metal-Ion Doped Spinels LiMxMn2.x04 362


12.3. Optimizing the Capacity and Rechargeability by Using
a Li-Mn-0 Phase Diagram 366
12.4. Capacity Fading on Cycling 369
12.5. Oxygen-Deficient Spinel LiMn204.y 373
12.5.1. Charge/Discharge Profile of Spinels with Different Li/Mn
Ratios and Oxygen Contents 373
12.5.2. Phase Transitions During Charge/Discharge 374
12.5.3. Phase Transition at Low Temperature 375
12.6. Summary 377
References 377

yered Manganese Oxides as Cathodes


mmundsen
13.1. Introduction 381
13.2. Overview of the Structure and Stability of Layered Manganese 383
Oxides
13.2.1. Layered vs. Orthorhombic Structure of LiMn02 383
13.2.2. Instability with Respect to the Spinel Structure 384
13.2.3. Alternative Layered Structures 387
13.2.4. Layered Lithium Manganese Oxides with Tetravalent
Manganese 388
13.3. Layered Manganese Oxides Based on LiMn02 389
13.3.1. Orthorhombic LiMn02 389
13.3.2. Lithium Manganese Oxide with the 03 Layered Structure
Prepared by "Soft Chemistry" Routes 390
13.3.3. Substituted LiMn02 with the 03 Layered Structure
Prepared by High Temperature Processing 392
13.3.4. 02 Layered Structures 395
13.4. Layered Solid Solution Cathode Materials Based on Tetravalent
Manganese 397
13.4.1. Overview of Solid Solution Approaches 397
13.4.2. Solid Solutions with LiCr02 399
13.4.3. Lithium-Rich Solid Solutions with LiCr02 402
13.4.4. Solid Solutions with LiNi02 and LiCoxNi 1.x02 402
13.4.5. Further Work 406
13.5. Summary and Outlook 406
References 407

hodes Based on LiCo02 and LiNi02


ark, Y. J. Kim and J. Cho
14.1. LiCo02 Cathode Materials 410
14.1.1. Introduction 410
14.1.2. Capacity Fading Mechanisms in LiCo02 Cathode Materials 414
14.1.3. Electrochemical Properties ofLiCo02 Cathodes 416
14.1.4. Doping the LiCo02 Cathode 420
14.2. LiNi02 Cathode Materials 422
14.2.1. Introduction 422
14.2.2. Structure of LiNi02 422
Contents

14.2.3. Electrochemical Properties and Capacity Fading


Mechanisms of LiNi02 423
14.3. Metal-Oxide Coating on LiCo02 Powders 426
14.3.1. Introduction 426
14.3.2. Preparation of Metal-Oxide Coated LiCo02 Powders 426
14.3.3. Cycle-Life Performance of Metal-Oxide Coated LiCo02 427
14.4. Thin-Film LiCo02 Cathodes 43 I
14.4.1. Introduction 431
14.4.2. Electrochemical Properties of AhOrCoated LiCo02 Thin
Films 431
14.4.3. Future Work 441
References 442

yanion-Based Positive Electrode Materials


Masquelier, S. Patoux, C. Wurm, M. Morcrette
15.1. Introduction: from Oxides to lonically Conducting
Polyanionic Frameworks 445
15.2. Tuning the M"+/M<n-1)+ Redox Couple in the NASICON structure
by Changing the Chemical Nature of the XO/. Groups: Inductive
Effect 448
15.2.1. Relative Position of Various M"+tM<n-1)+ Redox Couples
(M =Fe, Ti, V, Nb) in NASICON Phosphates 450
15.2.2. Position of the Ti4+/Ti3+ Couple vs. Li+/Li and Na+/Na 451
15.2.3. Relative Positions of the Ti4+/Ti 3+, Fe3+/Fe2+, Nb5+/Nb4+,
Nb4+/Nb3+, V4+tv 3+ and V 3+/V2+ Couples vs. Na+/Na and Li+/Li
in the NASICON Structure 453
15.3. Extension of the Concept to Other Polyanionic Structures 456
15.3.1. The Monoclinic Forms ofFe2 (S04h and Li 3M2 (X04h
(M=Fe, V,X=P,As) 457
15.3.2. The Rhombohedral Form of Li3Fe2 (As04h 460
15.3.3. The Diphosphates and Diarsenates Li,MX207 (M =Fe,
V, Ti; X= P, As) 461
15.3.4. Amorphous or Crystalline Iron Phosphates: FeP04 .nH20
and Fe4(P207h.4H20 463
15.3.5. V5+/V4+ and V4+/V 3+ Couples in LixVOX04 (X= P, As) 466
5 4
15.3.6. Nb +/Nb + Couple in LixNbP05 467
15.3.7. The Olivine LiMP04 (M =Fe, Mn, Co) 469
15.4. Conclusions 473
References 474

erstanding Phase Transformations in Lithium Battery Materials by


nsmission Electron Microscopy
Shao-Horn 478
16.1. Introduction 481
16.2. Transmission Electron Microscopy 481
16.2.1. Electron Diffraction of Crystals 483
16.2.2. TEM Imaging 484
16.2.3. TEM Sample Preparation 484
16.2.4. Caveat toTEM Techniques

16.3. Lithium and Vacancy Ordering 484


16.3.1. Lithium and Vacancy Ordering in 03 Li,Ni02 485
ts xi

16.3.2. Lithium and Vacancy Ordering in 03 L,Co02 487


16.3.3. Lithium Ordering in 02 derived Li,Co02 489
16.4. Spatially Localized Phase Transitions 492
16.4.1. Jahn-Teller Induced Phase Transition in Li,[Mn2 ]04 493
16.5. Phase Transformation Between 2D Layered and 3D Spinel Related
Configurations 494
16.5.1. Intermediate Layered-Spinel Cation Configurations in LT-LiCo02 497
16.5.2. Layered to Spinel Transformation in Cycled Li,Mn02 499
16.6. Perspectives 500
16.6.1. High-Resolution TEM Imaging and Simulation 500
16.6.2. EELS Analysis and Imaging 502
16.6.3. In-Situ TEM Imaging 502
References 503

lectrolytes
uid Electrolytes: Some Theoretical and Practical Aspects
Nazri 509
17.1. Introduction to Solvents 511
17.2. Coulombic Forces Between Ions and Dipolar Solvents 511
17.2.1. Ion-Dipole Forces 513
17.2.2. Dipole-Dipole Interactions 513
17.2.3. Dipole-Induced Dipole Interactions 514
17.2.4. Instantaneous Dipole-Induced Dipole Interaction Forces 515
17.2.5. Hydrogen Bonding
17.3. Electron Pair Donor-Electron Pair Acceptor Interactions 516
(EPD/EPA Interactions) 517
17.4. Solvation 518
17.4.1. Solvation Number 518
17.4.2. Selective or Preferred Solvation 519
17.5. The Basic Requirements of Electrolytes for Lithium Batteries 520
17.5.1. Electrolyte Conductivity 525
17.5.2. The Electrochemical Stability of Organic Electrolytes 527
17.6. Conclusions 527
References

vanced Liquid Electrolyte Solutions


Aurbach and A. Schechter

18.1. Introduction 530


18.1.1. Types of Advanced Liquid Electrolyte Solutions 530
18.1.2. Scope of Subjects of Interest 532
18.2. General Properties of Liquid Electrolyte Solutions 532
18.2.1. On the Physical Properties of Polar Aprotic Electrolyte
Solutions 532
18.2.2. How to Evaluate Solvents for Electrolyte Solutions 535
18.2.3. On the Conductivity of Polar Aprotic Solutions and
Diffusion of Ions in Them 539
18.3. Electrochemical Windows of Nonaqueous Electrolyte Solutions 541
18.3.1. On Cathodic Reactions of Polar Aprotic Electrolyte
Solutions 545
Contents

18.3.2. Oxidation Reactions in Polar Aprotic Electrolyte 547


Solutions
18.3.3. A Short Summary of the Anodic Limit of Nonaqueous 552
Electrolyte Solutions
18.4. Liquid Electrolytes Solutions for Rechargeable Li (Metal) 553
Batteries 553
18.4.1. Problems with the Use ofLi Metal Anodes
18.4.2. On the Choice of Electrolyte Solutions for Rechargeable Li 556
(Metal) Batteries 560
18.5. Liquid Electrolyte Solutions for Rechargeable Li-Ion Batteries
18.5.1. The Requirements of Suitable Solutions for Li-Ion 560
Batteries 561
18.5.2. Standard Electrolyte Solutions for Li-Ion Batteries 564
18.5.3. Advanced Electrolyte Solutions for Li-Ion Batteries 567
18.6. Molten Salts 567
18.6.1. Introduction
18.6.2. Electrochemical Properties of Molten Salt Solutions and 568
Battery Applications 568
References

ymeric Electrolytes: An Overview


. Kerr
19.1. Introduction 574
19.2. Lithium Transport in Lithium Batteries 575
19.2.1. Solvent-free, Ion-Coupled Systems 577
19.2.2. Effect of Polymer Molecular Structure (Architecture) 579
19.2.3. Effect of Polymer Solvation Structure 582
19.2.4. Effect of Surfaces on Polymer Electrolyte Behavior 587
19.2.5. Gel Polymer Systems 591
19.3. Polymer Electrolytes in Lithium Batteries 592
19.3.1. The Effect of Transport Properties on Cell Performance 595
19.3.2. Polyelectrolyte Single-Ion Conductors 602
19.3.3. Chemical and Electrochemical Stability of Polymer Electrolytes 604
19.3.4. Dendrite Growth 609
19.3.5. Mechanical Properties 613
19.4. Conclusions 615
References 617

s and Ceramic Electrolytes for Lithium and Lithium-Ion Batteries


. Dudney
20.1. Introduction 623
20.2. Glass Electrolytes 625
20.2.1. Oxide Glasses 626
20.2.2. Oxynitride Glasses and Lipon 626
20.2.3. Sulfide and Oxysulfide Glasses 628
20.2.4. Thionitride Glasses 629
20.2.5. Lithium Halide Doped Glasses 629
20.3. Crystalline Ceramic Electrolytes 630
20.3.1. Perovskite Electrolytes 631
20.3.2. Nasicon-Type Phosphates 632
20.3.3. Lisicon-Type Materials 633
ts xiii

20.3.4. Lithium Metal Halides, Nitrides, and Phosphides 633


20.3.5. Other Compositions 634
20.4. Models for Ion Conduction 634
20.5. Conclusion 635
References 637

tery Systems and Applications


on Batteries for EV, HEV and Other Industrial Applications
Broussely
21.1. Introduction 645
21.1.1. Specific Properties Required of Industrial Li-Ion Batteries 646
21.2. Which Li-Ion Chemistry for a Large Battery? 646
21.2.1. Positive Materials 646
21.2.2. Negative Materials 651
21.3. General Technology and Manufacturing Processes 651
21.3.1. General Considerations for Battery Assembly 652
21.4. EV Applications 652
21.4.1. EV Battery Requirements and Technology Comparison 653
21.4.2. Battery Monitoring and Management 654
21.4.3. Li-Ion Technology for EV 655
21.5. HEY Applications 663
21.5.1. Application Requirements 663
21.5.2. Competing Battery Technologies 664
21.5.3. High Power Li-Ion Technology Challenges 664
21.6. Stationary Applications 671
21.6.1. Standby (Float) Operations 671
21.6.2. Intermittent Charging (Cycling) Applications 673
21.6.3. Buffer Operation 673
21.6.4. Stationary Battery Trials 674
21.7. Space Applications 674
21.7.1. Battery Requirements for Satellites 675
21.7.2. Competing Technologies 676
21.7.3. Saft Cell and Battery Design 677
21.7.4. Other Battery Designs 680
21.7.5. Launchers 683
21.8. Conclusions 684
References 684

ium Batteries for Medical Applications


. Takeuchi, R. A Leising, D. M. Spillman,
ubino, H. Gan, K. J. Takeuchi and A C. Marschilok
22.1 Introduction 686
22.2 Primary Batteries 687
22.2.1. The Use of Lithium Metal as an Anode 687
22.2.2. Lithium/Iodine Systems and their Medical Applications 688
22.2.3. Lithium/Thionyl Chloride Systems and their Medical Applications 689
22.2.4. Lithium/CFx Systems and their Medical Applications 691
22.2.5. Lithium/Silver-Vanadium-Oxide Systems and their Medical
Applications 691
22.2.6. Lithium/Mn02 Systems and their Medical Applications 694
Contents

22.3. Secondary Batteries 694


22.3. I. Lithium-Ion Systems - General Considerations 694
22.3.2. Lithium-Ion Systems- Current and future Medical Applications 697
22.4. Summary 699
eferences 699

rent Issues and Market Trends of Li-Ion Batteries for Consumer Applications
acArthur
23. I. Introduction 70 I
23.2. Lithium-Ion batteries 702
23.2.1. The Market 702
23.2.2. Different Technologies 704
23.2.3. Targets: Small and Large Batteries 705
References 706

Index 707
f Contributors

Chapter Name Chapter

Amatucci
mundsen
rbach
Besenhard
oussely
der

osnier
Dudney

ugeon
Huggins
ikawa
err
Kim
cher
uelle
Leising
cArthur
nthiram
Marschilok
squelier
Moeller
orcrette
ce:

The science and technology of lithium batteries have dominated the


f advanced power sources and replaced many other batteries in the
, particularly in the areas of communications, computers, electronics,
n more power demanding devices such as power tools and
rtation. The significant progress of lithium batteries is mainly due to
merous innovations in materials, design and safety aspects of the
s. Solid-state chemists, material physicists, materials scientists and
chemists are among the main contributors to the field of advance
batteries. Potential improvements in performance and application of
ost yet safer materials in lithium batteries are in near horizon.
This book provides the most current knowledge and recent concepts
anced lithium batteries. The book is designed to serve the researchers
ield also as a text for academic teaching. The emphasis is on materials
of advanced lithium batteries. Applications of the lithium batteries in
l field and transportation also have been reviewed. The general
ts of the device are discussed first and detailed electrode and
lyte materials are covered in the subsequent chapters.
Chapter one is providing a general background for the advanced
batteries and an over view of electrode materials, electrode
mances, and materials engineering. This chapter is highly
mended for students and practitioners in the field. Chapter two is a
overview of advanced theoretical approaches currently in use for
understanding of lithium battery electrodes and provides a guide for
ng new electrode materials. The pros and cons of each theoretical
, and the mechanism of charge transfer and structural modification of
lation electrodes and contribution of anions are discussed. Chapter
provides a general overview of advance synthesis for electrode
ls. Both traditional methods such as ceramic and solution techniques
ntraditional methods such as hydrothermal and mechanochemistry
s are covered in this chapter.
Part two of this book is a comprehensive discussion on alternative
materials for lithium batteries. Chapter four provides a general
ound on alternative anodes with a detailed analysis of intermetallics,
sites, metal oxides, nitrides and phosphides anodes. Chapter five
chemistry and physics of lithium intercalation into graphitic anode.
ation of carbonaceous materials and various graphitic materials are
scussed. Chapter six is an overview of carbonaceous materials with
sis on reactivity of lithiated graphite with organic electrolytes.
lyte decomposition on reactive anodes and formation of SEI layer and
s species are also discussed. Chapter seven is covering the role of
articles in reactivity of transition metal oxides anodes. This chapter
s a comprehensive discussion on mechanism, thermodynamics and
ii

s of the reversible redox process in transition metal oxide with lithium.


uilibrium voltage values and overpotentials for various metal oxides
apped in this chapter. The reaction pathways and mechanism of
on metal oxides reaction with lithium are clearly illustrated by in-situ
iffraction, magnetic and electrochemical measurements. Chapter eight
with most recent advances in metal nitrides and metal silicides anodes.
nism of reversible lithium insertion - extraction process in these
of materials is discussed. The role of nano-particle in enhanced
ity of transition metal nitrides are also presented. Chapter nine is
ng the fundamentals of lithium alloys and intermetallic anodes. The
diagrams of alloys also complement the voltage profiles of this class of
anodes. Chapter ten provides a general background on metallic lithium
and reviewed recent progresses made in understanding the nature of
anode - electrolyte interface. The role of various additives, stack
re and temperature are also discussed in this chapter.
In part three the cathode materials are reviewed. Chapter eleven
es a general background and trends in rechargeable cathode materials. r
twelve deals with synthesis, characterization and performance of
nese oxide spinel as cathode materials. Potentials and limitations of
cathodes, particularly their performances at elevated temperatures are
sed in this chapter. Chapter thirteen is a comprehensive review of the
pment of advanced layered transition metal oxide based on manganese
. Chapter fourteen is covering the structure, and performance of the
d lithium cobalt and lithium nickel oxide cathodes. Various synthesis
for preparation of layered transition metal oxides are also presented.
r sixteen is covering the electrochemical performances of layered
denum oxides. The role of hydrated water molecules on
chemical performance of the hydrated molybdenum oxide are
ted. Thermodynamic parameters are extracted from temperature
ent voltage profiles of the molybdenum oxide-based cathodes.
r seventeen is covering the microstructure of various cathode
als and providing a general background on application of transmission
n microscopy for analysis of battery electrodes.
Part three deals with various aspects of non-aqueous, polymeric and
c electrolytes. Chapter eighteen is a general overview of fundamentals
-aqueous electrolytes. The conductivity of various multi-blend organic
ates is presented. The dynamic nature of solvent-solvent and lithium
olvent molecule interactions is discussed. Numerous tables with
al properties of organic solvents are presented. This chapter also serves
ference for physical properties of aprotic solvents. Chapter nineteen
es a comprehensive analysis of liquid electrolyte and fundamentals of
de-electrolyte interface. A general over view of polymeric electrolytes
sented in chapter twenty. Recent advances are discussed and older ts
are challenged. Chapter twenty-one deals with synthesis, fabrication
xix

erformances of ceramic electrolytes. Physical methods for preparing


lm electrodes and micro-batteries are also presented in this chapter.
Part five is devoted to the application of lithium batteries in
ortation and medical field. The market analysis of lithium batteries and
uture prospects are also presented in part five. Chapter twenty-two is a
l review of lithium battery for transportation with an emphasis on high
lithium ion technology for hybrid electric vehicles. The lithium ion
logy based on advanced nickel oxide based cathode and graphitic
are presented. Application of lithium batteries in medical fields and
iaturization are discussed in chapter twenty-three. Chapter twenty-four
es current market trends and future prospects for the lithium ion
es.
Authors would like to thank all contributors to this book and many
to the Kluwer Publishing Company, particularly Mr. Alex Greene for
dance and patience during the course of preparing this book. We also
thank our families for their continuous support while we were
g on this manuscript.

Gholam-Abbas Nazri Gianfranco Pistoia


GM Res. & Dev. Center Battery Consultant
Warren, Michigan, USA Rome, Italy
pter 1

MATERIALS ASPECTS: AN OVERVIEW


A. Manthiram

aterials Science and Engineering Program, The University of Texas at Austin,


Austin, TX 78712, USA

INTRODUCTION

The exponential growth in portable electronic devices such as cellular


s and laptop computers during the past decade has created enormous t
in compact, light-weight batteries offering high energy densities.
growing environmental concerns around the globe are driving the
pment of advanced batteries for electric vehicles. Lithium-ion
es are appealing for these applications as they provide higher energy
y compared to the other rechargeable battery systems such as lead
ickel-cadmium, and nickel-metal hydride batteries as shown in Figure
he higher volumetric and gravimetric energy densities of the lithium lls
in Figure 1.1 are due to the higher cell voltages (- 4 V) achievable e
use of non-aqueous electrolytes, which also allow a wider
ature of operation. Lithium-ion cells have become a commercial
after the initial announcement by Sony in the early 1990s because of
ense world-wide activity on lithium insertion compounds (electrode
als) during the past three decades. This chapter provides an overview
electrode materials aspects of rechargeable lithium batteries. A more d
discussion of the specific cathode and anode materials systems as
s the electrolytes is presented by various authors in the subsequent
rs.

BASIC CONCEPTS OF RECHARGEABLE


LITHIUM BATTERIES
Rechargeable lithium batteries involve a reversible insertion/
ion of lithium ions (guest species) into/from a host matrix
Chapter 1

ode material), called lithium insertion compound, during the


rge/charge process. The lithium insertion/extraction process occurring
a flow of ions through the electrolyte is accompanied by a
ion/oxidation (redox) reaction of the host matrix assisted with a flow
ctrons through the external circuit. This concept of rechargeable
m batteries was first illustrated with a transition metal sulfide, TiS2, as
2
thode, metallic lithium as the anode, and a non-aqueous electrolyte.
iS2 cathode has a layer structure as shown in Figure 1.2. During
rge, the lithium ions are inserted into the van der Waals gap between
fide layers and the charge balance is maintained by a reduction of the
3
ns to Ti +. During charge, exactly the reverse process involving the
tion of lithium from the van der Waals gap and an oxidation of Te+ to
ccurs. During the lithium insertion/extraction (discharge/charge)
s, the layer structure is maintained, resulting in good reversibility.

50
Smaller

00

50 1-o
..Q...).
Lithium-ion
00

C)
oO
50
Ni/Cd Ni/MH
Lead-acid
0
0 100 200 300 400
Volumetric Energy Density (Wh/L)

1.1. Comparison of the gravimetric and volumetric energy densities of various


able battery systems.
l Aspects: An Overview 5

s
Ti ............................
............................
s
Li 00
s

............................ TI

1.2. Illustration of lithium insertion/extraction into/from the layered TiS 2 during the
ge/charge process.

The open-circuit voltage Voc of such a lithium cell is given by the


nce in the lithium chemical potential between the cathode (f.lu<cl) and
ode (f.lu(a)) as:

V = f.lu(c) - f.lu(a)
(1.1)
oc F

F is the Faraday constant. Figure 1.3 shows a schematic energy


m of a cell at open circuit. The cell voltage Voc is determined by the
es involved in both the electron transfer and the Lt transfer. While
ergy involved in electron transfer is related to the work functions of
thode and anode, that involved in Li+ transfer is determined by the
structure and the coordination geometry of the site into/from which ns
3
are insertedlextracted. Thermodynamic stability considerations
e the redox energies of the cathode (Ec) and anode (Ea) to lie within
nd gap Eg of the electrolyte, as shown in Figure 1.3, so that no
ted reduction or oxidation of the electrolyte occurs during the charge
rge process. Thus the electrochemical stability requirement imposes a
ion on the cell voltage as:

(1.2)
Chapter 1

Although the concept is simple, the lithium insertion compound


satisfy several criteria in order for it to be a successful cathode
al in a rechargeable lithium cell:

e insertion compound LixMyXz (X = anion) should have a high lithium


mical potential (fJuccJ) to maximize the cell voltage. This implies that
transition metal ion Mn+ in LixMyXz should have a high oxidation
e.

LUMO JA.a(Li)

Jlc(Li)
eVoc

Cathode Anode
Electrolyte/separator

1.3. Schematic energy diagram of a lithium cell at open circuit. HOMO and LUMO
spectively, to the highest occupied molecular orbital and lowest unoccupied molecular
n the electrolyte.

insertion compound LixMyXz should allow an insertion/extraction of


rge amount of lithium, x, to maximize the cell capacity. This depends
the number of available lithium sites and the accessibility of multiple
ences for M in the insertion host. A combination of high capacity and
voltage can maximize the energy density, which is given by a
duct of the capacity and voltage.

lithium insertion/extraction process should be reversible with no or


imal changes in the host structure over the entire range x of lithium
l Aspects: An Overview 7

ertion/extraction in order to provide a good cycle life for the cell. This
plies that the insertion compound LixMyXz should have good structural
bility without breaking any M-X bonds.
e insertion compound should support mixed conduction. It should have
d electronic conductivity cre and lithium-ion conductivity cru to
imize polarization losses during the discharge/charge process and
reby to support a high current density and power density. This
ends on the crystal structure, arrangement of the MXn polyhedra,
metry and interconnection of the lithium sites, nature and electronic
figuration of the Mn+ ion, and the relative positions of the Mn+ and xn
rgies.

e insertion compound should be chemically stable without undergoing


reaction with the electrolyte over the entire range, x, of lithium
ertion/extraction.

e redox energy of the cathode in the entire range, x, of lithium


ertion/extraction should lie within the band gap of the electrolyte as
wn in Figure 1.3 to prevent any unwanted oxidation or reduction of
electrolyte.

m a commercial point of view, the insertion compound should be


xpensive, environmentally benign, and lightweight. This implies that
Mn+ ion should preferably be from the 3d transition series.

Following the initial demonstration of the concept of rechargeable


batteries with the layered TiS2, 2 several other sulfides and
4
genides were pursued during the 1970s and 1980s as cathodes.
ver, most of them exhibit a lower cell voltage of <2.5 V versus
ic lithium anode. This limitation in cell voltage is due to an overlap of
gher valent Mn+:d band with the top of the nonmetal:p band - for
le, with the top of the S:3p band as shown in Figure 1.4. Such an
p results in an introduction of holes into (or removal of electrons
2
the S -:3p band and the formation of molecular ions such as s;-'
in tum leads to an inaccessibility of higher oxidation states for Mn+ in
de LixMySz. The stabilization of higher oxidation state is essential to
ize the cell voltage. Recognizing this difficulty with chalcogenides,
nough's group at the University of Oxford focused on oxide cathodes
2
the 1980s.5 7- The location of the top of the 0 -:2p band much below
2
p of the S -:3p band and a larger raising of the Mn+:d energies in an
compared to that in a sulfide due to a larger Madelung energy (Figure
ake the higher valent states accessible in oxides. For example, while
an be readily stabilized in an oxide, it is difficult to stabilize Co3+ in a
Chapter 1

2 13
since the Co + + redox couple lies within the S2-:3p band as seen in
1.4. Accordingly, several transition metal oxide hosts crystallizing in
ty of structures (2-dimensional layered and 3-dimensional framework
res) have been pursued during the past two decades and Figure 1.5
res the electrochemical potential ranges of some selected lithium
on compounds versus metallic lithium. Cell voltages of as high as 5 V
metallic lithium have been achieved with oxide insertion compounds
n in Fifiure 1.5. The readers may refer to some of the review articles
6
ooks s- in the field to get a more detailed account of the various
insertion compounds that have been investigated over the past three
s.

E E

Co3+/2+

Co3+12+
Co4+/3+

Density of State N(E) Density of State N(E)

1.4. Relative energies of metal:d (for example, Co:3d) and nonmetal:p in (a) a sulfide
an oxide.

CELLS WITH INSERTION COMPOUNDS AS


BOTH ANODE AND CATHODE

Despite the development of several lithium insertion compounds


the 1970s and 1980s, the commercialization of rechargeable lithium
es was hindered for many years until the announcement by Sony in
ly 1990s. The delay was mainly because of the difficulties posed by
etallic lithium anodes. As an alkali metal, lithium is chemically
e with the non-aqueous electrolyte, which results in the formation of
l Aspects: An Overview 9

ivating film on the metallic lithium anode. Although the passivating


n the surface prevents the bulk from further corrosion, it leads to a
niform plating of lithium during charging. This results not only in a
ell failure due to dendritic short circuiting, but also in serious safety
ms due to local over heating. The difficulties associated with the
ic lithium anode prompted to pursue a strategy in which a lithium
on compound instead of metallic lithium could be used as an anode.

>
-s

g-
Q)
C)
ctS

LixGriaphite ILixCoke
0- - Li Metal
-LiAl

Insertion Compound

1.5. Electrochemical potential ranges of some lithium insertion compounds in


e to metallic lithium.

Such cells consisting of lithium insertion compounds as both cathodes


nodes are called lithium-ion cells or rocking-chair cells since the
ion shuttles or rocks between the cathode and anode hosts during the
/discharge process as illustrated in Figure 1.6. This strategy, however,
s a careful selection of cathode and anode pairs in order to maintain
eptable cell voltage of at least 3 V and to realize a reasonable energy
without unduly increasing the weight or volume of the cell through
ertion compound anode.
With this strategy, the anode and cathode insertion hosts should
espectively, the lowest and highest voltages versus metallic lithium in
to maximize the cell voltage while satisfying the other required
. Accordingly, among the various known lithium insertion
Chapter I

unds, LiCo02, LiNi02 and LiMn204 oxides having a high electrode


ial of 4 V ··versus metallic lithium, have become attractive cathodes
hium-ion cells. Although one might tend to prefer a cathode like
Co04 offering 5 V versus lithium (Figure 1.5), the long-term stability
h the electrolyte and the cathodes under such a high voltage need to be
assessed before they could be considered for commercial cells (see
On the other hand, graphite and coke having a lower electrode
ial of <1 V versus metallic lithium and lightweight have become
ive anodes. The lithium-ion cells are presently made with LiCo02
es and carbon anodes as shown in Figure 1.6. In such a cell, the
m ions migrate from LiCo02 cathode to the LixC6 anode through the
lyte and the electron flows through the external circuit from the
e to the anode during the charge process. An exactly reverse reaction
during the discharge process. Although the replacement of metallic
m having a huge capacity of 3860 rnAhlg by carbon having a capacity

Cathode

Discharge
u+
Charge

Electrolyte

1.6. Schematic illustration of the charge/discharge process in a lithium-ion cell


ng of lithium insertion compounds as both anode and cathode.

rnAh!g causes an important sacrifice in energy density, the lithium


lls involving the shuttling of lithium ions between the two insertion
without any metallic lithium offer significant advantages in terms of
and cycle life.
From a materials design point of view, the anode insertion
l Aspects: An Overview 11

und LixMyXz should also satisfy several important criteria like the
e insertion host: a large degree x of lithium insertion/extraction
capacity), high electronic and ionic conductivity, good chemical and
ural stabilities (reversibility), and affordable cost. The main difference
en the anode and cathode insertion hosts is that the former should have
lithium chemical potential (f.!u(a)) in order to maximize the cell
e, which implies that the Mn+ ion in the LixMyXz anode should have
xidation state.
Apart from the various intrinsic characteristics of the insertion
ode materials discussed, several other criteria are important in
ing a good lithium-ion cell that can offer high performance with long
life. The electrolyte should have high lithium-ion conductivity, but
be an electronic insulator in order to avoid internal short-circuiting.
h ionic conductivity in the electrolyte is essential to minimize IR drop
mic polarization and achieve good rate capability. With a given
lyte, the IR drop due to electrolyte resistance can be reduced and the
pability can be improved by having a higher electrode interfacial area
in separators. The electrolyte should also have good chemical stability
ould not undergo any direct reaction with the electrodes. Additionally,
gineering involved in cell design and fabrication plays a critical role in
erall cell performance. 12 For example, high electronic conductivity
hium-ion diffusion rate in the electrodes are essential to minimize cell
zations and the electronic conductivity of the electrodes can be
ved by adding electronically conducting additives such as carbon.
ver, the amount of additive should be minimized to avoid any undue
ce in gravimetric or volumetric capacity. Finally, cell safety,
nmental factors, and raw material and fabrication costs are additional
tant considerations in both materials selection and cell design.

LAYERED OXIDE CATHODES


Several oxides with a general formula LiM02 (M = V, Cr, Co, and Ni)
llize in a layered structure in which the u+ and M3+ ions occupy the
ate (111) planes of the rock salt structure to give a layer sequence of -
0-M-0- along the c axis as shown in Figure 1.7 for LiCo02• The
ure has an oxygen stacking sequence of ...ABCABC... along the c
nd the u+ and M3+ ions occupy the octahedral interstitial sites of the
close-packed oxygen array. This structure is designated as the 03
tructure since the u+ ions occupy the octahedral sites (0 referring to
dral) and there are three M02 sheets per unit cell. The structure with a
ly (covalently) bonded M02 layers allows a reversible
tion/insertion of lithium ions from/into the lithium planes. The
nnected lithium-ion sites through the edge-shared Li06 octahedral
Chapter 1

ement between the M02 layers provide fast two-dimensional lithium


ffusion leading to high cru. On the other hand, the edge-shared M06
dral arrangement with a direct M-M interaction can provide good
nic conductivity O'e depending on the electronic configuration of the
n. As a result, the LiM02 oxides crystallizing in the 03 structure have
e attractive candidates as cathodes and they are discussed below.

o Li
•co
c/2 Go

. 7. Crystal structure of LiCo0 2 having the 03 layered structure.

Layered LiCo02

LiCo02 synthesized by conventional high temperature procedures at T


C adopts the 03 layer structure (Figure 1.7) with an excellent ordering
u+ and Co3+ ions on the alternate (111) planes of the rock salt lattice.
ntrast, synthesis at lower temperatures (-400°C) results in a
3
erable disordering of the u+ and Co + ions leading to the formation of
iated spinel-like LiCo02 phase with a cation distribution of
c[Co2h6d04 as indicated by X-ray diffraction and single crystal
17 20
n diffraction studies. - This low-temperature form is designated as
Co02 and it exhibits poor electrochemical properties, making it an
21
ctive cathode. Thus heating the LiCo02 sample at high temperatures
00°C) is essential to have a good mobility for the cations and a
l Aspects: An Overview 13
3
uent ordering of the Lt and Co + ions on cooling to give the desired
ered structure.
The 03-type LiCo02 obtained by the high temperature procedure
ts good electrochemical properties and most of the commercial
-ion cells are currently made with the LiCo02 cathodes. A high
3 14
m chemical potential )..lu(c) associated with the highly oxidized Co + +
5
provides a high cell voltage of around 4 V, and the discharge
e does not change significantly with the degree of lithium
partially filled t;;x
tion/insertion x in Li1_xCo02 (Figure 1.8). The direct Co-Co interaction
band associated with the Co 3+14+ couple leads to
lectronic conductivity for Li 1_xCo0 2• Additionally, a strong preference
3
low-spin Co + (t;ge) and Co 4+ (tgge) ions for the octahedral sites
es good structural stability for Li 1_xCo0 2 without encountering a
3
ion of the Co +14+ ions from the octahedral sites of the cobalt plane to
tahedral sites of the lithium plane via the neighboring tetrahedral sites
ter). These features have made LiCo02 an excellent cathode for the
-ion cells.

c a
b-
3
0 50 100 150 200
Capacity (mAh/g)

1.8. Typical discharge curves of (a) layered LiCo02, (b) layered LiNi0.85Co0.850z, and
el LiMn204.

However, only 0.5 lithium ions per LiCo02 formula could be


bly extracted/inserted and cycling to (l-x)<0.5 in Li 1_xCo0 2 results in
ty fade. This translates into a practical capacity of around 140 mAh/g,
is 50% of the theoretical capacity. The limitation in practical capacity
en attributed in the literature to an ordering of lithium ions and
uent structural distortions (hexagonal to monoclinic transformation)
2
x=0.5 in Li 1_xCo0/ and side reactions at >4.2 V (versus metallic
Chapter 1

23
m). However, it has been found recently that the cyclability of the
o02 cathodes could be improved significantly down to (l-x)::::0.3,
g reversible capacities of close to 200 mAh/g, 24by29 modifying its
e with other oxides such as Ah03, Zr02, and Ti02. - For example,
1.9 compares the cyclability of Ah03-modified LiCo02 cathode
29 with
unmodified LiCo02 cathode to various cut-off voltages. As can be
he surface modified samples exhibit good capacity retention to higher
f voltages with practical capacities of close to 200 mAh/g. Cho et
attributed the improved cyclability from ex-situ X-ray diffraction data
uppression of both the changes in the c axis with (1-x) and the
onal to monoclinic phase transition arising from an ordering of the
m ions around (l-x)=0.5. However, in-situ X-ray diffraction data
te that the surface modified samples also exhibit changes in c axis
1-x) and the hexagonal to monoclinic 30 phase transition around (1-
just like the uncoated Li 1_xCo02. Also, Transmission electron
copic (TEM) studies show that the coating oxides such as29Ah03 30 and
re present as loose nanoparticles on the surface of LiCo02. ' These
gs suggest that the capacity fade commonly encountered by the
2 cathodes (uncoated) on cycling to (l-x)<0.5 may not be simply due
hexagonal to monoclinic transition at (l-x)=0.5 and some other factors
ay a role.

250

- 200
(f)
<E
-u
(e)
150 (d)
(b)
(a)
Bu 100

l
J
50

0
0 20 40 60 80 100
Cycle number

1.9. Comparison of the cyclability data of unmodified and Al 2 0rmodified LiCo02


s in different voltage ranges at C/5 rate: (a) unmodified LiCo02 (4.3 to 3.2 V), (b)
ied LiCo02 (4.5 to 3.2 V), (c) unmodified LiCo02 (4.7 to 3.2 V), (d) Al20rmodified
(4.3 to 3.2 V), (e) Al203-modified LiCo02 (4.5 to 3.2 V), (f) Al203-modified LiCo02
.2 V), and (g) Al20rmodified LiCo02 (4.7 to 3.2 V).
l Aspects: An Overview 15

The lack of a clear understanding of the factors that limit the practical
ty of the LiCo02 (uncoated) cathode to 140 mAhlg is partly due to the
22 31 34
hat most of the investigations in the literature • - have focused
on the structural characterization (both in-situ and ex-situ) of the
chemically charged Lh-xCo02 samples. No chemical characterization
uch as the variations of the oxidation state of Co and the oxygen
t with lithium content were available since it is difficult to chemically
terize the electrochemically charged samples as they are contaminated
arbon, binder, and electrolyte. To overcome these difficulties and to
p a better understanding of the factors that control the practical
ties, recent investigation by our group35 -38 has focused on both the
cal and structural characterizations of the Li 1_xCo02 samples that were
ed by chemical delithiation. The chemical delithiation reactions were
d out by stirring the LiCo02 powder under argon atmosphere with an
itrile solution of an oxidizing agent such as N02PF6 (or N02BF4) that
39
reduction potential of around 5 V versus metallic lithium and is
enough to extract all the lithium from LiCo02:

10 20 30 40 50 60 70 80

Cu Ka 2e (degree)

JO. X-ray diffraction patterns of the Li 1.xCo02 phases obtained by chemical


ion.
Chapter 1

Figure 1.10 shows the evolution of the X-ray diffraction patterns of


38
hemically delithiated Li1.xCo02 samples. The Li1.xCo02 system
ins the initial 03-type structure for 0.5 (1-x) l.O and a new phase
to form around (1-x)=0.45 as indicated by the appearance of a
er to the right of the (003) reflection. The new phase continues to
with decreasing lithium content and the end member Co02 consists of
ions corresponding to only the new phase, which could be indexed on
sis of a P3-type structure. In the intermediate region 0<(1-x) 0.45,
the 03-type and the P3-type phases coexist (Figure 1.11). The
ation of a P3-type structure for Co02 is in contrast to the 01-type
32 34
re reported in the literature - for the electrochemically synthesized
es. However, the P3-type structure observed for the chemically
sized Co02 sample is metastable and it transforms slowly to the 01-
tructure with increasing reaction time of >2 days with the oxidizer
37
F6• The formation of the metastable P3-type phase during chemical
ation is due to the rapid extraction of lithium in <15 min, which
tes into an extremely high charging rate of >4C, compared to the
slower electrochemical charging (<C/10 rate) process normally
2 34
• The P3- and 01-type phases have an oxygen stacking sequence of,
tively, ...AABBCC... and ...ABABAB... along the c axis compared
tacking sequence of ...ABCABC... in the initial 03-type LiCo02
(Figure 1.12). The P3- and 01-type phases are formed from the initial
e structure by a sliding

14.4
'$
CJ
14.8

14.0
• 000
--.
0
.. • •
0 0
13.6 0
IT1I] 3

....... •
2.84 0 0 0 oo
OJ
2.82 •
ca
2.80 •
0.0 0.2 0.4 0.6 0.8 1.0
Lithium content, (1-x)

1.11. Variations of the a and c lattice parameters of the chemically delithiated Li 1_


ith (1-x).
l Aspects: An Overview 17

e Co02 sheets as shown in Figure 1.13 without involving the breaking


Co-O bonds. The 03-, P3- and 01-type structures have, respectively,
nd 1 Co02 sheets per unit cell. While the alkali metal ions have an
dral coordination in both the 03- and 01- type structures (0 referring
ahedral), they have prismatic coordination in the P3-type phase (P
ng to prismatic).

•u


0
OCo

c c eo
0•

a a
03 P3

.12. Crystal structures of 03-type LiCo02, P3-type Co02, and 01-type Co02 viewed
e (100) plane.

A A
c BA AC B
c
. BA
AC
ce c
c B
ce
B A
A

B
A :!c
P3 01
.13. Schematics of the sliding of some Co0 2 sheets leading to the transformation of
tructure to P3 and 01 structures. The letters refer to oxygen stacking sequence along
s.
Chapter I
1.98

-
c ••• o•
0 o • •o
Q)
§ • (a)

u 1.92 • 0

ffi 1.86 00
0>
1.80 0
0 0
1.74
0

3.8 A (b)
AAA.a
Q)

iii 3.6 At:,.


iii
c 6.. r:,.t:.. t:..r:,.t:..l:i. A
0 3.4 6..
" " C
·x 3.2 A
0 A
3.0 6..

0.0 0.2 0.4 0.6 0.8 1.0


Lithium content, (1-x)

1.14. Variations of the (a) oxidation state of Co and (Ni 0_ 85Co0.15) and (b) oxygen
with lithium content (1-x) in Li 1.xCo02 and in Li1.xNio.8sCoo. 150z.

Figure 1.14 shows the variations of the oxidation state of Co and the
n content with lithium content for the chemically delithiated Li 1.xCo02
38
es. The data in Figure 1.14 were obtained by a wet-chemical analysis
40
ing iodometric titration and the application of charge neutrality
ple. The oxidation state of cobalt increases linearly with (1-x) and the
n content remains around 2 for 0.5s(1-x)sl.O in Lh.xCo02.s- For Os(l
, the oxidation state of cobalt remains nearly constant and the charge
nsation is achieved by a loss of oxygen from the lattice with a 8=0.28
e end-member Co02. 8. The loss of oxygen from the lattice signals
a cal instability for (l-x)<0.5 in Li 1.xCo02.0, which may be the
factor
g its reversible capacity. The increased reversible capacity for the
e modified samples in Figure 1.9 is due to a more stable electrode
lyte interface and the consequent improvement in the chemical
ty. Interestingly, the lithium content (1-x) at which the oxygen loss
to occur coincides with the lithium content at which the new phase
gins to form (Figures 1.10 and 1.11). The results indicate that the P3
is oxygen deficient with a shorter 0-0 distance across the van der
gap between the Co02 sheets, signaling an increased 0-0 interaction.
l Aspects: An Overview 19

. Layered LiNi02

LiNi02 crystallizes in the 03 layered structure shown in Figure 1.7


3 14
iCo02• The Ni + + couple with a high lithium chemical potential J..lu(c)
6
es a high cell voltage of around 4 V like LiCo02 as seen in Figure
iNi02 provides an important advantage compared to LiCo02 since Ni
expensive and less toxic than Co, but it suffers from a few problems:
3
ficulty to synthesize LiNi02 with all Ni + and as a perfectly ordered
3 41 43
without a mixing of u+ and Ni + ions in the lithium plane, - (ii)
eller distortion (tetragonal structural distortion) associated with the
3 7 44
in Ni +:d (t;ge) ion, '45 (iii) irreversible phase transitions occurring
32 46
the charge-discharge process, ' and (iv) exothermic release of
47
n at elevated temperatures and safety concerns in the charged state. '
a result, LiNi02 is not a promising material for lithium-ion cells.
ver, some of these difficulties have been overcome by a partial
ution of Co for Ni. For example, the composition LiNi0.8sCoo.IsOz has
ound to show a reversible capacity of around 180 mAh/g (Figure 1.8)
49
xcellent cyclability. This capacity is 30% higher than that of LiCo02
corresponds to a reversible extraction/insertion of 0.65 lithium per
ion metal ion (65% of the theoretical capacity). In situ X-ray
tion fine structure studies have shown that the substitution of Co for
44
ppresses the cation disorder and Jahn-Teller distortion. .4 5 The
ution also suppresses the phase transitions commonly encountered
ithium extraction from LiNi02 and LiNh-yCoy02 (0.15::;;y::;;0.2) is
vely being pursued particularly for electric vehicles due to its lower
mpared to LiCo02•
However, the LiNi 1_yCoy02 (0.15::;;y::;;0.2) cathodes have been found to
50
p impedance during cycling particularly at elevated temperatures.
ason for the impedance development is not fully understood, but it
be related to the migration of the nickel ions from the nickel plane to
hium plane during cycling. The nickel-rich Li 1_xNi 1_yCoy0 2 samples
51 52
ed by both chemical delithiation and electrochemical charging
een found to exhibit a decrease in cia ratio on heating at T >50°C
the Li 1_xCo02 system does not suffer from such a difficulty.53 Rietveld
is has shown that the decrease in the cia ratio is due to a migration of
kel ions from the octahedral sites of the nickel plane to the octahedral
f the lithium plane via the neighboring tetrahedral sites as illustrated
ure 1.15. The tendency for such a migration in Lh-xNi 1_yCoy0 2 and its
e in Li 1_xCo02 is due to a lower octahedral-site stabilization energy
3 7
) associated with the low-spin Ni +:d (t;ge) ions compared to that
3 6
e low-spin Co +:d (t g) ion (Table 1.1).53• 54 While a moderate
Chapter 1

•• •m 0 Layer
M Layer

0 Layer

OJ 0
-
Li Layer

oo
b_L
cP
•• •
1.15. Schematic representation of the paths for the migration of M 3+ ions in layered
2 (M = Mn, Co and Ni). The open squares and the dotted squares refer, respectively,
m ion vacancies and tetrahedral sites. T 1 and T2 refer to tetrahedral sites at (0, 0,
nd (0, 0, 0.375) respectively.

allows the Ne+ ions to migrate through the tetrahedral sites


mild heat, the stronger OSSE of Co 3+ hinders such a migration.
Nevertheless, the LiNi0.85Co0. 1502 cathodes exhibit a higher reversible
ty of 180 mAhlg compared to that of the analogous LiCo02 (140
) cathodes. However, the reason for the difference in capacity is not
understood in the literature. With an objective to develop a better
tanding, our group has focused on the structural and chemical
terizations of the chemically delithiated Li1 _xNi0.85Co0. 1502
samples comparison of the results with those of Li1_xCo02• Figures
1.16 and how the X-ray diffraction patterns of the chemically
delithiated Li1_ Coo.1502 samples and the lattice parameter variations
with the lithium t (1-x). The Li,_xNi0.85Co0.,50z system maintains the
initial 03-type re over a wide lithium content of 0.3 (1-x)1 and a new
phase begins
m at a much lower lithium content of around (1-x)=0.25 compared to
und around (1-x)=0.45 in the Li 1_xCo02 system (Figure 1.10) as
ed by the small shoulder to the right of the (003) reflection. The new
grows with decreasing lithium content and the end member
o0.,502 consists of only the new phase. However, the new phase could
indexed on the basis of an 03-type structure in contrast to the P3-
ructure found for Co02. The new 03-type phase of Ni0.85Co0.1502 has
l Aspects: An Overview 21

1.1. Crystal field stabilization energies (CFSE) and octahedral site stabilization
s (OSSE) of some 3d transition metal ions.

Octahedral coordination Tetrahedral coordination OSSEd

Configuration" CFSEb Configuration• CFSEb.c

tz eo -8 Dq ezto -5.33 Dq -2.67 Dq


2g g 2

3 0
t ge
2 g
(HS)
t3 el
2g g
(HS)
3 2
t2 geg
(LS)
t6 g
2g
eo (LS)

6 I
t2 geg

d HS refer, respectively, to low-spin and high-spin configurations.


g energies are neglected for simplicity.
ned by assuming t = 0.444 L\,; t and L\, refer, respectively, to tetrahedral and
ral splittings.
ed by taking the difference between the CFSE values for octahedral and tetrahedral
ations.

ler c parameter than the initial 03 phase as evident


38 in Figure 1.17, and
ve designated this new 03 phase as 03' phase. In the intermediate
0<(1-x) 0.25, both the 03 and 03' phases coexist. The lower c
eter of the 03' phase may again signal a stronger 0-0 interaction
the van der Waals gap between the (Co,Ni)02 sheets like in the P3-
o02. The overall trends in the c parameter variations of both the Li 1_
and the Lit-xNio.s5Coo.t502 systems are in general agreement with that d
for the electrochemically charged samples, despite the slight nces
in the type of phases observed for the two delithiation processes.

Figure 1.14 compares the variations with lithium content of the


e oxidation state of Ni0.85Co0. 15 and the oxygen content in Li1_
Coo.t502 with those of Li1-xCo02. The Lit-xNio.s5Co0.t502_0 system loses
Chapter 1

10 20 30 40 50 60 70 80
Cu Ka 29 (degree)

l.l6. X-ray diffraction patterns of the Li 1_xNi 0. 85Co0.1502 phases obtained by


chemical tion.

n at a much lower lithium content of around (1-x)=0.25, and the


ember Ni0.85Coo.Is0z-li has a much smaller 8=0.1 compared to that in
_xCo02_0 system. However, similar to that observed in the Lh-xCo02_0
, the lithium content (1-x) at which the oxygen loss begins to occur
des with the lithium content at which the new phase 03' begins to
indicating that the 03' phase is oxygen deficient with a shorter 0-0
ce across the van der Waals gap and an increased 0-0 interaction.
importantly, the realization of a higher capacity for the
5Co0. 1502_0 system (180 mAhlg) compared to the LiCo02 system (140
) could be due to the better chemical stability of the former without
g to lose oxygen from the lattice down to a lower lithium content of
0.3. Although the data presented in Figure 1.14 are for
cally delithiated samples, the data collected
with the
chemically charged samples also show a similar trend.38 However, it
be noted that neutral oxygen may not be evolved during an over
of lithium-ion cells, but rather the cathode might undergo a slow
ion reaction with the electrolyte during cycling.
The differences in the chemical stability (oxygen loss) between the
oOz and the Lit-xNio.ssCoo.1sOz systems can be understood
l Aspects: An Overview 23

14.8

.--,14.4 A A&
·::su 14.0 AA
Ae,.
A A

13.6 6. 4.
A 6. [I;] '

A
2.86 A

· 2.84 6.
ro 6. &A
2.82 J!ii.. A
6.

0.0 0.2 0.4 0.6 0.8 1.0


Lithium content, (1-x)

1.17. Variations of the a and c lattice parameters of the chemically delithiated Li 1•


o0.1502 with (1-x).

sidering the qualitative band diagrams for the Li 1_xCo02 and Li 1_xNi02
s (Figure 1.18). With a low-spin Co3+:3d6 configuration, the t2g band
pletely filled and the eg band is empty (t;
e ) in LiCo02• As
8
is extracted from LiCo02, the Co + ions are oxidized to Co4+ by a
3

al of electrons from the t 2g band. However, at deeper lithium


2
tion with (1-x) <0.5, removal of electrons may occur from the 0 -:2p
creation of holes) as well since the t2g band overlaps with the top of
-:2p band. The removal of significant amount of electron density from
2
-:2p band will result in an oxidation of the 0 - ions and an ultimate
3
t;
oxygen from the lattice. In contrast, the LiNi02 system with a low-
i +: econfiguration involves the removal of electrons only from
8
2
band. Since the eg band barely touches the top of the 0 -:2p band, the
i02 system loses a small amount of oxygen only towards the end of
extraction with (1-x)<0.2.35 In the case of LiNi0.85Co0.1502 with a
amount of Co, it loses oxygen slightly earlier for (l-x)<0.3. For a
rison, the band diagram of the Li 1_xMn 204 spinel system is also shown
3
t;
ure 1.18. With a high-spin Mn +: 8 econfiguration, the removal of
ns occurs only from the eg band in Li 1_xMn 204• Since the eg band lies
bove the top of the 0:2p band, the Li 1_xMn 204 system has been found
56
mical analysis data not to lose any oxygen. Also, while the partially
zg band leads to metallic conductivity for (l-x)<0.77 in Li 1_xCo02, the
etely filled tzg band leads to semiconducting behavior for 0::;(1-x)::; 1
Li,_xNiOzand Li,_xNio.ssCoo.Is02. 35
Chapter 1

E E
M n3+1 +:e8
Co3+14+:c8
Mn +14+:tz8
3
Ni 3+14+:e
Co3+14+:t z8
8

Ni 3+14+:tz8
o2-:2p o2-:2p o2-:2p
N(E) N(E) N(E)

Lio.sMnz04 Lio.sCo02 Lio.s NiOz

1.18. Comparison of the energy diagrams ofLi 05Co02, Li0_ 5Ni02, and Li0_5Mn 204•

The qualitative band diagrams shown in Figure 1.18 and the observed
n loss behavior are consistent with (i) the spectroscopic data that holes
roduced into the 02":2p band rather than into the Co:3d band in Li1.
, but into the Ni:eg band in Li1-xNiOz and Lii-xNio.ssCoo.IsOz during
57 59
chemical charging, - and (ii) the theoretical calculations that the
e charge on oxygen decreases with decreasing lithium content in Li1 _
60 61 Furthermore, the introduction of holes into the 0 2-:2p band
. '
ates the 0-0 interaction across the van der Waals gap between the
heets, which could in tum be the driving force for the formation of the
03' phases with smaller c parameters than the 03 phase (Figures 1.11
17). In fact, the P3 phase is generally believed to be inaccessible since
ide ions lie one above the other along the c axis (Figure 1.12), and the
ion of the P3 phase only in the case of Co02.8 could very well be due
2
presence of significant amount of holes in the 0 -:2p band and
erable amount of oxygen vacancies.

Other Layered Oxides


Both LiV02 and LiCr02 crystallize in the 03 structure (Figure 1.7),
e vanadium ions migrate to the lithium planes for (1-x)<0.67 in Li1.
due to the low OSSE (Table 1.1), while it is difficult to extract
from LiCr02• So, both LiV02 and LiCr02 are not promising cathode
als. LiTi02 is difficult to synthesize and both LiMn02 and LiFe0 2
sized by high temperature procedures do not adopt the 03 structure.
heless, the sodium analogs NaM0 2 (M = Mn and Fe) adopt the 03
re and the 03-type LiMn02 and LiFe02 have been obtained by ion-
l Aspects: An Overview 25

63 65
nge reactions of NaM02• - Also, a partial substitution of Cr orAl
n has been found to access the 03-type LiMn02 by direct ceramic
53 66 68
ures. • - Unfortunately, the 03-type LiMn02 transforms to spinel
hases during cycling due to the low OSSE of Mn 3+ (Table 1.1) and the
3
quent migration of the Mn + ions from the Mn plane to the Li plane.
rly, the orthorhombic LiMn02 that is obtained by conventional
69
ures also transforms to spinel-like phase, leading to poor cyclability.
3-type LiFe02 also exhibits poor electrochemical cycling properties
3 5
structural instabilities since the high-spin Fe +:3d with an OSSE
of zero (Table 1.1) can readily migrate from the octahedral to
dral sites.

SPINEL OXIDE CATHODES


A few oxides with the general formula LiM 204 (M = Ti, V, and Mn)
lize in the normal spinel structure (Figure 1.19) in which the u+ and
3 14
+ + ions occupy, respectively, the 8a tetrahedral and 16d octahedral
f the cubic close-packed oxygen array to give a cation distribution of
M2h 6ct04• A strong edge-shared octahedral [M2]04 array permits

0 Li (Sa site)

0 Mn (16d site)

• 0 (32e site)

.19. Crystal structure of spinel LiMn 2 04.

ble extraction of the u+ ions from the tetrahedral sites without


ing the 3-dimensional [M2]04 spinel framework. An additional
Chapter 1

m can also be inserted in to the empty 16c octahedral sites of the spinel
work to give the lithiated spinel Li2 [M2]04. However, an electrostatic
ion between the u+ ions in the 8a tetrahedral and 16c octahedral sites,
share common faces, causes a displacement of the tetrahedral Lt ions
e neighboring empty 16c sites to give an ordered rock salt structure
a cation distribution of {Lizh 6c[Mzh 6ct04. Thus theoretically two
m ions per LiM204 formula unit could be reversibly inserted/extracted.
the edge shared M06 octahedral arrangement with direct M-M
ction, as in the layered LiM02 oxides, provides good electrical
ctivity O'e, the interconnected interstitial (lithium) sites in the three
sional spinel framework provide good lithium-ion conductivity cru. As
lt, the spinel LiM204 oxides have also become attractive candidates
ey are discussed below.

. Spinel Manganese Oxides


Mn is inexpensive and environmentally benign compared to Co and
, therefore, the spinel LiMn 204 cathodes have become appealing for
-ion cells. The extraction/insertion of two lithium ions from/into the
7
2]04 spinel framework occurs in two distinct steps. While the lithium
tion/insertion from/into the 8a tetrahedral sites occurs at around 4 V
e 1.8) with the maintenance of the initial cubic spinel symmetry, that
nto the 16c octahedral sites occurs at around 3 V by a two-phase
nism involving the cubic spinel Li[Mn 2]04 and the tetragonallithiated
Liz[Mn2]04. Although both involve the same Mn 3+ 14+ couple, the 1 V
nce between the two processes is a reflection of the differences in the
ergies.3 A deep energy well for the 8a tetrahedral u+ ions and a high
ion energy required for the u+ ions to move from one 8a tetrahedral
another via an energetically unfavorable neighboring 16c site lead to
er voltage of 4 V. The cubic to tetragonal transition on going from
2]04 to Liz[Mnz]04 is due to the Jahn-Teller distortion associated with
3 4
gle electron in the eg orbitals of a high spin Mn +:3d (t;ge) ion
e 1.20). A cooperative distortion of the Mn06 octahedra with long
bonds along the c axis and short Mn-0 bonds along the a and b axes
wn in Figure 1.20 results in a macroscopic tetragonal symmetry for
nz)04.
The cubic to tetragonal transition is accompanied by a 16% increase
cia ratio and 6.5% increase in the unit cell volume. This change is too
for the electrodes to maintain structural integrity during the
rge-charge cycle and so LiMn204 exhibits rapid capacity fade in the 3
on.
l Aspects: An Overview 27

Therefore, LiMn204 could be used only in the 4 V region with a


d practical capacity of around 120 mAhlg (Figure 1.8), which
ponds to an extraction/insertion of 0.4 lithium per Mn. Unfortunately,
with a limited capacity, LiMn204 tends to exhibit capacity fade in the

Free Mnn+ ion Cubic Tetragonal

1.20. Illustration of the Jahn-Teller distortion in manganese oxides: (left) Mn4+:3d 3


bic symmetry (no Jahn-Teller distortion) and (right) Mn3+:3d4 with tetragonal
ry (Jahn-Teller distortion).

egion as well particularly at elevated temperatures (50°C). Several


s such as Jahn-Teller distortion occurring on the surface of the
70 71
es under conditions of nonequilibrium cycling • manganese
72 74
ution into the electrolyte, - formation of two cubic phases in the 4 V
76 77 78
,75 loss of crystallinity, • and development of micro-strain during
g have been suggested to be the source of capacity fade.
Several strategies have been pursued to overcome the capacity fade of
04. For example, increasing the oxidation state of Mn via (i) an
se in the oxygen content to give the defect spinel LiMn204+o (or
409_ 15)79 -81 which is actually a cation-deficient spinel Lh-yMn2_2y 3y04,
i) cationic substitutions to give LiMn2_yMy04 (M = Li, Cr, Co, Ni and
9 have been pursued with an aim to suppress the difficulties of Jahn-
4 3
distortion since Mn +:3d (t 8 e) does not undergo Jahn-Teller
ion. However, such a strategy leads to a decrease in capacity in the 4
on. For example, the end member (Li)[Mnl.67Lio.33]04 (or Li4Mn50n)
Chapter 1

M = Li has an average oxidation state of 4+ for Mn and does not t


any capacity in the 4 V region corresponding to the extraction of m
82 85
from the 8a tetrahedral sites. . It exhibits capacity only in the 3 V
corresponding to an insertion of an additional lithium into the 16c
dral sites to give {Liz}16c[Li0.33Mn ,67] 16d04• On the other hand, the
.yMy04 spinel oxides with M = Cr, Co, Ni, and Cu exhibit two
us for the extraction/insertion of lithium from/into the 8a tetrahedral
- : one around 4 V corresponding to the oxidation of Mn + to Mn +
89 3 4

he other around 5 V corresponding to the oxidation of the other


ion metal ions.
It is interesting to note that while the M = Co3+14+ and Ni3+14+ couples
around 4 V corresponding to the extraction/insertion of lithium
nto the octahedral sites of the layered LiM02, they offer 5 V
ponding to the extraction/insertion of lithium from/into the tetrahedral f
the spinel LiMn2.yMy04• The 1 V difference is due to the differences
3
site energies as discussed earlier. However, the 5 V capacity has
lly been observed only when the other transition metal ions are t
90 93
along with Mn in the spinel lattice. " For example, both
0 1
Ge150/ • 91 and LiCo20/ do not show any capacity above 4.5 V.
observations together with an examination in the 5 V region of spinel
such as LiMn2.yLiy04, LizMn409.1;, and Li4Mn5012 that contain no
ion metal ions other than Mn suggest that the participation of 02-11-
ossibly Mn4+tS+ couples could be involved in imparting the 5 V
94
ty.93• Also, it has been found that good crystallinity for the LiMn2.
samples by synthesizing at higher temperatures T>500°C is essential
94
ize capacities in the 5 V region. Finally, although cathodes with 5 V
pealing from an energy and power density points of view, the LiMn 2.
oxides may be prone to suffer from oxygen loss from the lattice
r to that observed for the layered Li 1.xCo02 for (1-x)<0.5 (Figure 1.14)
nsequent safety concerns in the 5 V region. However, the oxygen loss
ms may be minimized for M = Ni since the Ni + +:eg band barely
3 14

2
s the top of the 0 -:2p band (Figure 1.18).
Another strategy that has been pursued to improve the cyclability of
Mn204 spinel is the modification or coating of its surface with other
77
such as LiCo02, V205, Alz03, or Mg0 '95 -97 with an aim to suppress
solution of manganese in contact with the electrolyte. The modified
es exhibit improved cyclability at both ambient and elevated
ratures. However, firing at higher temperatures (-800°C) after coating
to much better capacity retention compared to firin§. at lower
9
ratures (-400°C) in contrast to the coated LiCo02 samples discussed
that requires firing only at low temperatures (-300°C). This suggests
a diffusion of the coating or modifying oxides MyOz into LiMn 204 is
al to achieve good cyclability and (ii) the improved cyclability need
simply due to the protection of the cathode surface from the
l Aspects: An Overview 29

olyte and the consequent suppression of manganese dissolution.


y, additional factors other than manganese dissolution could be
g a role in improving the cyclability on coating/modifying the
04 cathodes.
With an aim to fully understand the factors that cause capacity fading
Mn204, our group has recently focused on a number of LiMn2.yMy04
Mn2.2yLiyMy04 (M = Co, Ni, and Ti) compositions. Our data reveal a
98

relationship between the lattice parameter difference a between the


bic phases formed in the 4 V region and the % capacity loss (Figure
The % capacity loss decreases with decreasing lattice parameter
nce a. For example, compositions such as
LiMn18. 5Li0m 5Ni 0.07504
t excellent capacity retention at elevated temperatures (Figure 1.22)
a small sacrifice in reversible capacity (100 mAhlg). The
.85Li0.075Ni0.07504 sample also exhibits superior rate capability (Figure
and excellent capacity retention after storage at 60°C at different
of discharge (DOD) compared to LiMn204.98' 99 The compositions that
t good capacity retention and rate capability are found to maintain
98 99
crystallinity with sharp diffraction peaks after extended cycling, •
sting a suppression of the development of micro-strain that is normally
ntered during the cycling of LiMn204.77'78 The study reveals that the
e changes and lattice strain arising from the difference in lattice
eters between the two cubic phases formed in the 4 V region play a

120 •

·
0)
\

-
110

..c 100
•\ (b)

--
<(
E 90
(c)
(d)
'(3 >. 80
<tl
c.. 70
<tl
()
60
(a)
50
0 10 20 30 40 50
Number of Cycles

1.21. Cyclability data of LiMn2.2yLiyNiy04 at 60°C: (a) LiMn204, (b)


Lio.osNio.os04, (c) LiMni.ssLio.D7sNio.o?s04, and (d) LiMnl.8Li0.1Ni 0.104.
Chapter 1

l role in the capacity fading of LiMn204, which could be overcome


ptimum cationic substitutions such as LiMnl.85Li 0.o75Nio.o7504. These
gs are encouraging and with optimum cationic substitutions, it could
e possible to employ the spinel manganese oxides for electric vehicle
ations.

4.4

::.:: : : :=: , c - -<-


4C 2C IC C/2 C/5 CliO

-- > 4.4 C/2

-
C/5

C/10
Q)
C)
ctS 3.6
0
>
4.4

4.0

3.6

0 20 40 60 80 100 120
Capacity (mAh/g)

1.22. Discharge profiles of LiMn 2.2yLiyNiy04 at various Crates (C/10, C/5, C/2, IC,
4C).

Other Spinel Oxides


Both LiTiz04 and LiV 204 crystallize in the normal spinel structure
M2] 16d04 (M = Ti and V) and are metallic due to the direct M-M
tions with a partially filled t2g band. LiTiz04 inserts an additional
into the empty 16c octahedral sites to give the lithiated spinel
6c[Tiz]16d04, which occurs with a flat discharge profile (two-phase
100
n) at a much lower voltage of around 1.5 V. Accordingly,
il.67Lio.33h6d04 (or Li4Tis0tz), which is much easier to synthesize
all Ti4+ than LiTiz04, has become appealing as an anode [101].
it.67Lio.33h6d04 and the lithiated spinel {Lizh6c[Tit.67Lio.33h6d04 differ
l Aspects: An Overview 31

ir unit cell volume by 0.1%, which is attractive to maintain good


de integrity and capacity retention unlike in the case of LiMn204•
ver, the higher voltage (1.5 V) and lower capacity (175 mAh!g) of
012 make it difficult to compete with the currently used carbon anodes.
4 also inserts an additional lithium into the 16c sites. The lithium

0.08 •

0.06 • •
o<(
'-"
0.04
co
<l


0.02

0.00 ....
••r=--.---,.--.---,-----,.---r---.--.--
0 10 20 30 40
Capacity Loss (%)
1.23. Relationship between % capacity loss and lattice parameter difference (Lla)
the two cubic phases in Li 1.xMn2.yMy04 and Li 1.xMn2•2yLiyMy04 (M = Li, Ti, Co and

102 103
ould also be extracted from the 8a tetrahedral sites of LiV204. •
er, LiV204 suffers from a migration of the vanadium ions during
rocesses, which leads to poor capacity retention.
Both LiCr204 and LiFe204 are not known. LiCo204 could not be
y conventional high temperature methods, but it could be accessed as
al spinel (Li)8a[Co2h6ct04 by chemically extracting 50% of lithium
20 21 104
queous acid or N02PF6 in acetonitrile medium ' from the low
17 19
ature form of LiCo02 that has a lithiated spinel structure. ' LiCo204
is metallic due to the direct Co-Co interaction and the partially filled
3 14 104
d associated with the low-spin Co + +. While the extraction of
from the 8a sites occurs around 3.9 V, the insertion of an additional
21
into the 16c sites occurs around 3.5 V. However, the system
from a huge polarization loss as indicated by a large separation
n the discharge and charge profiles, which could possibly be related
low-temperature synthesis. Attempts to make LiNiz0 4 spinel by
ally extracting 50% of lithium from LiNi02 followed by heating at
°C result in a spinel-like cubic phase, but with the Ni3+14+ ions in both
and 16d sites. Heating at T>200°C results in a disproportionation to
iNi02 and Ni0.53
Chapter 1

OXIDE CATHODES WITH POLYANIONS


Iron oxides offer significant advantages compared to other 3d
ion metal oxides from both cost and toxicity points of view.
3 5
unately, the high spin Fe +:3d ion with a zero OSSE value (Table
nds to migrate readily from octahedral to tetrahedral sites as discussed
with respect to the layered LiFe02, causing structural instabilities.
problem could, however, be overcome by designing comfolex iron
2 2 05 106
consisting of poly ions such as (S04) - and (Mo04) -. • For
le, Fe2(S04)3 crystallizing in NASICON-related 3-dimensional
work structures was shown in the 1980s to exhibit a capacity of
105
110 mAh/g with a flat discharge voltage of 3.6 V. In these
res, the Fe06

1.24. Crystal structure of olivine (a) LiFeP04 and (b) FeP04 consisting of Fe06
ra and P04 tetrahedra (Ref. 62). The circles refer to lithium ions.

dra share comers with the S04 tetrahedra with a Fe-0-S-0-Fe linkage
thium ions could be inserted into the interstitial voids of the
2 13
work. The higher voltage of 3.6 V observed with the Fe + + couple
2(S04)3 compared to that found in simple iron oxide is due to the
6
ive effect caused by the counter cation S +. A stronger S-0 covalent
g weakens the 7t-bond Fe-0 covalence through inductive effect,
2 13
results in a lowering of the Fe + + redox couple and an increase in the
ltage. However, a poor electronic conductivity associated with the Fe-
-Fe (X= S or P) linkages leads to poor rate capability.
Following this initial concept of using poly anions, several phosphates
been investigated in recent years. 107- 109 Among them, LiFeP04
lizing in the olivine structure with Fe0 6 octahedra and P04 tetrahedra
l Aspects: An Overview 33

e 1.24) has been shown to be a promising material exhibiting a flat


109
rge voltage of around 3.3 V. However, LiFeP04 also suffers from
d rate capability due to poor electronic (cre) and lithium-ion (au)
ctivity compared to the layered and spinel oxide cathodes discussed
. While only around 0.6 lithium per iron could be reversible extracted
he samples synthesized by conventional solid-state synthesis, nearly
thium ion per iron could be reversibly extracted with materials
sized by low temperature procedures and having a good atomic scale
110 112
of carbon. - Unlike in the case of layered LiM02 (M =Co, Ni or
xides, the presence of covalently bonded P04 units as well as the
3
ion of Fe2 13 couple rather than M + + couples leads to good structural
14
+ +
emical stabilities resulting in good safety features. However, the low
apability may limit its use to low power applications. Recent
ments involving a doping of LiFeP04 with Nb or Zr have been
d to improve the electronic conductivity by several orders of
113
tude, but further studies are needed to confirm the finding and to
tand the mechanism of improvement in conductivity.

OTHER OXIDE CATHODES


The cation migration and structural instability encountered by ions
ow OSSE values such as Fe 3+ and Mn3+ in close-packed structures
d and spinel structures) could also be overcome by having non-close
structures. For example, Na 0.5Mn02 - designated as Nao.44Mn0z in
erature - adopting a non-close-packed tunnel structure does not
rm to spinel-like phases and shows extraordinary structural stability
114 115
peratures as high as 300°C. ' Although only a small amount of
could be extracted from the ion-exchanged sample Na0.5_xLixMnOz,
nal lithium could be inserted into Na0.5_xLixMn0 2, exhibiting good
ility.
Although both layered LiV02 and spinel LiV204 suffer from
ral instability and poor cyclability, a number of other vanadium
116 117
such as V02(B)- a metastable form of V02 - and exhibit
V6013
apacity with good cyclability. They can be considered to have shear
res derived from the hypothetical V03 having the Re03
118 119
re. ' The structure consists of distorted V06 octahedra sharing
s and edges. For example, the structure of V6013 (Figure 1.25)
ts of edge shared octahedra forming single zig-zag strings (denoted as
double zig-zag ribbons (denoted as II), which are then joined together
ring corners to give a 3-dimensional lattice. The resulting structure
ns tricapped cavities joined through shared square faces with the three
aces of the cavity permitting lithium-ion diffusion along (010). On the
hand, V02(B) contains one dimensional tunnel. Additionally, both
Chapter 1

20 121 122
· and LiV308 having layered structures have been shown
to t high capacity. The vanadium oxides generally exhibit good
chemical ty with better safety characteristics without releasing oxygen
from the
3 14
compared to the cobaIt or m.e keI ox1'des as th e V +ts+ and y + +
4
2
s lie well above the top of the 0 -:2p band.

1.25. Crystal structure of V 6013 consisting of single strings (I) and double ribbons (II).

Although it is difficult to charge the layered LiCr02, a few chromium


such as Cr205, Cr6015 and Cr308 having oxidation states of 2:5+ for
123
w high capacities. However, the synthesis of these oxides generally
es decomposition of Cr03 in an autoclave or under high oxygen
re and the products are often contaminated with undecomposed Cr03.
In addition to the various crystalline cathode hosts discussed so far, a
r of amorphous and nanocrystalline oxide compositions LixMyOz with
u6,124,125 Cr126,127 Mn128-133 Fe134 and Fe Cu 135 have been shown to
' ' ' ' 1-T] T]
t good cyclability. Among them, the manganese and vanadium oxides
t remarkably high capacities of around 300 mAh/g. However, the
ty occurs over a wide voltage range of 4.3 to 1.5 V with a sloping
rge profile as the lithium insertion is not limited to specific
lographic sites and grain boundaries are involved in amorphous and
ystalline oxides. Nevertheless, a moderate capacity of around 200
could be readily utilized with these oxides. Also, the amorphous
nese oxides have been found (i) to accommodate the lattice (Jahn
distortions more smoothly compared to the crystalline manganese
136
as indicated by spectroscopic studies and (ii) not to transform to
like phases during electrochemical cycling. However, the large
e area associated with the smaller particle size may aggravate
ted electrode-electrolyte reactions, which could become an issue for
rm cyclability and charge efficiency particularly at elevated
atures. Surface modifications that can provide a more robust
l Aspects: An Overview 35

de-electrolyte interface could help in this regard. Also, more in-depth


terizations by spectroscopic and other techniques are needed to fully
tand the mechanism of lithium insertion/extraction and the origin of
h capacities in the amorphous and nanocrystalline hosts.
Although some of the oxides discussed in this section are appealing as
xhibit high capacities with good safety characteristics compared to
2, most of them do not contain extractable lithium. The as-synthesized
are in the charged state and they are not suitable for fabricating
-ion cells with carbon anodes. However, development of new
-containing anodes may make these cathodes viable for lithium-ion
Also, these cathodes may be attractive for lithium polymer batteries
ying metallic lithium anode as the lower discharge voltage associated
many of them is advantageous to achieve good stability with the
er electrolytes.

ANODE HOSTS
Carbon has become the material of choice for anode in the present
tion of lithium-ion cells. 137' 138 The lightweight and low
chemical potential lying close to that of metallic lithium (Figure 1.5)
made carbon an attractive anode. It has a theoretical capacity of 372
, which corresponds to an insertion of one lithium per 6 carbon atoms
in LixC6). One of the drawbacks with the carbon anodes is the
ence of significant amount of irreversible capacity during the first
rge-charge cycle due to unwanted, irreversible side reactions with
lyte. Also, with electrolytes consisting of propylene carbonate (PC),
l graphite cannot be charged as it leads to an evolution of gas at
1 V. However, with electrolytes consisting of other solvents such as
ne carbonate (EC) and diethyl carbonate (DEC), the side reactions are
ssed and it can be cycled without much difficulty.
Carbon materials can be classified into soft carbon (graphitic carbon)
rd carbon (glassy carbon). The hard carbons are typically obtained by
mal decomposition of phenolic and epoxy resins and products from
um pitch. They have significant amount of open rnicropores, which
become closed on heating at higher temperatures, and some of them
t of single graphene sheets. Generally, hard carbons show higher
ties than graphite, which is thought to be due to the adsorption of
on both sides of the single graphene sheets, accommodation of extra
into nanometer size cavities, and storage of additional lithium at the
and surfaces. Also, hard carbons can be used with PC-based
lytes unlike graphite. However, the hard carbons show a sloping
rge profile between 0 and 1 V unlike graphite, which shows a nearly
scharge profile between 0 and 0.3 V. With an aim to improve the
Chapter 1

mance of carbon anodes, structural modifications such as texture


l, surface modification by mild oxidation and coating, and
oration of other elements such as B, 0, Si, and P have been studied.
A few oxides, nitrides, phosphides, and intermetallic compounds have
een investigated as anode hosts. Metal nitrides and phosphides offer
voltages versus lithium due to the covalent character and the
zation of lower oxidation states. As discussed earlier in section 5.2,
101
Li4Ti5012 offers 175 mAh/g at around 1.5 V, but it is less attractive
red to carbon due to its lower capacity and higher voltage. Sn02
a reversible capacity of as high as 600 mAh/g at 0 to 2 V, but it
139
ts a high irreversible capacity loss during the first cycle. Rutile-type
140 141 14 143 144
and WO2 ' '23' Fe 0 MnP4 and intermetallic compounds such
6Sn5 having NiAs-type structure have also been investigated. These
s, including carbon, do not contain Li and they can be coupled only
athodes such as LiCo02 and LiMn204 that already contain lithium.
respect to finding anodes that could be coupled with cathodes free
ithium, some lithiated transition metal nitrides 137' 145 and intermetallic
unds 146 have become appealing. For example, Li7.xMnN4 and Lh.
exhibit capacities of around 200 mAh/g with a flat discharge voltage
und 1.2 V. Lh6-xCoo.4N, Lh6-xCUo.4N, and Lh7-xFeo.3N that have
res similar to that of LhN exhibit much higher capacities of around
Ah/g at 0.2 to 1.3 V due to the formation of an amorphous phase
the initial stages. Two lithium per formula unit could be reversibly
146
ted from LhCuSn. However, further work is necessary to assess the
otential of these anodes. If successful, they have the possibility of
coupled with some of the lithium-free cathodes discussed in Section

CONCLUSIONS
After providing a brief introduction to the basic concepts of
geable lithium batteries, this chapter presented an overview of the
s cathode and anode materials. In view of maximizing the cell voltage
nergy density, transition metal oxides offering around 4 V versus
have emerged as the choice for cathodes while the light-weight
with an electrochemical potential close to that of metallic lithium has
e the anode. With carbon anode that does not contain lithium, the
d LiM02 (M = Co and Ni), spinel LiMn204, and olivine LiFeP04
ning lithium have emerged as the leading cathode candidates.
er, only 40 to 65% of the theoretical capacity of the layered LiM02
inel LiMn204 could be practically utilized due to the chemical and
ral instabilities encountered by these cathodes at deep lithium
ion. Although recent studies indicate that 100% of the theoretical
l Aspects: An Overview 37

ty of LiFeP04 can be utilized, the added weight of the P04 units and
oor electronic conductivity lower the energy and power densities
cantly.
The future challenge is to develop simple oxide cathodes without
elements such as P in which at least one lithium ion per transition
ion could be reversibly extracted/inserted to give close to 300 mAhlg
keeping the materials cost and toxicity low. Such cathodes can double
ergy density compared to the present level. There are also possibilities
rease the capacity of anodes perhaps by focusing on amorphous
als and metal nitrides, pnictides, borides, and carbides with significant
nt character. An alternative approach is to develop cells with lithium
ning anodes and lithium-free cathodes. This strategy will allow the use
e of the already known high capacity cathodes such as the vanadium
and nanocrystalline manganese oxides that offer higher capacity with
chemical stability and safety characteristics compared to the currently
iCo02 cathode. From a safety, and cycle and shelf life points of view,
es with a lower voltage (3 to 4 V), but with an increased capacity are
ble for future applications. Such cathodes would also be attractive for
er batteries from a stability point of view.

NOWLEDGMENT

Financial support by the Welch Foundation Grant F-1254 is gratefully


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pter 2

THE ROLE OF ELECTRONIC PROPERTIES IN


THE ELECTROCHEMICAL BEHAVIOR OF
INTERCALATION COMPOUNDS FROM A
FIRST PRINCIPLES VANTAGE POINT

A.Vander Ven and G. Ceder


Department of Materials Science and Engineering,

Massachusetts Institute ofTechnology, Cambridge, MA, U.S.A.

INTRODUCTION

Lithium transition metal oxides are remarkable intercalation


ounds, exhibiting an array of intriguing electronic and phase
ormation phenomena. Their ability to undergo large variations in lithium
ntration, often without suffering irreversible changes, makes these
ials ideal electrodes for rechargeable lithium batteries. Lithium
ion metal oxides consist of a metal oxide host with a crystal structure in h
lithium ions occupy a relatively open network of interstitial sites. e
some lithium transition metal oxides can serve as an anode in
rgeable lithium batteries, most are more suited for the role of cathode as
typically exhibit a high voltage with respect to a metallic lithium anode,
deal theoretical reference electrode. In a rechargeable lithium battery,
m ions are shuttled between an anode and a cathode, whereby lithium
are removed from and inserted into the electrodes. During deintercalation
ithium transition metal oxide, vacancies are created on the lithium sites
e host. During intercalation, these sites are refilled by lithium. Removal
insertion of lithium ions can lead to several phenomena that can
icantly affect the electrochemical properties of the compound. For one,
ions in lithium concentration alter the electronic properties of the
ole of Electronic Properties ... 43

ition metal oxide host. The valence electron of each lithium ion is
rally donated to the host where it can either shift the valence state of the
ition metal ion and/or alter the nature of the bonds between the transition
l and the oxygen ions. Simultaneously, lithium removal from the host
structurally destabilize the metal oxide structure or may lead to order
der phase transitions between lithium and vacancies once a critical
ncy concentration is reached. These phenomena often affect the voltage
cteristic or the lattice parameters of the compound in important ways.
Within the last decade, much attention has been devoted to
1
rstanding the properties of LixCo0 2, LixNi02, LixMn02, LixMn204 and
ePO/, currently among the most important candidate cathode materials
echargeable lithium batteries. Other compounds receiving attention are
ally doped variants of the Co, Ni and Mn compounds. While many
m transition metal oxides have similar crystal structures, either a layered
or one derived from the spinel structure (LixFeP04 has the olivine crystal
ture), they are often characterized by very different electrochemical
rties owing to the unique electronic structure of each transition metal.
o02, for example undergoes a concentration driven metal-insulator phase
ormation whereby the electrons over much of the lithium concentration
(x<0.75) are delocalized and exhibit metallic properties? In contrast, the
n204 compound in important lithium concentration regions is
cterized by more localized electrons with large magnetic moments
46
ng to phenomena such as charge ordering and Jahn-Teller distortions. -

, phenomena such as these can be rationalized with crude crystal-field


molecular orbital models. More subtle properties such as the relative
ity of similar crystal structures, stable ordered lithium-vacancy
gements and charge-ordered and magnetic-ordered electronic states are
difficult to predict or rationalize with intuition based on simple
onic structure models. It is here that first-principles numerical-schemes
olving the Schrodinger equation of solids are proving invaluable. The
d of the last decade of first principles studies of lithium transition metal
Chapter 2

es has demonstrated that these methods are an important new tool in


40
cting and understanding the properties of these materials. 7-
The state of the art in first principles electronic structure methods for
s is based on density functional theory (DFf).41- 43 Density functional
y casts the problem of solving the many-body Schrodinger equation of
olid into an equivalent problem of solving for the electronic charge
ty of the solid. While density functional theory is exact in principle, its
ical implementation for real solids requires approximations, the most
mon of which are referred to as the local density approximation (LDA)
he generalized gradient approximation (GGA). The properties that can be
tly derived with density functional theory are the charge (or spin) density
he total energy of the solid. Other properties can only be calculated if
cal models relating them to energies or charge densities exist. By using
7 8 10 12 15 17
odynamic and statistical mechanical models, voltages • • • • • ,

ve stabilities 11'14' 18' 27 and kinetic properties such as atomic migration


33 36

anisms and rates31' ' can be predicted. The first principles study of
m transition metal oxides has also received an important boost with
opments in alloy theory during the last twenty years, most notably the
opment of the cluster expansion27' 44.4 5 which enables the statistical
anical treatment of solids with significant configurational disorder. In
alation compounds this capability is critical due to the many degrees of
om of distributing lithium ions and vacancies over the interstitial sites.
arly, the disorder in mixed compounds with multiple transition metal
28
ents can only be described properly with cluster expansion techniques.
combination of accurate DFf calculations with sophisticated statistical
anics techniques have enabled accurate calculations of phase diagrams
'
39
tercalation compounds, 18 28' voltage intercalation curves 12' 15' 17 and
m diffusion coefficients.31•36
In this chapter, we focus on a description of important electronic
rties of LixCoOz, LixNi02 and LixMn02 • Most of our information will be
ed from first principles calculations. The chapter starts with an overview
ole of Electronic Properties ... 45

and-field and molecular orbital theory, and continues with a description


rst principles density functional theory. We next illustrate how each
y can be used to understand and, in the case of density functional theory,
ct the electronic properties of LixCo0 2, LixNi02 and LixMn02. We
asize the electronic properties that are predicted by density functional
y but would not be a priori expected from ligand field or molecular
al models. In the case of LixCo02, density functional theory has shown
important role of covalency in influencing the structural and
odynamic properties of the host. In LixNi02, DFT calculations have
sed the existence of an intriguing long-range attraction between lithium
of different lithium planes mediated through a Jahn-Teller distorted Ni+3
edron. This long-range attraction, termed a 180° interaction, leads to
ochemical properties in LixNi02 that differ significantly from those
ved in LixCo02 even though both compounds have the same crystal
ure. Finally, in LixMn02, DFT calculations have predicted a charge
oportionation reaction between the Mn ions, creating Mn+2 that favor
edral sites. This mechanism is responsible for the rapid transformation
inel that occurs during cycling of layered LixMn02, an irreversible
ormation that has prevented commercialization of layered LixMn02 for
m battery applications.
In all three examples, the first principles predictions expose
anisms that play a central role in determining the electrochemical
rties or stability of these materials as cathodes. Understanding the link
en electrochemical properties and their electronic origins is invaluable
imizing these materials.

GENERAL ELECTRONIC STRUCTURE OF


OCTAHEDRAL TRANSITION METAL IONS

The ability of lithium transition metal oxides to undergo large


ions in lithium concentration is attributable to the flexibility of the
Chapter 2

ce electronic structure formed by the transition metal and oxygen ions.


7
um is generally completely ionized within the oxide, having donated its
ce electron to the host. The electronic properties of the transition metal
e are dictated to a large extent by the number of valence electrons and by
nteraction of the d-orbitals of the transition metal with the p-orbitals of
xygen ions.
In both the layered and spinel crystal structures, the transition metal is
edrally coordinated by oxygen. Figure 2.1 illustrates the electronic e
densities of hydrogenic d-orbitals within an octahedral oxygen
onment. Although the five d levels when occupied by a single electron
de of a closed shell core are degenerate in a free transition metal ion, in
tahedral environment, this degeneracy is broken. Crystal field theory 46-49 ,
xample, shows that the interaction of the d orbitals with the electrostatic
tial due to the negatively charged oxygen ions of the octahedron
ces an increase in the energy of the d 3z2-r2 and dx2-y2 orbitals with
ct to the energy of the dxy• dxz and dyz orbitals. This occurs because the
2 and dx2-y2 orbitals have lobes pointing toward the negatively charged
en ions while the lobes of the dxy• dxz and dyz orbitals point between
en ions.
Only considering the effect of the electrostatic field of the oxygen ions
cts the important role of covalency that can exist between the transition
and oxygen orbitals. A more accurate picture of the interaction between
ansition metal ion with the surrounding oxygen ions arises from
4649
cular orbital theory. The d3z2-r2 and dx2-y2 orbitals directly overlap
he Px• Py and Pz orbitals of oxygen forming bonding and antibonding
evels referred to as egb and eg*· These levels are illustrated
matically in Figure 2.2. Since the energy of the p orbitals are below the
y of the d orbitals, the bonding egb levels are predominantly of oxygen p
cter while the antibonding eg* levels (frequently referred to as simply eg)
st mainly of metal d states. This dichotomy in character between the
ole of Electronic Properties ... 47

2.1. Hydrogenic d-orbitals within an octahedral oxygen environment. (a) The d3z2-,2
) the dx2-y2 orbitals have lobes pointing toward the oxygen ions. (c) The dxy orbital,
is symmetrically equivalent to the dxz and dyz orbitals, has lobes pointing between
n ions.

ng and antibonding levels becomes more pronounced as the difference


energy of the metal d-levels and the oxygen p-levels widens. The dxy•
nd dyz orbitals which do not directly overlap with oxygen p orbitals to
cr bonds, are frequently said to form a set of nonbonding levels denoted
46 49
. - A band gap llo separates the t 2g levels from the antibonding eg levels.
octahedral environment, the t2g levels are below the eg levels. Although
y• dxz and dyz orbitals do not form cr bonds with the oxygen ions, they do
n bonds with the oxygen p orbitals.46
Instead of being non-bonding levels, t2g energy levels of Figure 2.2,
accurately correspond to the bonding levels of the 1t overlap between dxy•
d dyz and the oxygen p levels. Increased covalency of this n bond will
in a lowering of the energy of the t2g levels and hence an increase in the
gap L10 •46
Other levels arise from the overlap of oxygen p-levels with the
tion metal 4s and 4p levels. These are referred to as t 1u and a 1g. Since the
y of the oxygen p levels are again below the energy of the metal 4s and
els, the bonding t 1u and a 1g levels are predominantly of oxygen character.

Chapter 2

it: \
\
4p \
\
\ \ .... ---..;a;:;_g...., \
\
\

4s ---...--';-- e*
\
\
\
\
\ \
g \ \

.
\ \ \ \
\ \ \ \
\ \ ' \ \ \
\ \ ,' \
\
\
\
\
\
\
>' \ \ \ \

-:.' g
\ _,,\ =
\ \\

3d \\\
\ ,,
,,,
,,
_ \ \ \
\
\
\
\
\
\
b
,,
\ \ \

\ \ ':==l:i§u= ---,",',
\ \ \ 2p
:-
\ \
\ \
'
,','
\ \
\ \ b
alg '
''
\ \

\ ''--"'-- '
''
\
\
''
\

' Oxygen
Metal '·===='

2.2. Schematic illustration of the bonding and antibonding levels that arise for a
ion metal ion in an oxygen octahedral environment due to the hybridization between the
e electronic states of the transition metal ion with those of the oxygen ions.

In a crystal, the levels of Figure 2.2 become bands. Furthermore,


ugh the transition metal ions reside in octahedral interstitial sites, the
inder of the crystal outside of the octahedral site generally does not
it the symmetry of a perfect octahedron. Hence the degeneracy of the
s is further broken. Nevertheless, the schematic picture of Figure 2.2 is
ly still identifiable in the band structure.
While general trends can be rationalized with simple crystal field and
cular orbit models, more accurate numerical methods based on density
ional theory are necessary to understand and predict the relationship
en the electronic structure of a compound and specific electrochemical
rties.

FIRST PRINCIPLES METHODS

Calculating properties of solids from first principles without


ole of Electronic Properties ... 49

imental input involves solving the many body Schrodinger equation for
50 • 51
olid. The time-independent Schrodinger equation (in this section, all
ions are expressed in atomic units) is an eigenvalue equation

(2.1)

e H is the Hamiltonian operator for the solid, '¥ is the many body wave
ion describing Ne electrons and E is the total energy of the solid. Within
Born-Oppenheimer approximation, the electrons are assumed to
ntaneously adjust their state to any change in the positions of the nuclei.
coordinates of the nuclei Rn then serve only as parameters in the
dinger equation and the Hamiltonian can be written as

H = T +Vee+ L v(;:;)+ L L
-ZnZn:_ I
j n m<n
Rm -Rn

he electronic kinetic energy operator

(2.3)

ee describes the Coulomb interactions between the different electrons

(2.4)

the rj refer to the positions of the electrons. The sums in Eqs. (2.2),
Chapter 2

and (2.4) are over all the electrons in the solid. The third term in Eq.
describes the coulomb interaction between the electrons and the nuclei
e solid and the last term is the Ewald energy arising from the coulomb
action between the nuclei having charge Zm· The Ewald energy is simply
ditive term and does not affect the electronic wave function \f. It can be
ped when solving the eigenvalue equation for the electronic ground state
nly needs to be added to the electronic energy to obtain the total energy
e crystal.
For solids of practical interest, solving the many-body Schrodinger
ion is intractable. One approach to solving Eq. (2.1) is with density
ional theory (DFT).41-43 As was shown by Hohenberg and Kohn (and
41 52
ded by Levy), ' the ground state properties of a crystal are uniquely
mined by the electron density p(r) (which is determined by the many-
wave function \f). The fundamental theorems of density functional
y state that the ground state energy of a solid is a functional of the
on density41

E[p] = F[p]+ fp(r)v(r)dr (2.5)

(2.6)

versal functional and v(r) the coulomb potential due to the nuclei of the
The lJ' in Eq. (2.6) is the electronic wave function that minimizes

+ Vee I' ') subject to the constraint that lJ' produces the electron density

ccording to DFT, if the functional F[p] were known, the ground state
y of the solid with external potential v(r) is obtained by variationally
mizing the functional E[p] with respect to p41•42 The minimization
eds over the set of all densities p that can be obtained with
mmetric wave functions.5 2
ole of Electronic Properties ... 51

F[p] is not known and approximations to it are therefore necessary.


ally, F[p] can also be written as

(2.7)

e the kinetic energy and the electron-electron interaction energy are


idually expressed as functionals of the electron density. Of the two terms
. (2.7), the kinetic energy T[p] is the most elusive to approximate as a
42 43
ional of p. 53 introduced a
' To side step this difficulty, Kohn and Sham

rent separation of F[p] by writing it as:

F[p] = Ts [p ]+ J[p]+ Exc [p] (2.8)

e T8 [p] is the kinetic energy of a system of non-interacting electrons with


ame density p. J[p] is often referred to as the Hartree term and is a
ical Coulomb energy given by

J[p] = _!_ ffp(r)p(r')drdr'. (2.9)


2 lr -r'l
last term Exc[p], called the exchange-correlation energy, which can be
n as

(2.10)

cludes the difference between the kinetic energy of the actual system of
cting electrons with density p and the kinetic energy of a system of
endent electrons with the same density. This difference, though, is
42
ally expected to be small and Exc primarily accounts for a correction to
arising from the correlations between electrons. Since the electron
ty corresponds to a probability distribution and not a charge density in
Chapter 2

lassical sense, J[p] is a mean-field approximation to the electron-electron


actions. Embodied in J[p] is the assumption that the probability of having
electrons at r and r' respectively is equal to the probability of having
lectron at r times the probability of having another electron at r' .
ected are the conditional probabilities resulting from the fact that if an
ron is already present at r , the probability of having another electron at
ill be different than the average probability. These correlations between
of electrons are implicitly accounted for by Exc[p].
Correlations between electrons, which become more important as r
r' approach each other, arise from two effects. The first type of
lation results from electrostatic repulsions which ensure that electrons
the vicinity of other electrons. These are called direct correlations. The
nd type of correlation has its origin in the Pauli exclusion principle which
ds electrons with parallel spins from having the same spatial position
inates. This effect does not arise from the many body Hamiltonian, but
forced by the fact that the wave function is antisymmetric. Since the
function is continuous, the Pauli exclusion principle implies that the
bility of having electrons with the same spin approach each other is
. This correlation is referred to as an exchange correlation. The energy
ibution of exchange correlation is typically an order of magnitude larger
that of direct correlation.43
The advantage of introducing the non-interacting kinetic energy
ional T.[p] is that it can be calculated exactly with a Slater determinant

f independent electron orbitals If/ 1(r). The independent electron kinetic

y functional then becomes42

r,fp] = (' 'niTI'Yn) = t Jvj(r{- v 2


) (2.11)

vj(r)dr
1
e '¥0 and the If/ 1 are such that they produce the electron density p.
ole of Electronic Properties ... 53

e it is possible that more than one 'I'n could produce the same density, the
cular 'I'n appearing in Eq. (2.11) is the one that minimizes ('PviTI'Pv)
xed p.
With the 'I'n and p expressed in terms of the independent orbitals
Kohn and Sham53 variationally minimized the energy functional

(2.12)

obtained what are now referred to as the self-consistent Kahn-Sham


ions

(2.13)

Veff
(- )r -V
Jipr (_rr')'l d-'
+
Vxc .
(-) (2.14)

( -)
r
+ T T

q. (2.14), v xc (r) is the exchange correlation potential and is the


ional derivative of the exchange correlation energy functional

-)- &'xc[p] (2.15)


Vxc (r - Jp(r)

An equation of the form of Eq. (2.13), exists for each electron in the
The Kohn-Sham procedure replaces the many body eigenvalue equation,
(2.1) and (2.2), with a set of independent-electron-like eigenvalue
ions. Despite their appearance, however, the Kohn-Sham equations are
dependent due to the dependence of Veff on the density p (Eq. (2.14))
Chapter 2

h itself is determined by all the orbitals 1f1 j. This means that the Kohn
equations are to be solved self-consistently.

1. The Local Density Approximation (LDA)

The Kohn-Sham equations as represented in Eq. (2.13) are exact


ded the universal functional Exc[P] (and hence its functional derivative
r)) is known. As with F[p] of Eqs. (2.5) and (2.6), Exc[P] is not known.
most common approximation to Exc is the local density approximation
53
A). Within LDA, Exc is written as

(2.16)

e Exc is the exchange correlation energy per electron at r. exc(p(r)) is


qual to the exchange correlation energy per electron of a homogeneous
on gas with the same density p(r) . LDA therefore assumes that Exc is
and neglects the effects of non-uniform charge densities around r.
e are different parameterizations of Exc as a function of the homogeneous
ron gas density p. The local density approximation has proven
rkably successful considering its simplicity. Typically though,
ibrium lattice parameters, volumes and band-gaps of solids are under
cted within LDA.

. The Generalized Gradient Approximation (GGA)

The generalized gradient approximation (GGA) includes in the


ximation to Exc[P] a term that depends on the gradient of the electron
ty at each point. While the inclusion of gradient corrections to the local
ty approximation often improves the accuracy of predictions, this is not
ole of Electronic Properties ... 55

ally guaranteed and for some solids, properties predicted within LDA
more with experiment than those predicted within GGA. Typically,
predicts lattice parameters and volumes that are slightly larger than
observed experimentally.

. Spin Polarization

Many solids, especially transition metal oxides, are characterized by


magnetic moment produced by an unequal electron population of +112
1/2 spin states. This is true of many atoms as well, as filling of the
ic orbitals according to Hund's rules often results in a net electronic spin.
of Hund's rules arises from exchange and correlation interactions
en electrons. Due to the Pauli exclusion principle, two electrons with the
electronic spin cannot occupy the same position in space. Hence,
ons with parallel spin do not occupy atomic orbitals with the same l
distribution, minimizing direct electrostatic repulsion. No such
um-mechanical restriction exists on a pair of electrons with opposite
Electrons with opposite spin can therefore occupy atomic orbitals with
cal spatial distribution but are then energetically penalized by enhanced
ostatic interactions.
To account for the possibility of spin polarization within practical
mentations of density functional theory, the total electron density is
ated into an electron density pa(i=) for the spin +112 electrons and an
on density p/3 (r) for the spin -112 electrons. While such a separation is
rictly necessary within exact density functional theory, it enables more
ate approximations to the exchange-correlation functional whereby a
ent exchange-correlation potential is introduced between electrons with
el spins and electrons with opposite spin.

. Caveats About Approximations to DFT


Chapter 2

At this point, several caveats of DFf and LDA and GGA in


cular deserve attention. The orbitals If/ j and orbital energies c j of the
n-Sham equations do not correspond to real electronic states and
ronic energy levels. It is only the total energy and electron density that
any physical meaning. Nevertheless, the Kohn-Sham energy levels often
ive a good characterization of the band structure of crystalline materials
are frequently compared to quasi-particle energies measured in photo
sion experiments. The kinetic energy as expressed in terms of the If/ j by
2.11), is not the real kinetic energy of the solid, though it is a close
42
oximation of it. The local density approximation is exact for a uniform
ron density and a good approximation for a slowly varying one.
ermore, for many solids exhibiting rapidly varying electron densities,
has proven surprisingly accurate. Yet, for solids in which the electronic
s are highly localized in space, we can expect LDA to break down since it
ot be expected to capture the strong correlations between the localized
rons.
For systems with well localized electrons, specific inadequacies of
cal density approximation can be identified. One inadequacy is that the
ximation to the exchange-correlation potential Vxc depends only on the
density and not on the specific orbital that a particular localized electron
pies. In the Hartree-Fock approximation for example, the exchange
y, which is exact within the approximation of the anzats wave function
er determinant consisting of single electron orbitals), is a non-local
ral between different electron orbitals. These integrals not only depend
e local electron density, but also on the shape of the different orbitals.
ar orbital dependencies can be expected to arise from direct correlations.
54
ods such as LDA+U attempt to remedy this deficiency of LDA.
her major inadequacy of LDA is that it has self-interaction (see, e.g., Ref.
In reality, electrons interact with other electrons. They do not interact
ostatically with themselves. In the Hartree term J[p] defined by Eq. (2.9)
ole of Electronic Properties ... 57

e energy functional Eq. (2.12), a coulomb interaction of each electron


itself is included. For the exact Exc[P] functional, this self-interaction
onent is canceled out. (In the Hartree-Fock approximation, the self
action in the Hartree term is explicitly canceled out by an identical term
e exchange term). When an approximation for Exc is used, however, the
nteraction does not cancel. This error becomes severe for well localized
onic states. LDA calculations with self-interaction corrections were
ered by Perdew and Zunger 55 and have been used to investigate the
onic properties of several transition metal oxides56 and
57
conductors. Incorporating self-interaction corrections leads to orbital
58
ndent effective potentials which complicates the numerical solution of
nergy and charge density, and as a result it is rarely done.

. Different Numerical Schemes

Many different numerical techniques exist for solving the Kahn


equations. For oxides, the most reliable methods have proven to be the
r Augmented Plane Wave (LAPW) method59 and the pseudopotential
60 61
od. • The LAPW method is currently considered the most accurate and
the standard, yet it is computationally the most costly. In the LAPW
od, all electrons of the solid are treated and their states are expanded in a
consisting of both local atomic-like orbitals and plane waves. In the
opotential method, the effect of the core electrons around the ions that
ot participate in bonding are replaced by a pseudopotential. The
opotentials are designed such that the valence single electron pseudo
functions have the same scattering properties as the actual valence
ons would have with the core electrons. The pseudopotential
ximation is valid as long as the core electrons do not participate in the
ng of the solid - that is the changes in their wave functions and energy
are negligible when the atom is placed in different environments. For
solids this approximation is valid. Comparisons of energy differences for
Chapter 2

ixCo02 system has shown that the pseudopotential method and LAPW
62
lations agree to within 10 meV per LixCo02 formula unit. Modem
dopotentials are determined from all electron calculations of atoms,
63 68
ng the pseudopotential method a first principles approach. -

The general procedure of solving the Kahn-Sham equations is to


nd the orbitals 1f1 j (r) in terms of a set of basis functions. In
dopotential calculations, these basis functions are usually plane waves.

ELECTRONIC STRUCTURE OF LixCoOz

LixCo02 is currently the most important transition metal oxide


ound for battery applications and is ubiquitous in commercial lithium
atteries. In this section, we describe important electronic properties of
o02 as predicted with DFf-LDA calculations. Striking is the important
hat shifts in covalency play in determining relative stability and lattice
meter variations with lithium concentration.

. Covalent bonding in LixCo02

Figure 2.3 illustrates the LDA-calculated electronic band structures


o02 and LiCo02.8 "69 The lowest six bands correspond to the egb• t 1u and
vels of Figure 2.2 which we will refer to as the oxygen p-levels. The next
levels are the t2g levels and the highest two levels correspond to the anti
ng eg bands. In LiCo0 2, the Fermi level lies between the t2g and the eg
s, making the compound a semiconductor. This is consistent with the
70
imental observations of van Elp et al. When all the lithium ions are
ved, the Fermi level resides in the t 2g bands as one electron per Co02
ula unit is removed.
The band structures of LiCo02 and Co02 are qualitatively similar.
mportant difference between the two band structures is the distance
en the oxygen p like levels and the t 2g levels which is larger in LiCo02
ole of Electronic Properties ... 59

in Co02. The electron donated by Li when inserted in the Co02 host


es in a t2g level. Through coulombic interaction, the addition of the extra
on to the t2g levels raises the energy of the other occupied t 2g levels thus
asing the energy difference between the metal d-states and the oxygen p
. This results in a reduction in the hybridization between the Co d-levels
the oxygen p-levels which translates into a change in the nature of
ing from a more covalent character in Co02 to a more ionic character in
02•
To better understand this shift in bonding characteristics with Li
18
ion, it is useful to inspect a charge difference plot. Figure 2.4 shows a e
difference plot between LixCo02 at x=l/4 and Co02 both in the layered
tructure of Figure 2.5. Electronic charge densities were calculated with
seudopotential method in the local density approximation for both
18
o02 and Co02 • The lattice parameters and the positions of Co and 0
the same in the two structures to enable a point by point subtraction of
harge density of Co02 from Li 114Co02• The resulting difference shows
the electron distribution changes when Li is added to the host, and in
ular, where the electron of the added lithium resides. The plane
ated in Figure 2.4 corresponds to the shaded plane shown in Figure 2.5.
plane cuts through Li, Co and 0 ions.
The charge difference plot illustrates that lithium intercalation
17' 18
es a significant redistribution of charge within the Co02 host. Figure
hows that there is an accumulation of charge density around all the Co
n lobes pointing in directions between oxygen ions. This increase in e
results from an electron addition to the partially filled t2g bands as m
is added to the host. The charge accumulation occurs around all the
t ions indicating that these states are delocalized. Figure 2.4 also shows
here is a significant depletion in electron density around the Co ions
st to the lithium ions. The charge depletion occurs in regions that
ble the charge density of a dx2-y2 atomic orbital (see Figure 2.1). The
atomic orbital together with the oxygen p orbitals form the cr bonding
Chapter 2

-> 5
>.
0
...... l
O
(])
c
UJ
-5

z r F L r
(a)

> 0
-
>.
Ol
Cii
c
UJ
-5
p
r--....
-- " =--
"
--------- - - -:::::::
-10

z r F L r
(b)

2.3. The partial band structures of (a) Co0 2 and (b) LiCo02 as calculated within the
ensity approximation. The dashed line shows the Fermi level.

nd anti-bonding eg * bands. The depletion around the Co ions coincides


a significant increase in charge density in atomic p-like orbitals on
en ions which point toward the lithium ions and also overlap with the
ted cobalt dx2-y2 like lobes.
The simultaneous depletion of charge in dx2-y2 like orbitals around t
and accumulation of charge around oxygen indicates a change in the
ization of the cr eg bonds between oxygen and cobalt. Since the
onding eg * bands are unoccupied in LixCo02, the polarization of the cr
reflects changes in the nature of the bonding egb bands. As lithium is
, the egb bands obtain more of an oxygen character and less of a Co
ole of Electronic Properties ... 61

2.4. Charge difference plot between Li 114Co02 and Co02• Dark shade signifies regions
rge accumulation and light areas correspond to regions of charge depletion.

--c o cobalt
•Lithiu

--B
Qoxygen

--A

c
--c

--B

--A

2.5. The 03 crystal of LiCo02. The crystallographic plane on which the electronic
density difference is viewed in Figure 2.4 corresponds to the shaded plane in this figure.
Chapter 2

cter. This causes the cr bond between Co and oxygen to become less
ent and more ionic with increasing x. The result is a significant increase
e electron density at the oxygen sites immediately surrounding the
m ions. The net effect is that the electron transfer from lithium to the
s very local and occurs predominantly to the oxygen ionsY
The conventional picture of lithium transition metal oxides is that the
on donated to the host by lithium is transferred to the transition metal
7 8 17 18
e it shifts its valence state. First principles work within LDA ' ' • show
he electronic changes of the host with x are in fact more subtle. The
ion of lithium to the Co02 host causes a shift in the nature of the bond
een oxygen and cobalt from a covalent character at low lithium
entration to a more ionic character at high x. While the electron donated
hium is added to the t2g band, which is predominantly of Co d character,
ffect of this addition is to polarize the Co-O bond such that the charge
d the oxygen ions actually increases upon lithium insertion (it is
rtant to realize that oxygen is not in its fully ionized state of -2 in Co02).
e, while it is reasonable to talk about formal valence changes of Co upon
ertion/removal, one has to keep in mind that the rehybridization around
obalt ions occurs in a manner that ensures that the local net charge d
17
the cobalt ions remains fixed as the lithium concentration changes.

. Experimental Evidence for Shift in Covalency

Both X-ray absorption spectroscopy (XAS) and electron energy loss


roscopy (EELS) have been used to study the local electronic properties
xCo02 as a function of x and have provided evidence consistent with a
71 73
in covalency with varying lithium concentration. - Both XAS and
measurements rely on transitions of core electrons to unoccupied states
e the Fermi level. Of particular importance are the 0 K-edge, resulting
the excitation of an 0 ls cores electron into unoccupied 0 2p states, and
o Lz.3 edge, arising from the excitation of Co 2p electrons to unoccupied
ole of Electronic Properties ... 63

d states. As the lowest unoccupied states in LixCo02 are those made up of


ybridization of the Co 3d and 0 2p levels, the 0 K-edge and the Co
Lz.r supply useful information about the Co-O bond. Variation of
the rum with lithium concentration sheds light on the nature of bonding
and ates where the charge of the electron from the intercalating lithium
goes. xcitations of core electrons with XAS and EELS are local
phenomena election rules derived from electric dipole allowed
transitions isolate defined excitations. Hence the 0 K-edge spectra,
for example, offer mation about the unoccupied 2p states projected on
the oxygen sites as ansition from 0 ls to Co 3d is forbidden within
the electric-dipole ximation.
Measurements of the Co Lz.redge in LixCo02 as a function of lithium
ntration show only minor variation of the spectra with lithium
ntration.71 -73 The Co Lz.3 spectrum consists of two major peaks, Lz, and,
rising from excitations of Co 2p312 and 2p112 core electrons to unoccupied
d states. The splitting of Co core 2p levels is induced by spin-orbit
ing. While Graetz et al.72 were unable to discern a variation with x in the
73
ity of the Lz.3 peaks, Yoon et al. were able to quantify a very slight
se to higher energy in the peak positions as LixCo02 is deintercalated.
The variation of the 0 K-edge spectra with lithium concentration is
more pronounced 71- 73 than that of the Co Lz.redge. Even in fully
ed LiCo02, a well defined transition from the core 0 ls state to the
upied 2p state is observed, a feature that is absent in completely ionic s
where the oxygen 2p states are locally fully occupied. This result tes
some degree of covalency between the Co-O bond in LiCo02• As
02 is deintercalated, the 0 K-edge spectra change dramatically.71 -73
ercalation is accompanied by an increased broadening of the 0 K near
pre-peak as well as an increase in the integrated intensity of the pre
2 In fact Yoon et al.73 identified the growth of three new shoulder peaks
deintercalation that emerge around the original peak corresponding to
ls to 2p transition of fully lithiated LiCo02•
Chapter 2

The pronounced variation of the 0 K-edge spectra compared to the


r variation of the Co .redge spectra indicates the important role that
en plays in the states near the Fermi level. The increase in integrated
sity of the 0 K near edge pre-peak upon deintercalation implies electron
tion of the 0 2p states and hence a reduction in the local charge density
71 72
nd the oxygen ions. •

The increase in covalence with decreasing lithium concentration plays


portant role in determining the structural properties and the sequence of
e phases with x observed experimentally and predicted from first
iples for layered LixCo02• It is also of importance in understanding the
negligible concentration dependence of the activation barrier for lithium
sion.

3. The Role of Covalency in Determining Thermo


dynamic, Kinetic and Structural Properties of
LixCoOz

Delithiation of LixCo02 leads to phase transformations and lattice


meter changes that are closely linked to the accompanying changes in
70
ronic structure. LiCo02 is a semiconductor but within a delocalized
structure picture should become metallic upon lithium removal due to
reation of holes in the t2g valence bands. Experimentally, though the
val of lithium for x ranging between 0.93 and 1.0 is found to result in the
on of electronic-hole states that are localized in space and exhibit an
ated conduction mechanism? The actual transition from the semi
ucting state to a metallic state is obscured by a first order structural phase
74
formation between x=0.93 and 0.75. Below x=0.75, LixCo02 exhibits
3 3 18 27
lic properties. It has been argued • • that the semi-conducting to metal
tion induces the structural phase transformation between x=0.93 and
as the electronic transition is likely to break the convexity of the free
y in part as a result of additional configurational entropy from localized
ole of Electronic Properties ... 65

18 27
on-hole states in the semi-conducting state. ·

Further delithiation of LixCo02 leads to a series of ordering and


ural phase transformations along with a dramatic contraction of the e
parameter perpendicular to the oxygen planes below .x=0.5. 75•76 Reimers
74
ahn were the first to observe an ordering phase transformation at .x=l/2
eby rows of lithium ions are alternated by rows of vacancies. Amatucci et
demonstrated the stability of fully delithiated Co02 but observed that
is stable in the 01 crystal structure which is characterized by an
77
B oxygen stacking sequence. Comprehensive first principles
2,
tigations 15" 17" 18 of phase stability in LixCo0 confirmed the
odynamic stability of the ordered phase at x=l/2 observed by Reimers
74
Dahn as well as the 01 phase observed by Amatucci et al.76
ermore, a staged phase in the vicinity of .x=0.15 was also predicted to be
18
odynamically stable from first principles. 15 • The predicted staged phase,
d Hl-3, 15 18· is characterized by a stacking sequence that is a hybrid
en 03 and 01. Alternating lithium planes in Hl-3 have an 03
onment (i.e. lithium sites are edge sharing with Co octahedra) and are
lly occupied by lithium while the remaining lithium planes have an 01
nment (lithium sites share faces with Co octahedra) and are vacant. The
ity of the H1-3 phase has recently been confirmed experimentally. 78•79
The progression in stability in layered LixCo02 from 03 to H1-3 to
ring delithiation can be attributed to the increased covalency of the Co
d with decreasing x. In the delithiated state, 03 Co02 is isomorphic to
, a relatively ionic compound, while 01 Co02 is isomorphic to Cdl2, a
covalent compound. The H1-3 phase at low lithium concentrations
es accommodation of the increased covalency of the Co-O bonds in the
ty of the 01 like stacking while simultaneously accommodating the
m ions within the alternating planes locally having the 03 stacking. H1-
be thought of as a local phase separation between a delithiated 01 block
Li-richer 03 block.
Part of the significant contraction of the lattice parameter c of layered
Chapter 2

o02 upon deintercalation can be attributed to a reduction in the number of


m ions which electrostatically pull the 0-Co-0 sheets together. Another
ficant factor contributing to this contraction, though, is the change with x
e electronic properties of the compound. The increased covalency of the
bonds with delithiation results in a contraction of the cobalt-oxygen
nces and, therefore, a reduction in width of the 0-Co-0 slabs as x is
ased. Furthermore, the increased covalency is accompanied by a
tion in the polarization of negative charge toward the oxygen ions.
e the electrostatic repulsion between negatively charged oxygen ions of
ent 0-Co-0 slabs diminishes as lithium is removed from the host.
Kinetic properties such as the migration barrier for Li diffusion are
ted by changes in the electronic properties with varying lithium
entration. First principles calculations31'36 predict that lithium diffusion in
ed LixCo02 occurs with a divacancy mechanism whereby the lowest

0- ------------:0
o::·:::::.....>:o-.-.-::::: : ------ :0

0 ...- - ·· · ··o
···o:::·:.-_·_·_·_· . ·_--:::o·········
- --- - . . .. - . ...... -.-- --

2.6. The dominant migration mechanism in layered LixCo0 2 is by means of a divacancy.


resence of a divacancy enables lithium to pass through an adjacent tetrahedral site as
ted above (filled circles are lithium, empty squares are lithium vacancies, large empty
are oxygen and small empty circles are cobalt).
ole of Electronic Properties ... 67

y migration path between neighboring octahedral sites passes through an


ent tetrahedral site as illustrated in Figure 2.6. First principles
lations also predict an increase in the activation barrier upon delithiation.

The tetrahedral site along the lithium migration path shares a face with
jacent octahedral site containing positively charged cobalt. The resulting
rostatic repulsion energetically penalizes the tetrahedral site relative to
ctahedral site. This electrostatic repulsion is screened to some extent by
egative electronic charge on the oxygen ions. Nevertheless, the screening
nishes with decreasing lithium concentration because of the
mpanying reduction of the charge on oxygen. As the Li concentration is
ed, the accompanying reduction of screening, along with the contraction
e c axis, which results in a reduction of volume of the tetrahedral site,
to a dramatic increase of the activation barrier for lithium migration.

ELECTRONIC PROPERTIES IN LiNi02: THE 180°


INTERACTION

As is the case for LiCo02, LiNi02 is also stable in the 03 crystal


ure. Nevertheless, nickel has one extra valence electron which
atically alters the properties of layered LixNi02 as compared to those of
o02• LiCo02 is a semiconductor with occupied t 2g bands and unoccupied
nds. Upon delithiation, holes are introduced in the t2g bands. In LiNi02,
dditional valence electron resides in one of the eg bands. Within crystal
theory, the two eg states in an octahedron are degenerate, and single
ancy of the eg states can potentially lead to a Jahn-Teller distortion of
ctahedron. The distortion lifts the degeneracy of the eg levels lowering
nergy of the occupied level while raising the energy of the unoccupied
As described above, molecular orbital models characterize the eg states
ti-bonding levels which are typically more localized electron states.
these simple models we can anticipate distortions of Ni octahedra in
Chapter 2

02 and local charge ordering on the Ni ions upon delithiation. While


ctive distortion of the crystal due to Jahn-Teller activity has not been
ved experimentally,80 83
- evidence exists for the presence of
ordinated locally distorted octahedra.80'81 In fact, accurate first principles
lations within the generalized gradient approximation have predicted a
energetic preference for a collective Jahn-Teller distortion of LiNi0 2
al.35 Furthermore, at intermediate lithium concentrations charge ordering
een Nt 3 and Nt 4 ions accompanied by local Jahn-Teller distortions has
predicted from first principles. 34 •39 40

While accurate first principles calculations confirm the conclusions


emerge from crystal field and molecular orbital models, detailed first
iples calculations also predict an unexpected electronically induced long
attraction between lithium ions in different lithium planes.34 39• 40• A
4
matic stud/ of the energies and local distortions of Ni octahedra in
ures of LixNi02 with different lithium-vacancy arrangements showed a
rkable attraction between lithium ions at opposite ends of a distorted Ni

Q Oxygen

e Lithium
• Nickel

2.7. In LixNi0 2 a long range attraction between a pair of lithium ions of different lithium
is mediated by a Jahn-Teller distortion of a Ni+ 3 octahedron.

edron as illustrated in Figure 2.7. 180° Li-0-Ni-0-Li configurations


ole of Electronic Properties... 69
3
nd Ni+ ions along the elongated axis of the Jahn-Teller distorted
edra were consistently present in low energy configurations of LixNi02•
A similar long range interaction between four lithium ions was also
rned in which four lithium 2s orbitals hybridize with the eg molecular
34
al made of Ni d,2.y2 and oxygen p orbitals as illustrated in Figure 2.8.
3
ctahedron containing Nt and coordinated by four lithium ions as in
e 2.8 are characterized by a negative Jahn-Teller distortion in which the
Ni-0 bonds pointing to Li ions are elongated and two Ni-0 bonds
ing to Li vacancies are contracted.
3
The stability of the 180° Li-O-Ni+ -0-Li configurations around
34
rted octahedra can be rationalized as follows. The presence of lithium
at opposite corners of an octahedron lowers the energy of an occupied eg
due to hybridization between the Li-2s, 0-2p and aNi eg orbital (either

2.8. Attraction between four lithium ions over long distances in Li,Ni0 2 is mediated by
tive Jahn-Teller distortion of a Nt 3 octahedron (legend as in Figure 2.7).

2 or d3z2.,2). Although a Jahn-Teller distortion in any environment


dy leads to a lowering of the energy of an eg level, the presence of Li ions
posite corners of the oxygen octahedra further stabilizes this eg orbital
gh hybridization. Hence the occurrence of the long-range 180° Li-Li
tion and the Jahn-Teller distortions are coupled, one reinforcing the other.
Chapter 2

energy gain from a Jahn-Teller distortion is maximal when the occupied


bital is localized. This favors localization of electronic charge around the
ns, which upon deintercalation leads to charge ordered states consisting
ell defined Nt3 and Ni+4 ions. Due to the 180° Li-O-Nt3-0-Li attraction,
4
ithium-vacancy arrangements and the Nt 3 and Nt arrangements are
gly coupled.
The 180° coupling between Jahn-Teller active ions and the lithium
of different lithium planes is in part responsible for the dramatically
ent electrochemical behavior between LixNi02 and LixCo02• 39
actions between different lithium ions in a transition metal oxide are
ally short-ranged due to extensive screening by the oxygen ions. The
coupling in LixNi02, which is absent in LixCo02, leads to a long range
ling between lithium ions of different lithium planes that are more than 8
art. The added long range interactions favor different lithium-vacancy
ing reactions than is observed and predicted in LixCo02• In fact, first
iples calculations predict a very stable ordered phase at x=2/5 in LixNi0 2,
suspected type of ordering on a triangular lattice.39
In reality, synthesis of ideal LiNi02 has proven elusive, with actual
mens invariably having an excess of Ni ions.80 The excess Ni ions
py sites within the lithium layer. So while it is possible to make
ctions from first principles about ideal LixNi02, the presence of excess
the lithium planes in experiment is likely to alter these predictions to
extent. Excess Ni ions in the lithium planes will certainly alter the
ogy of the phase diagram of ideal LixNi02 and may even change the
of ordered phases that occur. Nevertheless, the existence of the 180°
range lithium attraction should persist in some form, even in the Ni
s samples.
ole of Electronic Properties ... 71

LAYERED TO SPINEL TRANSFORMATION IN


LixMnOz

Most forms of LixCo02 and LixNi02 have the layered 03 crystal


ture. Lithium manganese oxide, however, is generally synthesized in the
l crystal structure with stoichiometry LixMn 204. The voltage profile of
pinel crystal structure is characterized by two plateaus, one around 4.2 V
<l and one around 3 V between .x=l and .x=2. The second plateau occurs
esult of a first order phase transformation. For many years, much effort
evoted to synthesizing layered LixMn02• 84' 85 Nevertheless, successfully
esized layered LiMn02 was found to transform to a phase resembling
l upon lithium removal.86- 89

. The Crystallography and Thermodynamics of the


Layered to Spinel Phase Transformation

The fact that the layered form of LiMn02 is observed to readily


orm to the spinel variant upon delithiation is not surprising from a
allographic point of view. Both the layered 03 crystal structure and the
l crystal structure have the same close-packed oxygen framework with
BCABC stacking sequence. The two phases only differ in the
gement of the lithium and transition metal ions over the interstitial sites
e oxygen skeleton. Transformation from layered to spinel therefore only
res a reordering of the transition metal and lithium ions.
In the layered phase, the transition metal ions occupy octahedral sites
ernating layers between close-packed oxygen planes, giving the phase a
bohedral symmetry. The lithium ions occupy the remaining octahedral
that also form alternating layers between close-packed oxygen planes. In
pinel crystal structure, the transition metal ions are distributed more
rmly among the octahedral interstitial sites: 3/4 of the metal ions reside
Chapter 2

lternating layers between close-packed oxygen planes, while the


ining 1/4 of the metal ions reside in the other alternating planes. This
cular metal ordering produces a transition metal oxide host structure with
symmetry. While the lithium ions can occupy the remaining vacant
edral sites in the host, energetically favorable tetrahedral sites are also
able; the metal ordering in spinel results in a set of tetrahedral sites that
ot share faces with metal-oxygen octahedra. Upon deintercalation of the
ed 03 crystal structure, channels within the oxygen framework open up
nable transition metal ions to migrate to the vacated lithium layers. For
yered phase to transform to spinel, exactly one in four transition metal
must migrate to the lithium layer. This transformation thus can occur
ut reconstruction of the oxygen skeletal structure.
First principles calculations have exposed that for many transition
oxides LixM02 (M=Ti, V, Mn, Fe, Co, Ni) 16' 27 the spinel crystal
ture is energetically more stable than the layered crystal structure at
. Figure 2.9, which illustrates the calculated free energy curves of 03
pinel LixCo02 as a function of lithium concentration/0 clearly shows the
odynamic stability of spinel around x=l/2 over the 03 phase. This
ve stability means that for layered lithium transition metal oxides a
odynamic driving force exists for transformation to the spinel crystal
ure upon deintercalation. Nevertheless, only LixMn02 is observed to
go this transformation at room temperature.86- 89 Layered LixCo02 for
ple, maintains its layered structure upon continued cycling. The high
lity of Mn ions which makes the transformation of LixMn02 to a spinel
ure at room temperature possible, has its origin in the particular
onic structure of the Mn ion in octahedral and tetrahedral environments.
ole of Electronic Properties ... 73

-> Q)
E........
100

0
...
>.
0 >
.... . -100
Q)
••
c
Q) -200 ••••
Q) ••••
Q )
.... .
LL
-300 ••••
••••••••••
-400

0 0.2 0.4 0.6 0.8 1


Li concentration

2.9. Free energy of layered 03 (solid line) and spinel (dashed line) LixCo02 as a
on of lithium concentration.

2. A Two Stage Transformation Mechanism

First principles calculations have shown that the layered to spinel


transformation in LixMn0 2 occurs in two stages?3 This is consistent
experimental observations.90- 93 The kinetics of the layered to spinel phase
formation relies crucially on the first step which is driven by a unique
e-disproportionation reaction predicted from first principles to occur
in LixMn02 and not in the Co and Ni layered compounds.33
A first step in the transformation from layered LixM02 to the spinel
nt is the migration of transition metal ions to adjacent tetrahedral sites.
e tetrahedral sites share faces with an oxygen-octahedra in the transition
layer and three octahedra in the lithium layer (Figure 2.10).
Chapter 2

Li layer

Mn layer

lli, 0 Oxygen
'
' o Lithium s:

: : : : : : e Manganese
'

'

2.10. The layered 03 host and spinel have the same oxygen skeletal structure.
ormation from layered to spinel can occur by a redistribution of the transition metal ions
this structure. The first step of such a transformation involves migration of 114 of the
ons to tetrahedral sites (thick dashed lines) in the lithium layer.

The migrating transition metal ion must then migrate further to an


edral site within the lithium layer. If one in four transition metal ions
te to the lithium layer in a coordinated manner (see Figure 2.11)
mpanied by lithium rearrangement to the non-face sharing tetrahedral
that result from the metal rearrangement, the transformation would yield
ect free spinel phase. Due to the thermal nature of such a reordering
ormation, however, we can expect the transition metal rearrangement to
in a more random way, creating a disordered spinel phase. Over time,
h, the intermediate disordered phase should gradually evolve to the
ct spinel ordering as a result of continued ion rearrangement within the
en skeletal structure.
ole of Electronic Properties ... 75

2.11. Projection of a metal layer (transition metals are the filled circles) and the oxygen
oxygen ions are the empty circles) above it in the 03 crystal structure. Transformation to
involves migration of 114 of the metal ions to the lithium layer. This leaves a vacant
site (empty squares) within the metal layer. The migrated metal ions must migrate to a
site above a triangle of metal ions (shaded circle). In order for this rearrangement to
o spinel, the arrangement of vacancies within each metal layer must be ordered as
ated in the above figure.

.1. Stage I of the Layered to Spinel Transformation in LixMn02

A tetrahedral site as in Figure 2.10 is only a viable path for transition


migration to the lithium layer if the three adjacent octahedral sites in the m
layer are vacant. Hence a precondition for the layered to spinel
ormation is some degree of lithium deintercalation such that the
taneous existence of three lithium vacancies around a tetrahedral site has
sonable probability of occurring. As the lithium concentration is reduced,
oncentration of such tri-vacancies increases. Typically the transition
s considered for cathode materials with stoichiometry LixM0 2 prefer
edral sites over tetrahedral sites. Migrating to a tetrahedral site is then
3
mpanied by an increase in the energy of the crystae and therefore
odynamically unfavorable. But first principles calculations predict that
Chapter 2

ons with a valence state of +2 behave differently, actually preferring


hedral sites over octahedral sites.
The formal valence state of transition metal ions in LiM02 is +3
h on average increases towards +4 as lithium is removed. Nevertheless,
33
e Li concentration is reduced, first principles calculations predict that
ions can form through a charge disproportionation reaction involving
3
ron transfer from a neighboring Mn+ ion according to

+3 +2 =4
2 Mnoct --7 Mntet + Mnoct
)

The above reaction equation should be interpreted as follows:


3
ation of a Mn+ ion from an octahedral site in the metal layer to an
ent tetrahedral site surrounded by lithium vacancies becomes
3
etically favorable provided that it is adjacent to another Mn+ ion from
2
h it can borrow an electron. The result of the reaction is a Mn+ ion in a
4
edral site within the lithium layer and a Mn+ ion in the metal layer. First
2
iples calculations predict that the valence electrons of the Mn+ ion in the
3 2
edral site have parallel spin? A high spin Mn+ ion has a half filled d
that chemically behaves similar to a closed shell ion. Hybridization with
oordinating oxygen ions then occurs predominantly with the empty 4s
3
p levels, which in a tetrahedral environment, hybridize into sp orbitals.
he ability of the Mn ions to form a closed d shell electron configuration
makes migration to adjacent tetrahedral sites energetically favorable. This
e electronic property of Mn is absent in other transition metal ions in
02 (M=Co or Ni) and is crucial in precipitating the first step of the
ed to spinel phase transformation. In the other layered transition metal
s, migration of the transition metal to a tetrahedral site is met with an y
33
barrier; in the Mn compound, it leads to a reduction in energy, and
will occur spontaneously as long as sufficient vacancies exist in the
ole of Electronic Properties ... 77

m layer and sufficient Mn+3 ions are available in the metal layer to feed
harge-disproportionation reaction of Eq. (2.17).
The availability of vacancies in the lithium layer and Mn+3 ions in the
layer are requirements that have an opposite dependence on lithium
entration. Decreasing the lithium concentration increases the number of
m vacancies but it decreases the number of Mn+3 ions. A maximum in
ctahedral to tetrahedral migration rate can therefore be expected at
mediate lithium concentration, the concentration which also happens to
ide with the maximal thermodynamic driving force for the layered to
l transformation.

.2. Stage II of the Layered to Spinel Transformation in LixMn02

In layered LixMn02, the migration of Mn to tetrahedral sites between


etal and lithium layer is predicted to occur spontaneously (without
y barrier) at intermediate lithium concentration.33 In fact, at .x=l/2,
ient Mn+3 ions exist for 1/4 of the Mn ions to migrate from the metal
to tetrahedral sites by means of the charge-disproportionation reaction of
2.17). The migration of Mn ions from octahedral sites in the metal layer
rahedral sites leads to other tetrahedral sites in the lithium layers to no
r share a face with Mn octahedra. These tetrahedral sites then become
etically favorable for lithium occupation. Spontaneous Mn migration to
edral sites is predicted to be accompanied by lithium migration to
33
edral sites. While migration of Mn ions to tetrahedral sites at .x=l/2
s spontaneously, this phase with 1/4 tetrahedral Mn+2 and some
edral lithium is still intermediate in energy between the 03 phase and
erfectly ordered spinel phase (all lithium in tetrahedral sites, cubic
ing of Mn ions over octahedral sites).33 We refer to this intermediate
at .x=l/2 as the "splayered" phase and emphasize that it has 1/4 of the
ons in tetrahedral sites distributed uniformly but in a more or less
dered arrangement. The existence of a partially transformed layered
Chapter 2

90 93
e with tetrahedral Mn has been observed experimentally. - Further
formation of the splayered phase to spinel occurs by thermally activated
hops within the lithium layers and therefore proceeds slower than the
ed to splayered transformation, which has no barrier.
In a battery, charging rarely stops at .x=l/2 but continues to lower
entrations. Further lithium removal from the spontaneously formed
2
ered phase would require oxidation of Mn+ ions, destabilizing the Mn
in the tetrahedral sites. Lithium removal below .x=l/2 therefore leads to
migration from tetrahedral sites back to octahedral sites. Nevertheless, a
on in a tetrahedral site can migrate to four neighboring octahedral sites,
which resides in the metal layer and three which reside in the lithium
. The higher availability of octahedral sites in the lithium layer leads to a
igration of tetrahedral Mn ions to octahedral sites in the lithium layer g
further deintercalation. Repeated cycling will enhance the migration of
ons to the lithium layers and this is observed experimentally where
ng of the material leads to an increased spinel formation.

3. Suppressing the Layered to Spinel Transformation

The electronic origin of the layered to spinel phase transformation in


n02 can be exploited to suppress this transformation by appropriately
g the compound. The crucial step in the layered to spinel phase
formation is the charge-disproportionation reaction fed by the presence
3
n+ ions. Doping of the compound to prevent the layered to spinel
3
formation should hence deprive the host of Mn+ ions. This can be done
elements that are more electronegative than Mn, therefore oxidizing
4
to Mn+ , even in the fully lithiated state. This has been successfully
94 0 0 2
ved by Amrnundsen et al. who found that layered LixMn .4Cr .4Li
0 .2 0

s without transformation to spinel. Substituting half the Mn with Ni has


95 96
been shown to suppress the layered to spinel phase transformation. • In
ed LixMn0. 5Nio. 502, Ni is predicted to have a +2 valence while Mn has a
ole of Electronic Properties ... 79
8
alence? Charging of the compound leads to the oxidation of Ni from the
ate to the +4 state. The absence of Mn+ 3 ions at all lithium concentrations
nts the detrimental layered to spinel phase transformation in this
ound.

CONCLUSIONS

We have reviewed theoretical models and tools that enable us to


rstand and predict the electronic properties of lithium transition metal
s. We have focussed in particular on a detailed description of density
ional theory (DFf), currently the most reliable and accurate approach to
ing the electronic properties of complex oxides from first principles. We
also reviewed results and insights derived from DFf studies of three
rtant lithium transition metal oxides, namely LixCo02, LixNi02 and
n02• In our discussion of these three compounds, we have focused on
rtant electronic properties exposed by DFf calculations which have a
ular bearing on the electrochemical properties of these compounds. In
o02, DFf calculations have shown the importance of covalent bonding
en oxygen and cobalt and the role of increased covalency with
asing x in affecting the thermodynamic and structural properties of this
ound. In LixNi02, a DFf study has predicted a long range attraction
en lithium ions of different lithium planes. This long-range attraction is
ated by a Jahn-Teller distorted oxygen octahedra containing a Nt 3 ion.
lithium-lithium attraction, termed the 180° interaction, is in part
nsible for the very different electrochemical properties of LixNi02 as
ared to those of LixCo02• For LiMn02, a DFf investigation has led to
ediction of a remarkable charge-disproportionation reaction between Mn
which leads to spontaneous migration of Mn ions to tetrahedral sites
n the lithium layer of layered LixMn02• It is this charge
oportionation reaction, identified from first principles, which is
nsible for the undesirable layered to spinel phase transformation that has
Chapter 2

nted the successful implementation of layered LixMn02 in lithium


ries.

KNOWLEDGMENTS

We are grateful to Elena Arroyo, John Reed, Chris Marianetti, Claude


as and Bing Joe Hwang for insightful discussions. We thank the
rtment of Energy (award no. DE-FG0296ER45571) andthe National
ce Foundation (award no. DMR 98-08941 and NPACI supercomputer
ort).

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pter 3

SYNTHESIS OF BATTERY MATERIALS

M. S. Whittingham

Chemistry and Materials Science


State University of New York at Binghamton, Binghamton, NY 13902, U.S.A.

INTRODUCTION
Synthesis is critical not only to the generation of new materials for
ation of new structures and fundamental properties, but also for the
ion of materials with the optimum electrochemical behavior for
ercial devices. The technique used is quite often very different for the
two cases. The initial synthesis of a material should provide it in a
enough state that its intrinsic behavior and properties can be
ined; it should for example be possible to accurately determine
er its structure is cubic spinel, layered or some other form. There is
tly much confusion in the literature because the synthesized material
sufficiently well-characterized. Once well characterized, the material
to be synthesized in a form suitable to be used in a battery, for
le it may be doped or coated to enhance the conductivity, its particle
nd morphology will be optimized for maximum reactivity but
um corrosivity and side-reactions.
Many battery materials are metastable phases, and therefore non
nal synthesis methods must be devised to allow kinetics to over-ride
dynamics. Hence, many soft chemistry techniques have come to the
uch as hydrothermal, ion-exchange, intercalation, etc. In addition, to
ze the formation of the desired material frequently the reactants are
mixed prior to final reaction by for example sol-gel formation or co
tation as hydroxides.
A number of critical synthetic parameters will be discussed in this
r. The temperature of formation of the electrode material determines
ect structure, for example in all the layered structures strict ordering
cations is desired. Thus, in TiS2 no titanium must reside in the lithium r
diffusion is limited. This restricts the final firing temperature to a
Chapter 3

um of 600°C, otherwise there is significant titanium occupancy in the


er Waals layer. A similar behavior is observed in the layered metal
, such as LiNi02, LiNi 1_yMny02 and LiMn02. In the nickel oxides it is
l to find about 7% nickel occupancy on the lithium sites. In the
tion of layered LixMn02, great care must be taken to avoid
ratures over 100°C otherwise manganese migrates converting the
al to the spinel phase. For the mixed metal oxides, the temperature of
sis has a marked effect on the reversible capacity of the electrode. n
materials such as LiFeP04, the temperature of formation is key; too
temperature and some of the iron migrates to the lithium sites.
The synthesis and manufacture of battery materials will be
ssed by looking at a series of examples of materials that have moved
curiosity to research to development. Amongst these the concept of
lation reactions from the 1970's will be considered, high temperature
ns, followed by hydrothermal and ion-exchange reactions, then a
of synthetic methods for conductively coating the lithium iron
hate class of material. Finally, the synthesis of anode materials will be
sed.
Although cost is not critical in the research phase of a project, it is
l for the cost-effectiveness of batteries, that not only the electrode
als be themselves low cost, but that the process costs for synthesizing
12
terials also be low in cost. •

THE SYNTHESIS AND MANUFACTURE OF


TITANIUM DISULFIDE
When a battery is being commercialized, the synthesis process used in
oratory often cannot be used because of the processing costs or cost of
rting materials. As an example, titanium disulfide will be considered
in the laboratory bulk titanium was used to provide electronic grade
m disulfide, and sponge titanium provided research battery grade
al. The latter could be produced a pound at a time in silica tubes, had a
2 2
e area of 5 m /g, and allowed current densities of 10 mA/cm to be
ed. However, both involved reaction with sulfur, which took from
for the sponge to days for the bulk metal. Such material would cost
than $100/lb. An inspection of the commercial process, shown in
3.1, for sponge manufacture revealed that the precursor was titanium
loride, a liquid at room temperature. This tetrachloride is available in
e quantities as it is used in the manufacture of titanium dioxide paint
nt. Therefore, a manufacturing process was devised by two european
nies that involved the formation of stoichiometric TiS2 by deposition
is of Battery Materials 87

he gas phase reaction of TiC14 with H2S. This produced a sulfide with
phology with many plates growing in three dimensions from a single l
point, which shows excellent electrochemical behavior.
The stoichiometry and ordering of the titanium is critical to the
chemical behavior of TiS2• Stoichiometric and ordered TiS2 has been
3
to exist if the temperature is kept below 600°C, and to have metallic
4
ctivity. The titanium disorder can be readily measured by attempting
ercalate weakly bonding species such as ammonia or pyridine. In
e a slight excess, :::;1%, is beneficial in that it reduces the
iveness of the sulfur without significantly impacting the cell potential
lithium diffusion coefficient. It is preferable to add this extra metal to
tial reaction medium.

ILMENITE
(+rutile)

CHLORINATION
850-950°C
PETROLEUM COKE
I
2
ENT ILE) H.,S 500-600°C

I
KROLL PROCESS
Mg metal
I
TITANIUM
SPONGE
s, l;jQQ-l;jl;jQOQ TiS2
24 Hours

I
ARC FURNACE
I
TITANIUM s gQQOQ TiS2
INGOT 1 Week

.1. Synthesis and manufacture of titanium and titanium disulfide.


Chapter3

SYNTHESIS OF ALKALI ION INTERCALATES


BY INSERTION INTO THE HOST LATTICE
(AND THE REVERSE)
Although the heavier alkali intercalates of the transition metal oxides
56
halcogenides had been extensively studied, ' the lack of a suitable
ng agent delayed the formation and characterization of the pure
compounds until the early 1970's. Although lithium had been
78
d by dissolution in liquid ammonia, • this also resulted in the insertion
ammonia, resulting in degradation of the host lattice as the sulfide or
9
layers must all shift relative to one another as indicated in Figure 3.2.
10 11
trast when lithium is inserted by electro-intercalation, ' from butyl
12 14
in hexane, - or from mercury amalgams no solvent is incorporated
e lattice simply expands. Just as in the case of ammonia solutions,
can also be incorporated from aqueous solutions either chemically or
chemically, 10' 11' 15' 16 then the water must be removed. The many
tic procedures possible for the layered dichalcogenides are shown
9
atically in Figure 3.3.

Li
...

n-Butyllithium
Electrointercalation

0
Ti Li

.2. 110 projections of the structural changes occurring during the lithiation of disulfide
in the presence and absence of a co-intercalating solvent such as ammonia.9
is of Battery Materials 89

Many materials of interest do not exist as the thermodynamically


phase in the desired structure, and so must be prepared at low
ratures where kinetics control the path of the reaction rather than
odynamics. For example, the stable phase of titanium disulfide is the
d structure for LixTiS2 for 0$x:S1 and batteries can be built in either the
d state Li/ffiS2 or in the discharged state C/LiTiS2• 17 In contrast,
gh the layered sulfides LiVS2 and LiCrS2 were well-known their
free analogs were not, and so researchers at Bell Labs synthesized
18
y de-intercalation of the fully lithiated compounds. They developed
19
range of chemical lithiating and delithiating agents. As noted above,
ered hexagonal close-packed form of TiS2 is the thermodynamically
20 22
phase; however a number of researchers - successfully synthesized
bic form by de-intercalation of, for example, the spinel CuThS4. This
structure can also be reversibly intercalated with lithium, although the
on coefficient is not as high as in the layered form.
The more ionic transition metal dioxides are not readily formed as
structures in the absence of cations between the M02 layers, other
being more stable such as in Ti02 where a range of phases such as
anatase and brookite are known but layered Ti0 2 is not. Goodenough
o-workers, whilst investigating the magnetic behavior of LiCo02
ized that it might be possible to also form a layered compound,
23
ous to the sulfides by lithium removal. They successfully formed a
d LixCo02 by lithium de-intercalation and showed that this material
reversibly incorporate lithium over at least a range of 8x of around 0.6.
ed to the first commercially successful lithium secondary battery by
4
The lithium cobalt oxides can be readily prepared by the high
ature firing of materials containing lithium and cobalt in the
riate ratio in an oxidizing environment. Amatucci et al. 25 more
y showed that all the lithium can be removed giving Co02, which has
me 1T structure as TiS 2•
A number of the layered dichalcogenides and oxides can incorporate a
lithium ion forming the phase LizMX2. This was first observed for
14 26
um diselenide, ' and can be accomplished either electrochemically
27
mically, for example by using butyl-lithium. LizNi02 was formed
lectrochemically and chemically using lithium benzophenone in
drofuran; it's structure switches from the 3R-LiNi02 phase to one
al to those of LizTiS2 and LhVSe2, where the lithium ions sit in all the
dral sites between the Ni02 sheets forming a 1T structure. In a similar
r LizMn0.5Ni 0.50z has also been synthesized in electrochemical cells,
th lithium ions can be cycled when part of the Mn is substituted by
28
m.
Another innovative synthetic approach was developed by Haering29
owed that 2H-MoS2, where the molybdenum is in trigonal prismatic
Chapter 3

Oxidation-MX 2 - Reduction

r .JC.-1---n- Butyl, lithium -----t,.r.....;:,.-1


1----A +Heat Ax MX 2

In NH3 i 00 H g -. --.-....--'

BD in Y
t

Polar solvent

z
A, , Y 11 _z., M X 2

.3. Schematic of the reactions of the dichalcogenides.9

nation, could be induced to change structure to the 1T TiS2 form by


oration and then removal of lithium. This structural form showed
improved cyclability over the 2H form which is poorly reversible, and
e basis of the MoliEnergy MoS 2 lithium battery. 30

HIGH TEMPERATURE SYNTHESIS OF LAYERED


OXIDES

The layered compound LiCo02 is made by the high temperature


23
n in air of the carbonates at 900°C. A number of other layered
metal dioxides, such as LiNi02 can also be formed by high
ature synthesis, but in this case there is significant nickel disorder so
is of Battery Materials 91
31
e lithium layer always contains some nickel, seven to ten % being
ypical. In contrast there is no measurable cobalt in the lithium layer
LiCo02 is formed at the optimum temperature. However, there is the
ility of forming spinel-like (some Co in the Li layer) or the spinel
32
sometimes known as LT-LiCo02, 33 when lower temperatures such
°C are used in the synthesis. It is not easy to distinguish between the
d and spinel forms of these layered oxides, as the X-ray diffraction s
look almost identical at a first look. A clue to spinel formation is the io,
which is around 4.90 for the spinel, while it is closer to 5.00 for the
ohedral layer structure; both have cubic close-packed oxygen lattices
hich the ideal cia ratio is 1.633 (= 4.90/3). A second clue to pure
d formation, which results from the non-ideal close packing in the
d structure, is the existence of a doublet in the X-ray powder pattern at
66° 28 associated with the 108 and 110 reflections; the spinel has a
reflection, the 440, in this region for CuKa radiation. The LT-LixCo1_
phases, also formed at 400°C, were found to have spinel-like
res where there is partial occupancy of the lithium sites by the
34
ion metal ions.
The synthesis of LiCo02 requires firing at temperatures from 850 -
C for one to two days. However, such high temperatures may not be
ary. For example, ion exchange between CoOOH and excess LiOH
in pure LiCo02 after firing to 280°C to remove residual carbonate and
35
ide. This ion-exchange was carried out in the solid state at 100°C
st a trace of water added as a transport agent. HT-LiCo02 was formed
denced by the doublet at 66° 28, the cia ratio of 5.00 and the
chemical fingerprint. The success of the synthesis in this case can be
ated with the structure of the starting reagent, CoOOH, which is
d and does not change under the low-temperature ion-exchange
ions. The electrochemical behavior was quite good, but the capacity
ss than that of the high temperature formed LiCo02; it was suggested
ere is some cobalt disorder, some of the lithium sites being occupied.
35
2 was similarly synthesized but no electrochemical or nickel ordering
ere presented, but the rather broad X-ray lines suggest significant
disorder. LiCo02 formed hydrothermally at 230°C from cobalt nitrate,
hydroxide and hydrogen peroxide, had rather poor cycling
teristics, the capacity dropping by more than 70% over 20 cycles at a
36
e.
37
The spinel LiNiz04 is also known, being formed when Li0.5Ni02
by electrochemical removal of lithium from LiNi02 is annealed at
; this structural conversion begins at 150°C just as observed for
38
d Li05Mn0z. The coalescence of the 108 and 110 X-ray reflections is
observed. This spinel is only stable until 300°C, when it decomposes
mixture of products.37 As noted above, neither Ni02 nor Co02 has
Chapter 3

ynthesized directly because of their thermodynamic instability. In the f


Ni02, the oxygen partial pressure is well over one atmosphere at so
it is inherently unsafe even under oxidizing conditions. In an
t to reduce the possibility of explosive interactions with the
lyte, additional elements can be used to partially replace the nickel.
ample, addition of a trivalent ion such as boron or aluminum prevents
mplete removal of all the lithium thus limiting the overall average
ion state of the nickel. Alternatively, part of the nickel may be
ed by for example cobalt as in LiNi1_yCoy02, which forms a continuous
olution. A combination of these two approaches has been extensively
9
d, as in LiNi0.85Coo.IAlo.osOl 40
' and LiNio.soCoo.1sAlo.os02.41 The LiNii
42
phases have been prepared '43 by the direct reaction of LhC03, NiO
o304. A finely ground mixture of the reagents is first fired at 500°C for
hours, followed by 48 hours in oxygen at 800-1000°C. A solid solution
d over the entire range of y from 0 to 1.
Manganese has also been substituted in the cobalt oxide, LiCo1 _
2 for O<y 0.2 using a combinatorial approach starting from an
us solution of lithium hydroxide, cobalt acetate and manganese acetate,
44
ed by firing at 730°C; the lattice parameter perpendicular to the
was found to expand with increasing manganese content. At higher
nese contents, second phases begin to be observed.
45
Spahr et al. showed that the replacement of some of the nickel in
2 by manganese also served the same purpose as cobalt in improving
clability and capacity of the nickel oxide electrode. They found that
mposition LiNi0.5Mno.502 was optimum. The synthesis of the logical
tep, LiNi1_y-zMnyCoz02 will be discussed below under manganese
.
46
Grenier et al. have shown that oxygen can be electrochemically
lated from strong basic electrolytes into some superconducting
als, thus increasing the oxidation state of the transition metal. If this
que can be extended to organic electrolytes at room temperature then it
be very useful in increasing the cell potential and possibly the
ty of cathode materials; the importance of such an oxidation was
when the capacity of N(CH3)4V307 was tripled when it was oxidized
47
CH3)4V308. Such oxidations must be performed below the
position temperature of the compound. A similar behavior has been
ed in the formation of hexagonal Mo03 by the thermal decomposition
hydrate, Mo03•0.6H20, formed by ion-exchange of the sodium form
6M nitric acid;48 this molybdenum oxide reacts reversibly with about
/Mo0349 similar to that of Mo03 itself.
is of Battery Materials 93

HYDROTHERMAL AND SOLVOTHERMAL


SYNTHESIS OF CATHODE MATERIALS
In this synthetic method, the reactants are dissolved in water or
r solvent and then heated above the boiling point of the solvent for the d
length of time. The heating may be performed in either a
ntional oven or in a microwave oven. This process is used
ercially for a number of materials, including zeolites in tonnage
ties daily.
Although the technique has been used for several decades, it is only in
st ten years that much effort has been focused on transition metal
50 51
unds for battery electrode use. The early work has been reviewed '
mphasized many tungsten, molybdenum and vanadium oxides. Thin
of tungsten oxides for electrochromic or sensor applications can be
52
d in-situ in the hydrothermal reactor. Vanadium oxides in a wide
47
of morphologies have been formed hydrothermally, including the
chemically active nanotubes.53. 56 The studies of vanadium oxides
d the critical role that pH plays in determining the structure. At high
lues, the structural building blocks contain predominantly V04
dra, at intermediate values vo5 square pyramids, and under the most
conditions V06 octahedra.57 As V04 tetrahedra are only stable in the
dation state, materials containing these are unsuitable candidates for
es. In contrast the V06 octahedra are stable over many oxidation
+5 to +2, and so are much more likely to provide rechargeable
e materials. Thus, the electrochemically active o-
V4010 phases and
ls are all made usually at pH values less than 3. The electrochemically
47
H2V 308 phase has also been synthesized solvothermally, and shows
lectrochemically behavior.
A number of layered structure manganese oxides, MxMn02, where
Na or K have been synthesized by hydrothermal and other soft
try approaches. When KMn04 aqueous solutions are hydrothermally
58
at 170°C, well-crystalline layered K0.27Mn02.nH20 is formed. The
may be readily removed by heating. In this reaction, KOH is also
ed and oxygen gas evolved according to the equation:

The corresponding lithium and sodium manganese oxides have also


38
ynthesized from the permanganate. ' 59 The alkali content of these
nese oxide compounds is very dependent on the alkali metal and the
n medium; thus, in water x in MxMn02 is 0.47, 0.35 and 0.27 for Li,
K respectively. In these compounds the manganese site occupancy is
o unity, and about 0.6 Li/Mn can be readily cycled in lithium cells.
Chapter 3

on of cobalt or nickel to the reaction medium, allows the partial


tution of the manganese. This substitution even at the 1 to 5% level,
60
ses the electronic conductivity by two orders of magnitude, and
61
cantly improves the recyclability. Heating of the lithium compound
rts it to the spinel phase; this conversion reaction begins even at
38
, and is rapidly completed on heating to 400°C.
The hydrothermal treatment of A.-Mn02 with 0.5 M LiOH or 4 M
aqueous solutions at 170°C for 24 days leads to the formation of the
l" Li0.63Mn .7304•0.4H20 with a=8.18 A and the layered
62
Mn02.15•0.6H20 respectively. If the LiOH solution is stronger than 1
n LhMn03 was formed.
Manganese dioxides can also be prepared 63 using a sol-gel reduction
64 of
nganate using a reductant such as sugar or fumaric acid. The
m compound, Na0.45Mn02•0.6H20, has been formed by the reduction
of
04 by oxalic acid formed in-situ followed by a 600°C anneal and a
65
oxidation. The sodium ions can then be ion-exchanged by lithium
65
ransition metals. After annealing at 300-600°C the material shows
-like characteristics and cycles well on the 3V plateau; the X-ray
ns are also best fitted by a cubic spinel structure with a=8.129A,
tent with a 600°C anneal of a Li0.45Mn02 composition.
66 layered ranceite-type manganic acid,67HyMn1.002•nH20, has been
The
d following the method of Tsuji et al. by the acid hydrolysis of
04 at 60°C. Ion exchange of the manganic acid for two weeks in a large
of an equimolar solutions of 1M MCl and IM MOH, where M=Li,
K, leads to the alkali compounds. The alkali metal contents of these
als are very similar to those formed in the one-step hydrothermal
s described above, namely 0.42 Li, 0.33 Na and 0.26 K per formula
Although the acid is reported to have the IT structure with a=2.83A
67
c=7.55A, these compounds almost certainly have the same
58
ohedral structure as found for the hydrothermal compounds, but their
rystallinity precludes an effective structural analysis.
The acid leaching of layered manganates formed at elevated
ratures, such as of NaMn02, results in both ion exchange and partial
68
ion. The degree of reduction and ion-exchange is surprisingly
ely dependent on the acid strength, for example IM HCl leads to
1
Ho. 13Mnmo.JMn vo.s6•0.6H20 whereas O.OIM HCl leads to
1
Ho.27Mnmo.27Mn vo.73•0.6H20.
is of Battery Materials 95

ION EXCHANGE METHODES FOR LITHIUM


MANGANESE OXIDE SYNTHESIS
Many sodium and potassium transition metal oxides had been
sized using standard high temperature methods in the 1970s and early
69
° 7
. These included KxMnOz, NaxMnOz, KxC00z, NaxCoOz,
73
71 72

72
2 and NaxCr02. The complete phase diagrams of these systems are
ell understood. Much less was known about the corresponding lithium
unds, and indeed the corresponding LiMn02 compound cannot be
sized at elevated temperatures.
Although ion-exchange methods had been used extensively in the
74 76
sis of solid electrolytes, in particular of beta-alumina - and beta" a
much less effort had been made to prepare lithium based cathodes
on-exchange until the 1990s. As noted above, layered LiMn02 cannot
nthesized at elevated temperatures because of its thermodynamic
lity. Thus, a number of studies have been made on ion-exchanging the
77 78
m analogs to the lithium form. Groups at Bordeaux • and St.
79
ws showed simultaneously that layered NaMn02 could be readily
ged to the layered form of LiMn02• In these experiments, the sodium
und is immersed in hot lithium salts dissolved in water-alcohol
es for periods of hours to days. Care has to be taken that the
ature is not too high, otherwise the spinel structure can be formed.
doped material has also been synthesized by the same approach of
80
reparing the sodium material followed by ion-exchange; • 81 these
81
containing materials show much enhanced cycling even though they
ally convert to the spinel phase even for LiMn0.5Co0.502•
The above layered LiMn02 phases have the same rhombohedral
re as the lithium, and other alkali phases formed by the hydrothermal
38
position of LiMn04, and other permanganates.58 However, these
hermal compounds have a lower alkali content, for example Li0.5Mn02
their initially being hydrates. A comparison for the potassium
nese oxides is given in Figure 3.4, which also distinguishes between o
high temperature regimes. Higher alkali contents can be obtained by g
out the hydrothermal reactions under very high alkali hydroxide
trations. The range of synthesis reactions and redox/intercalation
ns for the layered manganates are shown schematically in Figure 3.5.
2 85
- ion exchanged the Na 0.44Mn02 tunnel structure 86 giving
inantly the lithium analog, which shows excellent cycling with no
of structure unlike the layered manganese dioxides. These results
d convincingly that a stable manganese dioxide can be formed. The
can be improved by replacing part of the manganese by titanium, but
e capability is negatively impacted.87• 88 Pure Li0.44Mn02 was prepared
exchange,89 and also showed excellent cycling.
Chapter3

Lithium iron oxides, such as the layered LiFe02, have also been
90
sized by ion exchange of the sodium compounds. The sodium
und a-NaFe02 was formed by hydrothermal treatment of FeOOH
large excess of NaOH (Na:Fe = 250) at 220°C; this sodium compound
hen partially converted to the lithium compound by ion exchange

rothermal
Mn02 KxMn02 •nH20

3 block
C
Mn02 Ko.2sMn02 KxMn02-8 Ko.7Mn02 KMn0 2

• •
tunnel 3 block
• •
C
Mn02 Ko.2sMn0 2 KxMn02-8 Ko.7Mn02 KMn0 2

• •
tunnel 3 block 2 block • •
3.4. Composition of the potassium manganese oxides, both hydrotherma158 and high
69
ture forms.

90
hydrothermal conditions, with 80% conversion in four hours at
. Reaction between NaFe02 and molten lithium halides results in
complete ion-exchange results in the formation of LiFe02, but with
ic lattice constant of 4.162 A indicating that the lithium and iron have
91
e disordered giving a NaCl lattice. Reducing the temperature by
a eutectic mixture of LiCl and LiN03 resulted in the formation of a
phase. An extensive study of the formation of lithium-iron-oxygen
92
failed to synthesize the layered LiFe02 compound. However,
93
e et al. reported the formation of "layered" LiMn0 2 which consisted
layered a-NaFe02 phase and a spinel phase; they synthesized this by
change of a-NaFe02 in a LiCl/KCl molten salt at 400°C.
The electrochemically active vanadium oxide nanotubes are also
sized by ion exchange from the initially formed alkylammonium
55 56
giving the sodium or manganese compound.
is of Battery Materials 97

STABILIZATION OF LAYERED LiMn02 AND


THE MIXED METAL OXIDES Li(Ni,Mn,Co)02
Although layered LiMn02 would be an ideal cathode material, it is
le relative to spinel formation and so the structure must be stabilized.
yered form and the spinel form have essentially the same structure as
ther with cubic close packing of the oxygen as discussed above for
2. The difference lies in the atomic positions the manganese ions
y. Thus, a means must be found to prevent the manganese from

Heat Aqueous
phous Solid Solution at 170°C

AxMn1 2 •y"H20
wherey" >1

.5. Schematic showing the synthesis, redox and intercalation reactions for Mn02 .
Chapter 3

ng. There are two distinct ways of doing this: geometric and electronic
zation of Mn02 layers. In the former, the structure is prevented from
to ccp, for example by placing pillars between the Mn02 sheets, or by
a none ccp structure, such as a two-block structure. Here, one is trying
feat thermodynamics by making the transformation difficult -
ally controlled reaction. In the latter, the manganese is made to be
cobalt-like by doping the lattice with a transition metal to the right of
such as nickel. Whichever way is chosen presents a synthetic
nge, as in many cases a metastable structure must be formed.
In the geometric approach, cations larger than lithium must be inserted
en the sheets. The potassium manganese oxides, described above,
the potassium ions are in trigonal prismatic sites thus breaking-up the
n ccp are readily formed at elevated temperatures or by hydrothermal
ques (see Figure 3.4). Though potassium enhances the cyclability,
ions eventually diffuse out of the lattice and it reverts to a spinel
re. Thus, immobile ions must be inserted into the lattice, between the
. Vanadium oxide pillars, probably V-0-V groups, were successfully
d using a combination of ion-exchange resins to form the starting
94
al followed by hydrothermal reaction; the structure is believed to be r
to that of the pillared Zn3(0H)2V207•2H20.95 This vanadium pillared
re was stable and did not convert to spinel even at 5 volts; however,
e characteristics were poor relative to LiMn02 itself. Leroux et al.96
sized a similar Ranceite based compound, which also was stable but
had poor rate capabilities.
The second geometric approach again aims to prevent the formation of
97
lattice, by forming a LiMn0 2 in which the oxygen layer stacking is
ger the three-block IABICAIBCIABI structure, but for example is the
ock IABICBIABI structure or even the hexagonal close-packing found
iS2 or in Co02• As none of these structures are stable for lithium at
emperatures, the sodium or potassium compounds must first be
sized by standard high temperature techniques; these may then be ion
ged to give the corresponding lithium compound as discussed above.
itial composition of the sodium or potassium compound may be varied
a wide range of stacking opportunities (see Figure 3.4); moreover, in
potassium compounds and in some of the sodium compounds the
cation is in trigonal prismatic coordination; as the lithium ion must be
hedral coordination, there will be sliding of the Mn02 layers leading
further stacking opportunities. All these structures are inherently
dynamically metastable, as the Mn02 sheets can slide relative to one
r and the manganese ions are quite mobile.
In the electronic stabilization approach, the goal is to make the
nese look electronically more like cobalt where the layer structure is
rmodynamically stable phase, for example by doping with nickel. 98
is of Battery Materials 99

, the mixed phase LiNi1.yMny02. can be readily synthesized for y:S


The composition LiNi0.5Ni0.502, which is isoelectronic with LiCo02,
the optimum electrochemical behavior in the mixed nickel-manganese
45
, and its electrochemical profile is very similar to that of LiNi02.
compounds were synthesized by firing the monoxides of nickel and
99
nese with LiOH•H20 after mechanical grinding. As discussed above,
Ni02-LiCo02 system is completely miscible, and 20% of the cobalt
44
substituted by manganese giving LiCo0. 8Mn0.202. The logical next
100 101
was the synthesis of the system, LiNh.y-zMnyCoz02. ' These
unds are best formed by mixing the metals in aqueous solution, from
the hydroxides are precipitated before being fired at between 700 and
C in air. Just as with most of the other layered compounds, the
sis conditions are important in determining the metal ordering and in
bsequent electrochemistry. Figure 3.6 shows the effect of firing
ature on the 102 electrochemical capacity of the composition,
Mno.4Coo.zOz.
The synthesis of the spinel LiMn204 will not be specifically discussed
t is readily synthesized by the solid state reaction of stoichiometric
103 104
ies of Li2C03 and Mn02• ' A number of anneals at around 800°C
essary to produce the optimum electrochemical material.

ADDITION OF CARBON CONDUCTIVE


DILUENTS POST SYNTHESIS AND IN-SITU:
LiFeP04
Many cathode materials, unlike the metallic conducting TiS2, must be
d with a conductive diluent for use as a cathode. The challenge in
ases is to obtain an intimate mixture and contact between the active
e, the conductive diluent, and the electrolyte as it is only at this three
contact that reaction can occur. Thus, it is invariably best to try and
he cathode material itself electronically conductive so that the reaction
cur at the two phase contact between cathode and electrolyte. This
can either be added post the electrode material synthesis or during the
synthesis. Carbon black has been used in the synthesis of a number of
mm where 1.t was 1-1'0un to s1. gm'f1i cant1y reduce t he
'd
ox1 es, ·105 106 d
ation in cycling cells; the vanadium oxide is described as being coated
he carbon with an 8 wt% carbon loading. Carbons have been
vely studied in the case of lithium iron phosphate where a reducing
here is necessary during the synthesis process to prevent the oxidation
ous to ferric. This material, LiFeP04, will be discussed in some detail
Chapter 3

s it exemplifies well a number of synthesis procedures, some of which


nd others that are less successful.
107
Lithium iron phosphate, LiFeP04, has been reported to be an
ent cathode but with high a resistivity that limits the capacity to
0.6 lithium. This material is normally synthesized by the high
rature heating of lithium, iron and phosphate materials for example
acetate, iron oxalate and ammonium phosphate. Such salts can be
ssolved making an aqueous solution that can be dehydrated forming a
th the reactants in atomic contact with one another. This material is
red under an inert gas, to prevent oxidation of ferrous to ferric, at

5
4
3
2
1
0
,-.....
.>._.., 4
3
00
ro
....... 2
........
0
> 1
0
4
3
2
1
0
0 50 100 150 200
Capacity (mAh/g)
.6. Effect of synthesis firing temperature on the electrochemical capacity of
102
n0.4Co0.202.
s of Battery Materials 101

n 600 and 900°C forming LiFeP04. Such material has been well
erized,108 and has lattice parameters of a=10.329 A, b=6.007 A,
1 A and volume= 291.0 N. LiFeP04 can also 109 110been synthesized by a
of other techniques, including hydrothermal ' and microwave.
In the hydrothermal process, lithium acetate, ferrous oxalate and
horic acid dissolved in water are heated at around l20°C for up to 5
110 The reaction was found to be complete in much less than an hour. It
so be carried out under microwave heating. However, X-ray analysis
d that there is some iron on 111the lithium sites which restricts the rate of
insertion and removal, making the hydrothermal approach
able for LiFeP04 synthesis. Such disordering can be recognized from
tice parameters, a=10.403 A, b=6.023 A, c=4.726 A and volume =
N, which are significantly larger than the ordered material. A high
ature anneal appears to be necessary to cause the ordering of 112 the
and iron atoms. A recent report on the microwave processing of
04 would seem to have the same problem, as indicated by the rather
ectrochemical capacity even at elevated temperatures.
The original publication on the LiFeP04 electrode suggested that the
resistivity of the material was the cause of the rather low
chemical capacity, around 0.6 Li!Fe. Several efforts were directed at
ing the effective electronic conductivity, including modifying the
sis process so that a conductive coating is formed at the time of
sis - in-situ coating. Such approaches have been used in the case of
113 114
um oxides. Ravet et al. • proposed firing the initial reactants with
aceous materials such as sugar, so as to form a carbon coating thus
ing the overall conductivity of the composite so formed. These
sites allowed almost complete utilization of the lithium. Even more
sive results were obtained when a carbon gel was fired with the
leading to complete utilization of the LiFeP04 at 5 mg/cm2
115
ts,
116
gs. Masquelier showed the effectiveness of ball-milling carbon with
04 in giving complete capacity at elevated temperatures. A
rative study of the effect of synthesis/coating procedure, including in-
r bon ge I, sugar and aqueous ge1 versus post synthes1.s coatm. g
117

usm· g e range of techniques suggested that the coating procedure


is not
118
larly important at high cathode loadings, 20 - 70 mg/cm2.
er, the addition of carbon at high levels is very deleterious
119 to the
low volumetric energy density of the LiFeP04 cell. What may be
critical as the coating process, is the nature of the material formed,
ng its particle size and absence of ferric material and unlithiated
ate so as to enhance the lithium ion diffusivity.
An alternative to the in-situ coating of the lithium iron phosphate
the synthesis of the cathode material is to actually modify the intrinsic
nic conductivity of the phosphate itself by doping the lattice as
Chapter 3

bed above for the layered manganese oxides. ° Chiang et al. have
6 120

the lattice with for example 1 wt% niobium and showed that the
9
nce is reduced from around 10 ohm-em in very pure LiFeP04 to
2
10 ohm-em. The very low doping levels have a surprisingly large
t; the material is black, but there are apparently some carbonaceous
2
es present. The electrochemical capacity is around 80% at 0.4 mA/cm
2
2.5 mg/cm loading, significantly lower than that from the carbon gel
115
gs. The resistance of regular battery grade LiFeP04 formed from
5 6 118
t grade chemicals is around 10 -10 ohm-em, not significantly
60
nt than that of undoped manganese oxide. The impact of synthesis
ure on the lithium ion conductivity is still not known and this might
as critical if not more critical than the electronic conductivity.

SYNTHESIS OF ANODE MATERIALS


Lithium when used in the pure state is very prone to dendrite
ion on electrolytic deposition, thus metal alloys have been
gated for more than 30 years in organic electrolytes. Dey first
bed 121 the electrochemical formation in organic electrolytes of lithium
with a wide range of metals, including aluminum and tin. In these
ments, the cell was simply short-circuited externally or a 1 kohm
al resistor was used so that the voltage profile with time could be
ed. The compounds formed were shown to be same as those formed h
temperature metallurgical reaction. These intermetallic compounds
rmally very brittle, so it is not easy to form an electrode out of them;
xxon in its LiAl/TiS2 cells constructed the alloy anode in-situ by
g a sheet of lithium on top of the aluminum on cell construction. No
n occurs until the electrolyte solution is added to the cell, immediately
o cell closure. The formation and cycling behavior of the lithium
um alloys synthesized both electrochemically and thermally have
122 123
tudied. Wang et al. synthesized at high temperatures the lithium
of tin, antimony and bismuth in both a porous and dense state by
g the components together in molybdenum crucibles; they used these
als to determine the lithium diffusion coefficients and phase equilibria
nic electrolyte based cells.
Herold 124 first formed the alkali metal intercalation compounds of
te, but the electrochemical formation of the lithium compound LiC 6
mplicated by the co-intercalation of the electrolyte solvent. 125 126
• • Use
solid electrolyte, polyethylene oxide, allowed the formation at 80°C of
vent free sodium graphite compound NaC64; higher sodium content
127
als were not formed. This shows the importance of choice of solvent
synthetic process, or in the battery, where it may participate in the
is of Battery Materials 103

n even if only as a solvating specie. This can be equally true for the
e as for the anode. Thus, when propylene carbonate was used as the
lyte solvent in the LiffiS2 cell, if a trace of water was present then
ene carbonate was co-intercalated with the lithium expanding the
hree fold. The ether dioxolane was found to be a particularly ve
electrolyte solvent for lithium batteries, not being co-intercalated eing
128 129
very good for lithium electroplating. " Such solvents were
ed for use with the lithium-graphite anode. °13
Carbon based anodes
131
w used in essentially all commercially lithium-ion batteries, and
l to their success is choice of solvent with ethylene carbonate being
successful. Hard carbons rather than pure graphite are preferred for
132
cycle life and capacity. The batteries are constructed in the
rged state, and the lithium is electro-intercalated into the graphite on
st charge. Thus, the cathode material provides all the lithium for the
which means that excess anode cells are not constructed. Thus, any
side-reactions have an immediate negative impact on cell capacity.
133
et al. showed that the graphite surface is coated with a protective
n the first synthesis of C6Li which irreversibly consumes some of the
. This film is stable and so need not be reconstructed on each
chemical cycle but it does permanently reduce the capacity of the
. Hence, there is much interest in synthesizing other potential anode
als that have a higher capacity, and safer operation than graphite based
unds. The outstanding stability and rechargeability of graphite after
t cycle will be hard to surpass.

MECHANOCHEMISTRY AND MECHANICAL


GRINDING
Much emphasis has therefore been placed on investigating other
materials that might store lithium by a simple reaction around room
ature. A novel approach to the synthesis of new materials developed
inantly in Russia at the Institute for Solid State Chemistry and
134 135
nochemistry ' is that of mechanochemistry or mechanical
g. In this approach physico-chemical transformations and chemical
ns of solids are induced by mechanical action. Although the grinding
cally performed at room temperature, the actual temperature at the
e contact is probably substantial. Although most scientists were
al initially about mechanochemistry the technique has now gained
136 137
ete credibility. ' A number of anode materials have been
sized by this technique, and carbon has been effectively coated onto
116
04• The precursor
138
for LiFeP04 has also been formed using
nical grinding, which allowed the formation of LiFeP0 4 even at
Chapter 3

; the quality of the material in electrochemical cells has not been


bed.
A number of anode materials have been synthesized by
nochemical reactions. Many intermetallic compounds have been
sed for anode use using different concepts, one where the structure of
6ermetallic
5• 139 140is at least in part retained during reaction with lithium such
Sn ' A second approach is where the structure is destroyed but
omponent acts as a mechanical buffer and the other reacts with the
m, an example might be Sn2Mn. A third option is where a composite
e of intermetallics is used.
The phase Cu6Sn5 phase is very well characterized, being formed at
erface when copper is soldered using tin based materials. It has been
igated as a potential lithium anode, and has been synthesized in a
of ways. In a mechanochemical process, powders of tin and copper
and-grinding were mixed and about 3-4 wt % of carbon was added as
lubricant prior to milling for 20 hours; purity of phase was shown by
140
analysis. On cycling lithium is inserted into this compound forming
nCu like phase. Cu6Sn5 has also been prepared by reaction of copper
141
under argon at 400°C. An alternative synthesis approach has been
142
d by Tamura et al. They electrodeposited tin onto a copper foil,
nnealed the foil at 200°C for 24 hours in vacuum to form Cu 6Sn5. The
chemical behavior of some of these tin containing materials is
143
red in Figure 3.7, where it can be seen that the pure tin foil retains
142
me capacity as the annealed Cu 6Sn5 phase for the first ten cycles.

800 Tin foil 0.8 mA/cm


2

OJ)

600

-400
u
200

10
Cycle
.7. The electrochemical capacity of several tin based anodes, synthesized by different
es.
is of Battery Materials 105
144
The intermetallic InSb has also been prepared by ballmilling. In this
dium and antimony metals in a 1:1 ratio were ballmilled in air at room
ature for 20 hours; after which the resulting powder was annealed
flowing argon at 400°C for 12 hours. This material had a capacity of
220 mAh/g for the 2nd to 20th cycle.
Mechanical alloying is particularly amenable to producing
145 146
etallic alloys or mixtures of them. Mao et al. ' prepared
sites of SnFe2 and SnFe3C. Powders of tin, iron and carbon were
in hardened steel vials together with hardened steel balls; these were
in an argon environment, and then shaken for 20 hours. X-ray
tion showed that the resulting grain size was about 10 nm. In this case
e SnFe2 phase is electrochemically active, the carbide phase being the
matrix; the cell capacity which exceeds 1500 mAh/cc (around 200
) for 24% SnFe2 can be enhanced by increasing the ratio of active
nent but it is at the expense of capacity retention. The same
147
nical alloying process has also been used to reduce the particle size
e2 formed by high temperature processes. A recent review of tin-based
148
etallics details some of the other synthetic processes used.

NOWLEDGEMENTS

This work was supported in part by the National Science Foundation


US Department of Energy.

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pter 4

ANODES AND COMPOSITE ANODES:


AN OVERVIEW

L. F. Nazar and 0. Crosnier

Department of Chemistry, University of Waterloo,


Waterloo, Ontario, Canada N2L 3Gl

INTRODUCTION: LITHIUM METAL AND


CARBON-BASED MATERIALS

The past years have witnessed significant improvements in the nature


pability of energy storage systems. A combination of fundamental and
logically driven studies were responsible for these advances, which
een reviewed in Chapter 1. Motivation for the advancement has been
d by the ever-increasing demands that a multitude of applications are
g on the energy storage battery. In addition to the ever-popular needs
rtable energy electronics, future demands lie in rechargeable batteries
brid electric vehicles, miniaturized electronics; space exploration,
1 23
rupted power supplies, and medical devices. • • These various
ations differ in their requirements of the energy storage cell: some
g high power, and others needing high capacity. All demand safety,
er, and most require excellent stability of the cell over long-term usage. l
cells are still many years away from meeting the needs in most of
areas, lithium-ion rechargeable batteries offer the only technological
n at present, and the best long-term solution for the foreseeable future
ny of the areas. Developments in the positive electrode arena have
ed materials capable of gravimetric energy densities in the regime of
Ahlg; therefore anode materials are sought to match these high-capacity
es. This chapter is devoted to a review of the new technologies in the
at may address these issues.
nd Composite Anodes: An Overview 113

Issue of Safety: a Brief History

he problems of the lithium battery, and inception of the lithium-ion


as an alternative arose from well-known problems with the anode. In
ade before 1990, lithium batteries were introduced as novel, high
density cells whose promise lay in the low atomic weight of lithium
nd the high degree of reversibility of the systems. The first materials to
commercialization, TiS2 4, and MoS2,5 were used as positive
es versus lithium foil in several commercial products. These layered
n metal dichalcogenides benefited from relatively fast lithium ion
n, along with appealing cell voltages vs. Li (about 1.8V). The use of
metal as anode material in rechargeable solution-electrolyte batteries
carded in the late 1980's, however, after a few well-documented
ular failures of the Li/MoS2 cells in operating devices. The problem is
derstood to arise from reaction of the solution electrolyte with the
lithium surface. The electrode surface, passivated by the formation
um alkyl carbonates, sustains repeated non-epitaxial deposition of
after each cycle as a result of the complex surface chemistry. This in
sults in continuously increasing electrode surface area, and more e
surface reactions. The insulating, complex deposits that build up on
face of the electrode lead to the growth of uneven "fingers" or
s. Ultimately cell failure occurs when the dendrites reach the positive
e surface and/or the insulating layer causes a large rise in cell
nce, leading to an internal short-circuit.
The "rocking-chair" battery, pioneered in the mid 80's, solved the
problem by replacing the metallic lithium anode with a lithium
n compound. These "rocking-chair" or "shuttle-cock" batteries
ed on the principle of simultaneous lithium ion de-insertion and
n in both electrodes. Lithium ions shuttle back and forth across the
yte, in concert with electron transport through the external circuit.
ese cells contained no metallic lithium, they were much safer than the
battery. The choice of the anode is based on properties that include
ertion kinetics, and a redox potential vs. Li which is less than that of
hode to provide a sufficiently large cell voltage. In the earliest
ion, the anode employed was a low potential lithiated insertion
nd such as LixW02.6 Lower density carbon-based insertion materials
the oxide in batteries commercialized by Sony Energytech in 1991,7
ise to a series of patents and a product called a "lithium-ion" battery. l
capacities and cell voltages were obtained by marrying the
ceous material with a lithium-containing high-voltage cathode that
ed as the lithium reservoir, i.e., LiCo02• These cells have since
hed dominance in the lithium-ion battery market. Much effort has been
d in the last decade to improve these batteries, with research devoted
Chapter4

8 9 0 11 12
hree components of the cell. ' ,t , ' These have resulted in significant
vements in the performance (increase in energy density and rate
lity by a factor of two) and cost (more than a factor of two). Aspects of
sitive electrode are discussed in Part III and the electrolyte in Part IV of
ook. From the anode point of view, these directions have concentrated e
areas: improvement of carbonaceous materials; utilization of metallic m
in combination with stable electrolytes; and a search for new als.
The most suitable direction for new anode materials is not
ndent of the other components in the cell - for example, successful
mentation of a 5V cathode and electrolyte system would allow for
s that have working potentials above 1 V to be utilized. Similarly,
ons at improving the stability of metallic lithium anodes are directed
ds implementation of lower voltage cathodes that have the advantage of
lyte stability.

Carbonaceous Materials

Most of the improvements in anodes actually implemented over the last


have involved carbonaceous materials, in concert with LiCo02 or
layered oxides. This is partly based on the fact that graphite and
tic carbons, well known as intercalation compounds, have been
13
ghly studied in the past 30 years. The mechanism of lithium
lation that gives rise to a maximum uptake corresponding to LiC6 is
nderstood. The reasons that lie behind the commercial success of
-based negative electrodes include the relatively low inherent cost of
, its excellent reversibility for lithium insertion, and its formation of a
tive surface film with many electrolyte solutions. When a graphite
de is polarized to negative potentials during initial Li intercalation in an
ne carbonate based solution, the organic solvent reductively
14 15
poses on the graphite surface to form a stable surface film. • This
16
which is often called the solid electrolyte interface (SEI) effectively
ates the graphite surface and prevents further co-interaction and
position of solvent molecules, allowing only Li ion migration.17 As
ne carbonate is quite viscous, it is often used in combination with other
arbonate solvents such as dimethyl carbonate.
One form of carbon is the soft or poorly ordered carbons ("petroleum
products). For soft carbons heat-treated below graphitization
atures, turbostratic disordered carbons are obtained. Lithium cannot be
accommodated in the interlamellar graphene galleries and low
ties are observed. ' ' °
18 19 2
For graphitized soft carbons, the level of
er has a direct effect on the mechanism of the reaction with lithium.
isplay complex behavior due to surface effects, internal porosity and
nd Composite Anodes: An Overview 115

19 21
g surface bonds. ' Capacities well above the theoretical limit of 372
are observed, but are inevitably associated with a large hysteresis.
pecific new forms of carbon which have replaced petroleum coke and
rise to high capacity/rate capability anodes include MCMB
arbon microbeads or spherical graphite), MCF (microcarbon fiber),
ith natural and synthetic graphite flakes. MCMB's in particular, are
utilized. They exhibit large capacities after heat treatments at low
22 23 24
tures, as well as after graphitization at higher temperatures. • •
materials are derived from petroleum industry byproducts or coal
s, but are expensive owing to low yields. They, along with other
ceous and graphitic anodes are discussed in detail in Chapters Sand 6.

Looking to the Future


espite the advances made in carbons, it has been recognized for some
ow that new anode materials are needed. First, graphitic carbons can
rom solvent co-intercalation resulting in large interlayer expansions
subsequent degradation of the graphite structure. This, however, can
ressed by the adroit choice of solvent (i.e., alkyl carbonate mixture)
25
additives. More importantly, carbons suffer from a fundamental
on in gravimetric capacity, and particularly in volumetric capacity
ical limit of 1000 mAh/cc). Developments in cathode materials that
fectively doubled the capacity within the last few years demand an
o match. An increase in the operating voltage above the current values
bonaceous materials is highly desirable to inhibit lithium metal
on that can occur at fast rates. To date, no new non-carbon containing
have been commercialized however, as they currently are not
tive with carbon in terms of cost or stability on cycling.
onetheless, a large number of alternative possibilities for negative
es have been recently reported in the literature that may lead to new
ns in meeting the anode challenge. One important area is in the
ment of composite materials. It is apparent that promising
ristics can result from development of nanostructured domains within
s during the initial cycles of the cell. The partial disorder inherent to
aterials can have a substantial impact, affecting the kinetics and/or
ynamics of the materials in highly beneficial ways. In fact, the
ed development of materials over the past few years suggests that one
ent alone will not suffice. These composites fall into two categories:
eated in-situ as mentioned above, or those deliberately constructed
arious synthesis-by-design approaches. What follows is a brief w
of some developments that highlights key points in anode design n
these concepts.
Chapter 4

COMPOUNDS AND COMPOSITES OF Sn, Sb AND


AI
Amongst the first materials to be examined as electrodes for Li uptake
potential, well before carbon gained prominence, were other members
oup IV, and the neighboring Group III and Group V elements. These
e AI, Si, Ge, Sn, Pb, Sb and Bi, which all form alloys with Li at
ely low voltages vs. Li. Much of the early work concentrated on alloys
AI (Li9Al4 being the end member, although LiAl is observed in
26
e), and Group IV elements which display stoichiometries as high as
/M. Studies on the Li-Sn system, carried out at elevated temperatures
27
ggins and others, '28 show that seven line phases exist within the phase
m: LizSn5, LiSn, LhSn3, Li5Snz, Li 13Sns, Li7Snz and LizzSns. Based on
nown structures, Courtney et al. recently were able to calculate the
tical electrochemical voltage profile in the lithium-tin system using a
29
o-potential plane-wave approach. Their results were in good
30
ment with experiment. Silicon, being the lightest member of Group IV
from carbon, shows the highest gravimetric capacities (up to 4000
for the end member Liz 1Si5) although achieving this at ambient
rature is difficult. 31 A detailed re-examination of the crystal structure of
d members of the Li/Group IV compounds has shown, in fact, that
gh the end member composition for Si is correct, the precise
ometry for Ge, Sn and Pb is Li339Ge80, Li341Sn80, and Li340Pb80. The
composition can therefore be approximated as Li 17M4, not LizzM5. 32
Regardless of the element, the formation of alloys within Groups III, IV
is associated with a large volume expansion that results in pulverization
electrode material and loss of electrical contact between the material
on prolonged cycling. The degree of volume expansion depends on the
nt, as shown in Table 4.1. In all cases the resulting rapid capacity fade
s their practical use as electrodes. To overcome this problem, efforts
urned to the encapsulation of the main group metal center in a matrix
is conducive to u+ transport (and/or ideally, to electron transport) in
n to possessing mechanical flexibility; and also to the formation of
systems based on intermetallics.
nd Composite Anodes: An Overview 117

. Capacities and volume changes of different elements.

material c AI Si Sn Bi

d phase LiC6 Li9Al4 Li21Si5 Li 17Sn4 Li3Bi

ical specific
372 2235 4010 959 385
y (Ah/kg)

ical volumetric
y (Ah/1) 833 6035 9340 7000 3773

changes(%) 12 238 297 257 115

Intermetallic Composites and Binary Phases


Comprised of Sn, Sb and AI
ultiphase electrode materials composed of MM'compounds, in which
ne component forms an alloy with lithium, exhibit better cycling
ance than a single phase host. This has been attributed to the
on of an "inactive" M' matrix that surrounds the "active alloying M
nd helps maintain the integrity of the microstructure of the composite
e during the (de-)alloying process. Much of this work has been
out using a transition metal as the inactive component and a main
metal as the active alloying centre: these are termed "intermetallics"
gh strictly, the name applies to Al compounds and other true metals.
ncept was based on the first "matrix" approach involving main group
xides, in which the LhO that is formed on reduction acts as the
matrix component. Another approach is to use intermetallics MM'
w strong structural relationships to their lithiated products.
hese are discussed in the following sections.

Tin Oxide Composites

TCO, a new anode material comprised of an amorphous, multi


composite oxide glass (SnxAlyBzPpOn), containing "active" Snn
inspired much interest in the area of main-group metal oxide
33
s. Studies on related compounds such as SnO, Sn02, and Sn2BP06
hed that the initial Li uptake results in an irreversible reaction to form
Chapter4

nd metallic Sn. The subsequent Li uptake that results in the reversible


y is based on alloying of the Li with the Sn centres, to ultimately form n
34 35
nanoparticles embedded in the LhO matrix. ' A similar mechanism
ought to be responsible for Li uptake in the tin-oxide composite glasses.
ed studies which followed, based on a variety of spectroscopic and
tion methods, revealed that the "Li-Sn" alloy nanoparticles are highly
38
36 37 The proximity of oxygen in
ered at the limit of deep discharge. '
'
trix (either on the bulk of the particles or within them) may give rise to
sorder - and in any case, certainly affects the thermodynamics of the
.
The reactions occurring within the tin composite glasses take place in a
miting regime, where the thermodynamics are strongly affected by the
36
urface energy of the particles." The reaction between Li and Sn, which
crystalline Li4.4Sn under high-temperature conditions can be much
omplex on a nanoscopic level. First, the kinetics of the system limit the
ion of ordered "bulk" phases at ambient temperature, even in tin oxide
but especially in the dilute tin-based glasses. Secondly, the tin clusters
d on Li uptake are in close proximity with both lithium and oxygen as a
of these particles having a very high surface area: volume ratio. We
suggested that partial oxygen incorporation within the bulk (as an
itial element) may be responsible for some of the disorder observed in
ray diffraction patterns of the fully discharged material, as well as
ally low frequency 7Li NMR shifts indicative of Li in the proximity of
36
duced Sn and oxygen. Oxygen is present as an interstitial component
n group compounds such as Zr5Sn30 and La5Sn30 and is implicated in
39
e of intermetallics. The possible interstitial, and surface oxygen can
te the reversibility of Li uptake by the Sn. The surface energy of these
es allows the "back-reaction" of lithium with oxygen to take place at a
potential than predicted from simple considerations that exclude surface
contributions.
37
This has been corroborated by Mossbauer studies, and EXAFS
36
, which give evidence of oxygen incorporation/disorder at low
al. The availability of matrix bound oxygen to participate (surface or
itial) will be determined by the surface energy of the electrochemically
particles, hence the smaller the aggregates, the more reactive they will

Other tin oxide composites (and negative electrodes in general) are


40
arized in a comprehensive review article by Tirado et al.
nd Composite Anodes: An Overview 119

Inactive/Active Composites. Reduction-Decomposition/


Alloying

1. Tin compounds

order to reduce the irreversible capacity observed in the case of


it was concluded that oxygen bonded to the electrochemically active
41
should be avoided. This approach, first suggested by Besenhard and
42
s , has been applied to several systems based on tin intermetallics,
43 44
where M is an electrochemically inactive transition metal (M=Fe '
47 44 44
Mn • Co, ). The fundamental concept is simple. Li uptake/reduction
dissociation of the starting material into an active component that will
ith lithium to form Li-M alloys, and an inactive part, as described
ion 4.1:
(4.1)

he role of M is mainly to provide a matrix that will absorb the massive


changes that occur within the electrode upon the lithiation
ion)/delithiation (contraction) processes. It therefore maintains the
ical integrity between the particles and also with the current collector.
contact is a major source of capacity fade. The role of the inactive
also to improve the electronic conductivity of the composite electrode
fectively than the insulating LizO-based matrix formed in the case of
However, this is at the expense of inhibiting lithium transport, which
ke place upon grain boundaries. Upon charge (lithium removal), two
es can occur based on the degree of back-reaction (see Figure 4.1):
he delithiation of the LixSn alloys leads to metallic tin dispersed in a
ork composed of theM atoms (equation 4.2); or the starting material is
d (according to equation 4.3):

LixSn + MSn + M +xLi+ +xe (4.2)


LixSn + MM-Sn + xLi+ +x e- (4.3)

he first example of the application of this concept was in iron-tin


43
nds where iron forms the inactive matrix surrounding the tin atoms.
57
s of Sn2Fe prepared by high energy ball-milling were shown by Fe
uer studies to decompose upon lithiation to nanosized iron and
tin alloys, as described in Figure 4.1. Upon charge (delithiation), the
s aid lithium removal by reacting with Sn to re-form small grains of
However, due to the large volume expansion during reaction with
some tin regions gradually lose connection, leading to an incomplete
Chapter4

4.1. Dissociation reaction of lithium with tin-based intermetallic compounds M-Sn.

ation of the starting material. Such compounds exhibit high specific


ties of 800 mAhlg and 650 mAh/g during the first discharge and first
, respectively, but capacity fading on long-term cycling. As noted for
35
ide-based materials, an improved cycle life (associated with lower
ties) of such electrodes can be obtained by reducing the voltage window
en 0 and 0.55V vs. Lt/Li.
The effects of increasing the Fe:Sn ratio were subsequently investigated
same group. They found that increasing the Fe:Sn ratio from SnFe to
5 also resulted in dissociation. However, owing to the higher iron
t, the Fe atoms form an impenetrable "skin" on the surface of the grains
hibits complete reaction of lithium with the tin and does not allow
ete dissociation of the Sn-Fe compound. The more iron in the alloy, the
active is the material towards lithium.
A compromise between the higher reactivity/greater fading of the Sn
aterials and lower reactivity/lesser fading of the iron-rich materials was
by generating composites of Sn2Fe (active component) and SnFe3C
ve component). These materials, prepared by mechanical alloying,
better cycling stability than the pure Sn2Fe compound, and higher
ties than SnFe3C. Thus the initial goal of tin atoms embedded in an
chemically inactive iron matrix was not completely achieved, but the
obtained with the active/inactive composite electrode on the Fe/Sn/C
suggest that this concept is promising. Similar results were obtained
47
same group in the Sn/Mn/C system. Again, increasing the ratio of the
ve' atoms in the alloys prevents the reaction of lithium with tin and
the capacity of these materials.
Development of nanostructured SnMn 3C led to the concept of grain
ary storage of lithium. SnMn 3C has a perovskite structure that is
e toward lithium. However, nanosized SnMn 3C particles (12 nm)
sized by high energy ball milling provide a 'host' for the reversible
on of lithium that can "intercalate" in the spaces between the grains.
thors showed that lithium can reversibly react at and within the grain
nd Composite Anodes: An Overview 121

ries, delivering 150 mAhlg with a good cycling stability. The


ck is the limited capacity obtainable by this approach. The concept,
r, may be also applicable to nanostructured anode materials as a
of additional Li capacity.
anocrystalline composite Mo 1_xSnx has been prepared as a thin film by
ring method. The films show solid solution behavior below x=0.45;
xistence of the above phase and nanocrystalline tin when x>0.45; and
of composition-modulated Mo1_xSnx and nanocrystalline tin when the
48
tin content is >40%. Relatively stable electrochemical cycling is
49
d with promising electrochemical properties.

.2. Antimonides

ater work continued with antimony-based intermetallic compounds.


to tin, antimony itself exhibits high capacities associated with alloying
50
s to form LhSb (theoretical capacity of 660 mAhlg). It also exhibits
e expansion/contraction problems on Li cycling (see Table 4.1 above),
refore poor capacity retention is improved by the use of an inactive
provided by a transition metal element to improve the cyclability.
most cases, the reaction of the MxSb compounds can be summarized
ariation of equation 4.1 above: namely simple dissociation of the
material into M and Sb to form LhSb alloys and metal particles. The
tion reaction seems independent of the stoichiometry or structure of
ting phase, as it is observed for all transition metal antimonides.
for example, crystallizes in the skutterudite structure, comprised of
hared CoSb6 octahedra (similar to the Re03 structure except with f
51
the octahedra; see Figure 4.2). During the first discharge the uptake
ium takes place at ca. 500 mV vs. Li+/Li, corresponding to a specific
52 53
of 800 mAhlg. ' The process leads to destruction of the crystalline
e and formation of Li3Sb alloys dispersed in a Co matrix, as confirmed
54
b Mossbauer spectroscopy. On charge, a large irreversibility of
hlg is partially caused by the formation of a SEI layer. Upon
ent cycles, the lithium reactions occur at higher voltages (-800 mV
2 V vs. Li+/Li for discharge and charge processes respectively) and are
to the formation/dissociation of lithium antimony alloys. Despite the
e of highly dispersed cobalt clusters within the electrode, the capacity
fades to 200 mAhlg after 20 cycles.
44
Similar dissociation behavior is also observed for MSb2 (M = Ti, V)
stallize in the 8-AhCu structure, and MSb2 (M = C , Fe ) that
5 56
57 58
ze in a marcasite-type structure. • The latter is comprised of comer
e joined MSb6 octahedra that form small channels (see Figure 4.2).
Chapter4

.2. CoP 3 skutterudite structure with comer-joined CoP6 octahedra (left) and FeP2
structure with edge-joined FeP6 octahedra (right).

imilar to CoSb3, the first reaction step (which takes place at 0.6 V and
vs. Li+/Li for CrSb2 and FeSb2 respectively), leads to a complete
ization of the structure and the formation of LhSb alloys as shown by
tterns (Figure 4.3).

3500

3000

2500

2000
c::1"' 1500
0
(.)
1000

500

0
50 60 70
10 20 30 40
20( 0
)

.3. XRD patterns of FeSbz (a): reference, (b): pnstme material synthesized by
g, (c): after 5 cycles stopped at the end of discharge and (d): after 5 cycles stopped at
charge. (*) and ( )represent Li3Sb and Sb peaks respectively.
nd Composite Anodes: An Overview 123

ore stable cycling behavior was noted for FeSb2 than in CoSb3,
r as a capacity of 300 mAhlg can still be obtained after 30 cycles at a
e.56
eversing (increasing) the M:Sb ratio provides similar outcomes,
ified by Li uptake in Mn 2Sb which also gives simple dissociation of
59
ting material into Mn and Sb to form LhSb alloys (equation 4.1).
n be contrasted with the behavior of copper antimonides, such as the
tural Cu2Sb (see below), where the apparent limited region of Li-Sn
Cu solubility initially leads to ternary phases.

Intermetallic "Insertion" Hosts: Reduction/Insertion- Alloying

1. Cu-Sn and Cu-Sb Intermetallics

n contrast to the active/inactive concept, the copper/tin system was


proposed by Thackeray et al. as a potential intermetallic Li-insertion
60 61
., a host capable of topotactic Li intercalation. ' Such a compound
principle, exhibit high specific and volumetric capacities without the
ck of the massive volume expansion problems consecutive to an alloy
on. The mechanism of lithium insertion into TJ-Cu6Sn5, is now thought
r in two distinct steps which are a function of the voltage; in the first
u6Sn5 initially undergoes a phase transition involving Li insertion to
known LhCuSn-type structure. This transition is observed at 400 mV
i, corresponding to an idealized reaction that can be written as:

n fact, distinction between LhCuSn and "Liz.17CuSn0.83" is not made,


wo are probably isostructural. This process has been confirmed by in
62
RD studies, recent theoretical calculations using the FP-LAPW
63 119 64
s and by Sn Mossbauer spectroscopy. To explain the insertion
ism, Figure 4.4a describes the NiAs-type hexagonal structure of the
material TJ-Cu6Sn5 in which layers of tin atoms are sandwiched
sheets of copper atoms. During the lithiation, half of the tin atoms
laced to form columns of tin, while the copper and the other half of tin
emain spatially intact, creating small hexagonal channels in which
can be inserted to form Li2CuSn (Figure 4.4b).
his "topotactic" reaction is associated with a 61 % volume change.
he voltage is curtailed at 0 V during discharge, the decomposition of
ary LhCuSn phase occurs according to the equation:
Chapter4

b.

e• Copper 0 • Tin e• Lithium

4.4. Phase transformation of'YJ-Cu 6Sn5 during lithiation (a) to form "Li2CuSn" (b).

At deep discharge, LixSn alloys (i.e., Li4.4Sn) are ultimately formed, as


62
by in-situ XRD studies. The specific capacity corresponds to
Ahlg for a fully lithiated electrode. As observed for the Fe/Sn/C system,
partial reformation of the starting material occurs, and both copper
on and a large volume expansion lead to a poor cycling life of such
des.
The behavior of copper antimonide, Cu2Sb, is related to the above
s. Thackeray et al. demonstrated that it reacts to form LizCuSb
uctural with LizCuSn) before transforming to Li3Sb.65 The transition of
to LizCuSb takes place with extrusion of 50% of the Cu atoms, and a
structural change to yield the zinc blende phase of CuSb, and then
Sb. Further lithiation results in a Liz+xCuJ_xSb solid solution that
ates in the end member, LhSb at x=l. The reaction is highly reversible,
ing a capacity of 290 mAh/g that is 90% of the theoretical. The
ce of the extruded copper particles is thought to impart good electronic
ctivity to the electrode. Most important in this work, and that of InSb
Sb that follow, is the principle of the reversible lithium insertion/metal
ement reactions within a face-centered cubic (fcc) Sb host structure.
ore in the case of Cu2Sb, the absence of significant internal
ement of the fcc Sb during the transformation aids the reversibility.
hium and copper, of comparable sizes, can be considered to move in
t of the lattice with little disruption to the framework. This interesting
nd Composite Anodes: An Overview 125

66
has been recently reviewed, and details are given elsewhere.

2. IhrSb (Where IM is an lntermetallic)

he same principle of strong structural relationships between parent and


compounds governs Li insertion into both InSb and SnSb to some as
66
noted by Thackeray et al. Of note is that both components in ases
can partake in lithium alloying reactions, but they occur ially.
he zinc blende structure of InSb has a favourable three-dimensional
ial space for lithium diffusion, and two crystallographic sites for Li
n, as described by the first authors who reported its uptake of
67
' The reaction of Li with InSb occurs in several steps which can be
classified as 1) a reaction of Li to form Liyin 1.ySb, accompanied by
n of In from the framework, and 2) a second step that involves
of the extruded In with Li to form Lixin. The precise details of the
hemical reaction during the initial stages are subject to controversy,
68
r. The original authors have concluded, on the basis of in-situ XRD
69
AFS studies, that Li is inserted into, and In extruded from, a fixed
framework to give Lix+yin 1.ySb (0=x<2, O<y<l). They propose that,
is inserted into the interstitial sites of the zinc blende structure to give
. Second, further reaction of lithium induces extrusion of In and
ment by Li to give Lix+y+zin 1.ySb + y In. The extent to which Li is
before In extrusion occurs is not yet accurately known, and is the
of the controversy. EXAFS measurements do not support early In
n, but other author's detailed XRD measurements suggest that In
70
n occurs at x=0.27. Irrespective of the details, both agree that
ly LhSb is formed at the end of the first stage, and that the last step
s formation of Lixin.
he good performance of the electrode (300 mAhlg after 25 cycles) has
ributed in part to the reversible lithium insertion/indium extrusion n
68
the fcc Sb host, as described above for the Cu-Sn compounds; i.e.
uctural similarity of InSb and Li3Sb. The small increase in
ographic volume of the electrode after full discharge (taking into
the extruded indium) is only 46.5%, suggesting that appropriate
ring of the materials might yield a system with good stability.
nately the extensive crystal growth of the extruded indium and
on of Lixln alloys compromises the reversibility of the electrochemical
Li3Sb transformation.
he reaction of Li with SnSb can be described in similar terms to that
g InSb. The reaction can be summarized as Li insertion into, and tin
ment from, an fcc Sb host structure.66 LhSb is formed after the first
Chapter4

nd the second step involves reaction of the extruded tin with Lito form
71 119 7
alloys. A recent study using Sn Mossbauer combined with Li MAS
spectroscopy confirmed the dissociation of the starting material during
rst discharge and also demonstrated that a partial recovery of the
ure occurs upon charge for SnSb single phase electrodes.The good
lity of this system can be attributed to the fact that 1) both components
equentially: LhSb formation at 700 mV vs. Li+!Li is followed by LixSn
41
ormation at lower voltages as shown in the first report on this system.
fore at each step of the reaction, the lithiated phase is embedded in an e
72
matrix; 2) the extruded tin and subsequent LixSn alloys are more ble
for reaction than in the case of InSb, since bulk tin crystallites are ntly
not formed on the surface. However, low voltage reaction ing
formation of tin alloys result in further electrode expansion and loss
erparticle contact between LhSb and Sn, causing irreversibility and
ty fading.
The best results were obtained for a Sn/SnSb mixture with a reported
73
-limited specific capacity of 360 mAh/g during 200 cycles. However,
materials exhibit a large irreversibility during the first cycle due to the
ion of a SEI layer and also because of residual impurities inherent in
nthesis process.74 '75

Synopsis. In summary, both tin and antimonide intermetallic


unds show high specific and volumetric capacities, but problems with
sibility and capacity fading. Different reaction mechanisms can be
ed depending on the composition. Where the materials are of type M
M-Sb (M =transition metal), inactive/active composites can be formed
by Li uptake. The transition metal that is extruded during reduction
s the inactive component, and the Sn or Sb participate in alloying
ns with the Li. These composites can also be prepared "by design" by
illing selected components. Alternatively, the binary intermetallic host
sert Li concomrnitant with extrusion of the inactive component, which
followed by alloying of Li with the "active" component that generates
nal capacity. When both components are "active", a combination of
on, extrusion and alloying occurs.
Despite experimental specific capacities often lower than for graphite,
lumetric capacities obtained with intermetallic compounds are usually
higher than the 830 Ah/1 observed for graphite (i.e., 4500 Ah/1 for
1650 Ah/1 for lj-Cu6Sn5) due to their high density (greater than
3 3
, 2.24 g/cm for graphite). Moreover, since 21 elements can form
with lithium, and up to 70 metals can form intermetallic compounds,
ncept offers some future prospects. However, composite electrodes
ed in situ during cycling are still insufficient in terms of cycle life of the
de. Such compounds need to be improved to replace graphitic materials
nd Composite Anodes: An Overview 127

mercial batteries.

. Aluminides

lthough ternary intermetallic phases are known for Al-Cu-Li, such as


u, LhCuA16, and LiAlCu, AhCu is completely inactive towards Li
n. The reasons for this were addressed in a systematic study of A2B
unds that all have the 8-AhCu structure (Sb2Ti, Sb2V, Sn2Co Sn2Mn,
and AhCu). The authors concluded that even though thermodynamics
that the alloying reaction should proceed, the large activation energy to
break anAl-transition metal bond hinders reactivity.

Silicides
everal efforts have also been undertaken on silicon-based electrodes.
76 77 79
on has been given to Mg2Si, ' 78 ' ' but despite much effort its
ies have proven disappointing. More promising are silicon-based
ites prepared/designed by a variety of techniques.

MgzSi

any authors have investigated Mg2Si due to its anti-fluorite structure


was reported to be amenable to Li insertion. The reaction mechanism
ever, still unclear. Moriga et al. proposed a lithium insertion into the
sites, leading to the formation of a ternary phase LiMg2Si, followed by
76
i , along with extrusion of Mg atoms that will react to form Li/Mg
This process is in78 conflict
79 with the simple dissociation reaction
d by other groups, • followed by the formation of lithium alloys
g and Si. Despite a large initial specific capacity of 1370 mAhlg at an
voltage of 350 mV vs. Li+/Li, the mechanical instability of the
de causes a drastic fade of 80
the capacity upon cycling, even by reducing
age window of the study. Extended studies were also performed on
81 82
tural compounds, such as Mg2Sn and Mg2Ge , showing better
behavior (in the case of the tin compound) than Mg2Si with capacities
mAhlg after 60 cycles in an appropriate voltage window.

Si-Based Composites

s noted above in Section 4.2.1., Si displays the highest gravimetric


Chapter4

olumetric capacity of all of the Group IVN elements. Much attention


erefore been devoted to preparing composites of Si with various
unds/elements, by different methods that allow good dispersion of the
hin the matrix. Early work in this area devoted to C/Si composites d
chemical vapor deposition to produce highly dispersed Si clusters a
carbon matrix; these materials showed promising electrochemical
83
ior.
Ball-milling has since been used with varying success to prepare
sites of Si with both hard and soft materials. Mechanical milling of Si
itanium nitride, known for its conductivity, mechanical strength and
84
ss, has recently been reported. TiN plays the role of the inactive
nent, and also aids in preserving the morphology of the electrode. The
site obtained by high energy mechanical milling (HEMM) that exhibits st
electrochemical properties (Si:TiN ratio of 1:2), is comprised of
rystallites of TiN (5-7 nm) agglomerated with amorphous Si to generate
es a few hundred nanometers in diameter. It exhibits good cycling
ty over 20 cycles associated with a specific capacity of 300 mAhlg. This
ty is still lower than the theoretical of 776 mAh/g (assuming reaction to
Li21Si5), apparently owing to a large fraction of inaccessible Si buried
the TiN matrix. However, the electrode structure is relatively stable
cycling, as little cracking/crumbling was observed after 30 cycles.
-energy ball-milling has been employed to prepare composite
des with silicon and "soft" materials such as graphite. The Si/C
sites recently reported, namely C 1_xSix powders with Si contents
g from 10-20% made by milling crystalline Si and graphite, were
d to contain Si microencapsulated by a thin layer of amorphous carbon.
display reversible capacities of up to 1040 mAhlg which fade to 800
85
after 20 cycles. The increase in Si content in those composite
als is accompanied by the coexistence of inactive SiC during their
sis. Better materials were obtained using nanocrystalline Si, prepared
86
er-induced silane decomposition, ball-milled with carbon black.
were shown to exhibit high initial reversible capacities up to 2000
, but extensive fading over 20 cycles was still observed.
Composite electrodes can also be prepared by coating or sputtering
ds. The use of thermal vapour decomposition (TVD) has been recently o
87
obtain carbon coated graphite. The resultant materials display sed
rate capacities and decreased irreversibility by comparison to
aceous materials, where graphite layer exfoliation often limits
bility. Thermal vapor decomposition has been more recently extended
88
formation of Si/C composites. Composites containing 20% carbon
g exhibit excellent performance. Up to 800 mAh/g can be obtained
n excellent cyclability. This method also inhibits the decomposition of
lytes, which can be a problem on the surface of unprotected Si-
nd Composite Anodes: An Overview 129

es, and furthermore provides a conductive network.


owever, in general (as noted above) obtaining stable cycling for alloy
e electrodes is an unattainable goal, unless the capacity is constrained
s near that of graphite. The reason for cycling instability is believed to
to inhomogeneous volume expansion in coexisting regions of phases
ferent lithium concentrations. Another approach to anode composites
ed in a patent application,89 is based on using amorphous metals and
ids. The advantage of amorphous materials lies in the potential
tion of the two-phase regions between phases of different lithium
ration, which can lead to homogeneous volume expansions and
ed charge-discharge cycling behavior. Such materials, based on
ous Si/Sn alloys have been prepared using a magnetron sputtering
. 90 The authors showed through electrochemial and in-situ XRD
ents that the materials remain amorphous at all times during cycling,
t the two local environments for Si and Sn are distributed evenly
out the bulk. These are believed to be the reasons that the materials
stain large volume expansions without drastic cracking and
ation. These materials were found to readily uptake up to 4 lithium
xSnx formula when cycled to 0 V vs. Li+/Li, leading to a specific
of 3000 mAh/g for the composition .x=0.33.
hese materials, and the new Si-carbon composites seem amongst the
romising as negative electrodes in lithium-ion batteries, although
ion of large-scale amounts of materials by sputtering technique may
hallenging.

METAL OXIDES
etal oxide anode materials can be divided into two classes. One is the
ertion compounds: metal oxides capable of intercalation chemistry at
ential. These materials are characterized by relatively high potentials
between 1.4-1.8 V), low lithium capacities and often highly
le insertion reactions. The other class of metal oxides display Li
es derived from reaction with the lithium to form another material,
s usually the reduced metal oxide encapsulated in a matrix of LhO,
to the case of the tin oxides described above. These materials also
a relatively high average charge potential, but also a large hysteresis
nt with the necessity of oxygen transport within the bulk during
n. Critical to the functioning of these materials, therefore, is the
mixture at the nanoscale regime, of metal sub-oxide (or pure metal,
ng on the degree of Li uptake) and oxygen from the lithium oxide
hat facilitates the oxygen recovery process.
Chapter4

. Transition Metal Oxides: Where Insertion Governs the


Process
As these are not strictly "composite" anode materials they will be
oned only briefly.
The most widely considered metal oxide for low potential applications
Ti5012, described as a zero-strain insertion material owing to the almost
ible changes in the unit cell on insertion of up to one lithium into the
91
ure. The formula can be written as Li[Li 113Ti513]04, illustrating the
g of Li and Ti on the octahedral 16d sites, and occupation of the
ning Li on the tetrahedral 8a sites. To account for the virtually zero
es in volume on Li insertion, Ohzuku et al. have suggested that Li is
d into the unoccupied 16c sites, which are also additionally occupied
to migration of Li from the tetrahedral sites. The combination of little
ral hysteresis and rapid lithium diffusion result in good electrochemical
ties for this material, despite an average insertion potential of 1.5 V.
ally, capacity values close to 150 mAh/g are observed. Materials
ting such capacities at very high rates can be obtained from in high
e area modifications, such as in nanocrystalline films made by sol-gel
92
ds or in commercial nanomaterials prepared by spray drying or other
ques. Li[CrTi]04, with a related structure, also shows similar
93
teristics.
The other oxide that has received attention is Ti02 as the anatase
94
orph, and particularly as a nanocrystalline material. Many reports
been devoted to preparing nanostructured anatase, with techniques
ng the gamut of spray drying, sol-gel chemistry, and the polyol
95
d. A synthetic polymorph of Ti02 produced by "chimie douce"
96
ds, known as Ti02(B), shows slightly better behavior than Ti02
e. All these material suffer, however, from a higher insertion potential
97
e spinel Li4Ti5012, and less efficient lithium mobility.

Transition Metal Oxides: Where Reduction of Metal


Oxide to Metallic or Semi-metal Occurs

The first reports of a metal oxide being subjected to deep discharge


ed lithium insertion in a-Fe203 or Co304, which were reported to lead
extrusion of the transition metals and formation of Liz0.98 For the iron
this occurs in a series of stages involving progressive formation of
d spinel structures, with reversibility implied in some of the steps.
uent studies on metal oxides concentrated on "complex" oxides,
ng LiMV04 (M = Zn, Cd, Ni),99 LixMO, and LixMyV 1_pz (M =
nd Composite Anodes: An Overview 131
100 101
on metal) and amorphous or semi-crystalline RV04 (R =In, Fe),
102 103
(M =Fe, Mn, Co), and AxMo03•
hen these materials were first reported, the mechanism responsible
Li uptake and reversibility was not understood; however great strides
nce been made. A beneficial mix of metal and metal-oxide on the
le appears to be responsible for promising properties exhibited by a
g number of transition metal oxides. The initial work on Li uptake in
y reduced molybdenum
7 oxides such as Li0.25Mo03 showed by means
ombination of Li NMR, XRD and XAS probes, that a complex
ous nanocomposite is formed at low potential. It consists of a
red, highly oxygen deficient lithium/molybdenum-oxide (a "lithium/
enum sub-oxide") in intimate association with lithium oxide. 103 The
ccounts for the irreversible capacity observed by electrochemical
Subsequent EXAFS and XANES studies revealed that although
Mo is formed on deep discharge, a molybdenum oxide is re
104 105
ed on oxidation. ' The depth of discharge is important in
ing the metal-oxygen environment. At potentials deep enough to result
plete reduction of the metal, the molybdenum retains most of its
coordination environment. The latter is only lost at repeated discharge
low potential. Thus, if the voltage window is restricted above this
the Mo essentially shuttles between oxygen poor/lithium rich
ge) and oxygen rich/lithium poor (charge) amorphous phases with
ed cyclability being the result. Complementary findings in Fe and Co
e systems on Li uptake have also been revealed by in-situ X-ray,
106
, Mossbauer and microscopy studies. The recently reported
r of iron borates such as Fe3B06 and Fe3B03 as low-potential Li
107
materials is also based on similar principles.
hese findings led to investigation of simple nano-sized metal oxides
ed on the rock-salt structure (M = Co, Fe, Ni). High-resolution TEM
of the material at deep discharge demonstrated the presence of metal
ticles about 20 A in diameter. Again, the highly divided, high-surface
nature of the nanoparticles facilitates the back-reaction with oxygen
e lithium oxide matrix
108 to reform the metal oxide on charge, this time
i-crystalline form. The reaction, particularly reversible for Co, but
for Fe and Ni, can be simplified as reaction between Li and MO to
O + M, which is reversible if the materials are on the nanoscale.
Chapter4

Mixed Transition Metal Oxides - Where Both


Reduction and Alloying are Responsible for Li
Capacity

The Sn-oxide, transition metal oxide, and Sn/Fe intermetallic studies


above opened avenues to investigate oxide materials containing both
ion metal and main-group metal active centers. An interesting class of
als based on the inherently open architecture of CaFe204 are suitable
109
ates. This structure exhibits partial solid solution based on Sn
ution for Fe with accompanying removal of Ca for Li, the end member
the stoichiometry Li0.6Ca0.4Sn0.6Fe .404, and relatively high ionic
ctivity. On introducing Sn into the structure the reversible capacity is
ntially increased compared with the parent material, owing to the
nal reaction of the Sn. Although irreversible capacity is observed that
from the partial formation of LhO, reversible Li uptake is observed
ood stability. The materials sustain a stable reversible capacity of >600
105
for the optimized composition Li0.5Cao.5Sn0.5Fe1.504• The profile of
ferential capacity plots suggest there is no complete phase separation to
alloy phases on reduction, but that a lithium-rich, oxygen deficient
oxide matrix is formed. These results are also supported by XAS
rements which suggest that Sn-Fe alloy nanophases formed at
ediate potentials lie in close proximity with oxygen.

NITRIDES AND PHOSPHIDES

Nitrides

By contrast to metal oxides, where the high degree of electronegativity


nce between the metal and the anion tends to drive the reduction to the
ion of the metal on Li uptake, nitrides display more covalent bonding n
the metal and anion. Different behavior is expected - and observed.
cases, the mechanism of Li uptake/extraction is still subject to scrutiny.
ous binary, and ternary (Li-containing) nitrides are summarized in an
110
ehensive review by Gregory et a/. but most have not been found to be
chemically active.
The first examination of the electrochemical behavior of metal nitrides
111
ased on layered LiMoN2, isostructural to LiCo02• Despite this
ing similarity in structure to a known intercalation compound, LiMoN2
to show any electrochemical activity although chemical extraction of
was achievable using butyl-lithium. Subsequent studies involved
s of the first row transition metals. These Li-M-N structures follow a
nd Composite Anodes: An Overview 133

ble trend. For Ti through Fe, an antifluorite structure is favored with


112
M in the tetrahedral sites, M being present in a high oxidation state.
13 114
nitrides in this class such as LhMnN/ and LhFeN2 display
hemical behavior at about 1.2 V vs. lithium, with reversible capacities
ange of 300-350 mAhlg. For Co, Ni, and Cu, a structure based on a
formed, with M + substituting for u+ between the hexagonal LizN
1

These Liz(Lh.xMx)N compounds (M = Mn---+ Cu) are more promising.


ered morphology is advantageous, supporting fast Li-ion conduction
transition metal oxidation states. The first studies on Liz(Lh-xMx)N
nds (M =Co, Ni or Cu) suggested that the Co member showed the
capacity (480 mAhlg) and most reversible behavior. The significantly
performance of the Ni and Cu members has not been explained. Other
by Shodai reported that Liz.6Co0.4N can exhibit a capacity up to 760
in the voltage window 0-1.4 V. 115
wing to the high cost and toxicity of cobalt compounds, a better
l would be based on Fe or Mn. Both are unique in their behavior
ies between the two structural extremes described above. For example,
s both the antifluorite phase with iron in a high formal +3 oxidation
nd layered phases with iron in lower oxidation states. Of the latter,
ports were of single crystals isolated as minor phases from mixtures,
y indicated the possibilities of intriguing chemistry. A "metastable"
2
phase Li eN2 contains layers of LizN with ordered Fe + and
116 1
es between the layers. Crystals of Liz(Li0.37Fe0.67)N (Fe +) have been
from a mixture formed from decomposition of the antifluorite phase
117
ium flux. We devised a synthesis route to a novel lower iron-content
layered Liz(Li0.7Fe0.3)N, that provides virtually gram-scale quantities
yield within a day, by simple reaction of Fe with LhN at 800°C. 118
aterial is isostructural with the layered Liz.6Co0.4N analogue.
hemical studies showed that Liz(Li0.7Fe0.3)N displays a capacity of up
mAhlg in a potential window of 0 ---+ 1.3 V, with relatively good
on cycling.
oth the antifluorite and higher capacity layered nitrides, however, are
to three concerns: 1) They are highly hygroscopic and moisture
e. 2) They become amorphous on lithium extraction, making it
to ascertain the mechanism responsible for reversible Li
on/uptake. Studies to determine the mechanism responsible for
ization and Li uptake suggest that reversible migration of the N atoms
119
uring charge and discharge. 3) They need to be "charged" first by
oval of lithium from the structure, and hence they act as a reservoir for
not a sink. This results in problems in finding a suitable cathode
, as most of the preferred materials exist as lithiated air-stable phases.
these concerns, Lh.6Co0.4N has been recently re-examined by groups
120
sonic/Matsushita and proposed as an anode versus LiMn204 in
Chapter4

121
-ion cells. In recent work, the material has also been coupled with
122
ntaining anode materials to compensate for irreversibility in the latter.
The electrochemical behavior of main group nitrides capable of acting
123
i "sink" have been recently described by the Telcordia group. They
that uptake of Li by Zn 3N 2 results in formation of LiZn in a matrix of
. On charge, complex reactions result in the oxidation of LiZn to
ic Zn, and reaction of -LhN with LiZn to form LiZnN which is the end
er phase for all subsequent cycles. This first-reported reversible LhN
rsion gives a reversible capacity of 555 mAh/g but the cycle life was
d.

Phosphides

Like nitrides in some respects and antimonides in others, phosphides


recently been shown to exhibit interesting chemistry that is a
nation of the other Group V members. In common is the fact that the
ying mixed anion-metal bands, and a high degree of electron
lization lead to a low formal oxidation state of the metal, and strong
nt character of the M-pnictogen bond. 124' 53 The materials therefore
an overall lower intercalation potential compared to the respective
. Differences within Group V compounds arise from the fact that
ides display more covalent bonding than the corresponding nitrides, s
than the predominantly semi-metallic antimonides. These bonding
nces are reflected in the band structure and chemistry, as shown in
4.5.

Oxide
Density of states Density of states Density of states

.5. Comparison of DOS for oxides, nitrides and phosphides.

n nitrides, the uppermost band is thought to expose nitrogen-based


s and hence result in holes appearing in the nitrogen-dominant band
xidation (and evolution of N 2 on overcharge). 120 In antimonides by
t the redox reactions involve the metal-Sb bond, and hence Li
nd Composite Anodes: An Overview 135

reduction results in phase separation to form metal and LixSb alloys.


sphides, the chemistry seems to lie midway between the two.
nces in the strength of the M-pnictogen (PN) bond, and relative
ution of the PwPN bond results in a paucity of transition metal-poor
nitrides (but plethora of transition metal antimonides). For example,
analogous to MnP4, does not exist. As no binary nitrides are known
n uptake u+te·, the lithium ions must first be removed from the
e to give reversible cycling, a drawback of these materials that also
in irreversible collapse to an amorphous structure. More importantly,
ative electrode in a cell should act as a reservoir for Lias MnP4 does,
urce. In this respect, phosphides have advantages over nitrides.
he electrochemistry that is responsible for reversible Li uptake varies
ng to element, and as to whether a lithiated ternary phase exists in the
iagram with the same M:P stoichiometry as the binary phase. Unlike
monides, the mechanism is dependent on the stoichiometry/structure
starting phase.The behavior exhibited can be separated into four
those in which the binary and ternary phases exist i.e.,MP <->LiMP;
which only either the binary or ternary phase exist, i.e., MP (FeP2) or
Li2CuP); and those in which Li uptake results in phase decomposition
etallic state, as in CoP3. These are discussed below.

Binary (MP <·> LiMP) Combination

here a fully lithiated end member exists, conversion between the


nd ternary crystalline phases can occur on lithium insertion. Such a
is exhibited by MnP4, which undergoes a first-order phase transition
125
crystalline LhMnP4• The mechanism by which this occurs is more
x than a typical intercalation reaction, however, as substantial
al differences exist between the two phases. The layered 8-MnP4
e is composed of infinite sheets of MnP6 octahedra linked by P-P
oth within the sheets, and between the sheets. LhMnP4 has the
rite structure. On u+te· uptake, P-P bonds between the layers are
ely cleaved (P"
1
p·\ and Li ions are inserted in the resulting
ellar voids. Translation of Mn from an octahedral to a tetrahedral site
ach coordination rhomboid provides space for additional tetrahedral
ial sites for u+, to give the antifluorite structure. A scheme illustrating
posed mechanism is shown below. Importantly, the process can be
reversed by reversing the voltage, resulting in "electrochemical
llization" of the original MnP 4 phase as a crystalline compound. The
ds in the MnP4 structure that are cleaved on Li insertion (reduction) to
MnP4, are reformed on re-oxidation to MnP4. Thereby, they act as an
storage reservoir.
Chapter4

The reaction is a quasi-topotactic intercalation process that represents


st unequivocal example of reversible lithium insertion of lithium at low
ial, aside from graphite. There are obvious differences, however. Li
on in graphite cleaves only the very weak van der Waals bonding
en the graphene layers, and is hence a facile process, whereas the
required to cleave and re-form the covalent P-P bonds is significantly
. Contrary to the pure intercalation process in graphite that can
ore proceed with little hysteresis, the phosphide reaction is kinetically
d by the structural rearrangement involved in the phase transition. The
ntial volume/density change also seen in other high-capacity anodes
esults in some cracking and loss of contact with the current collector.
reversible capacities (700 mAhlg) than theoretical (1050 mAhlg) are
ed on the first cycle, that fade on cycling.
Nonetheless, reversible capacities of 550 mAh/g, stable over >25
, can be sustained at C/4 rates in nano-sized particles formed by ball
126
g. Interestingly, Li can also be de-inserted from crystalline Li7MnP4
e similar electrochemical results. However, the MnP4 formed on
ion is very poorly crystalline (almost amorphous), as is the Li7MnP4
uently formed on re-insertion. This is presumably due to the fact that
nt ordering of Li and Mn is implied on insertion of Li in MnP4. This
be duplicated by starting in the opposite direction, due to the perfectly
m distribution of Li and Mn in LhMnP4.
Li de-insertion from Li7VP4 has also been recently reported to give
127
ible capacities of 550 mAh/g, on the first cycle at a C/34 rate. They
unusual stability of the VP4 framework to different lithium
sitions, based on the fact that de-insertion of Li appeared to result in no
ral change to the lattice. The authors, however, allowed for the
ility that the oxidized phase could be amorphous.

. Binary MP; No Stable LiMP Ternary

Where a binary MP exists but no stable LiMP ternary phase of the same
oichiometry, two possibilities for Li uptake can be predicted. The
n can either yield a metastable ternary phase, such has been proposed
hium insertion in FeP2; or decomposition to yield Li 3P and metal can
akin to the reaction in antimonides. The latter is exhibited by CoP3• In
ases, Li uptake (and subsequent extraction) results in an amorphous
al, making the nature of the Li uptake process difficult to discern.
nd Composite Anodes: An Overview 137

1. FeP2

he reaction of FeP2 with Li occurs with a remarkably low degree of


128
ibility on the charge cycle as shown in Figure 4.6.

2.5
+ 2.0
_J
rn
> 1.5
Q)
Cl
.l!! 1.0
g 0.5

0.0+- .- .--.----,r---"----r ---. ----r -i


0 2 3 4 5 6 7
x in Li.FeP2

6. Voltage vs composition for FeP2 cycled at a C/4 rate.

he process of Li insertion has been investigated using electrochemical


in concert with X-ray diffraction, XAS and magnetic measurements.
take of six Li during the first discharge leads to a specific capacity of
Ah/g, and an amorphous phase retaining substantial Fe-P bonding. It
s superparamagnetic behavior and an extremely low transition
ture below lOK. Upon charge, 5.5 lithium can be extracted from this
ble ternary "Li-Fe-P" phase, leading to a reversible capacity of 1250
56
To account for the presence of Fe-P bonding observed in the XAS -
experiments, the magnetic behavior of the particles on discharge, and
identifiable LhP, it was proposed that Li uptake occurs by expansion
hosphorus lattice, and incorporation of the additional lithium to form a
red, stuffed metastable "Li 3Fe05P" lattice that still maintains Fe within
cture. The low (ca. 10-15%) irreversibility exhibited by FeP2 makes it
esting material in the search for new negative electrode materials.
herefore, like in MnP4, the high degree of covalent bonding and low
of the metal induces a transformation more akin to "insertion", in to
the iron antimonide, FeSb2, where complete phase separation into um
antimonide and the metal occurs as described in Section 4.2.1.2.2
other metal phosphides, the possibility of a transition between a
LiMP phase and a metastable MP phase could be envisioned. Such a
mation appears responsible for the reversible de-insertion from
from Li2CuP to give "CuP" recently discovered in our lab.
Chapter4

2.2. CoP3

Phase separation of metal phosphides into metal and Li3P is observed


e phosphide, CoP3, however, as recently described by two different
129 130
ch groups. · Their conclusions are similar, although they differ on
arge process. The presence of Co particles is not apparent in the XRD
n of reduced CoP3 due to their small dimensions (well below the
ening limit of 500 A in XRD) but their presence was indirectly
sted by the clear presence of LhP in the diffraction pattern. TEM
rements revealed the presence of 10-20 A nanoparticles embedded
the original crystallite. As the SAED pattern showed only broad, weak
with d-spacings corresponding to LhP, and no interplanar spacings
able to cobalt crystallites, it was concluded the metal must be very
dispersed; perhaps
129 weakly bonded to the matrix as highly metal-rich
hide clusters. The metallic state of Co was revealed in XAS
rement of Alcantara et al.,130 however, who also showed the presence of
hrough MAS-NMR studies.
The process on charge appears to involve redox reactions of LhP, but
ticipation of the cobalt. The same mechanims as in the antimonides
ggested by Alcantara et al., involving a reaction based on formation/re
tion of LhP from its elements, Li + P. A reversible capacity of 487
was observed in this case. A slightly different mechanism was
129
ed by Pralong et al., in which cycling (400 mAhlg) was attributed to
nsformation between LhP and LiP on the basis of XPS measurements.
h cases the observed capacities are well below the theoretical.

p sis. The behavior of the phosphides represents a departure from


that ted by ionic negative electrode materials such as oxides (where the
high of the metal-localized bands drives the reduction to the metallic
state uptake); nitrides; and intermetallic negative electrode materials
where
ake relies on formation of alloys LixM (M = Sb, Sn). Furthermore,
covalent bond rearrangment and atom migration that lead to
chemical "recrystallization" (MnP4) or facile introconversion of
hous phases (FeP2) are a signature of these materials. New
unities are hence afforded by some phosphides, if difficulties with
lyte reactivity/SEI formation can be overcome which currently limit g
stability.

CONCLUSIONS
The task of finding alternate materials for anodes in lithium-ion cells to
nd Composite Anodes: An Overview 139

ceous materials has proven to be a daunting and challenging task that


nned more than a decade of work amongst many research groups.
erview has attempted to summarize some of the major directions that
ominated the field, both in anode materials in general and in
ites in particular. It is clear that the goal of developing materials
of insertion/uptake of large proportions of lithium is incompatible
e difficulties of the large volume changes necessitated by such
s, and resultant capacity fading. However, clever approaches can be
ameliorate the problem, many of which lie in the composite approach.
sites-by-design (such as carbon coated Si materials) and the concept of
nactive materials provide good possibilities for the future, along with
synthesis of intermetallic compounds, nitrides, phosphides and
that may demand a composite (and/or combinatorial) approach to
e their electrochemical performance. Alternatively, designed
hes to nanostructured alternatives of these materials are needed.
anding of the mechanism of lithium uptake is critical to advancing s
in the area. Finally, attention must be given to reactions of these
s with electrolytes at low potential which can compromise
hemical performance. SEI formation with materials aside from carbon
ell understood, and the liquid electrolytes today that are optimized for
may prove less than ideal for other materials.

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apter 5

ARBONACEOUS AND GRAPHITIC ANODES

M. Winter, K.-C. Moeller and J. 0. Besenhard

titute for Chemical Technology of Inorganic Materials, Graz University of Technology,


Stremayrgasse 16, A-8010 Graz, Austria, e-mail: martin.winter@tugraz.at

CARBONS IN ION TRANSFER BATTERIES


In rechargeable lithium ion batteries the main1 application of carbon is
use as a host anode accessible by lithium cations via electrochemical
tion, the lithium being provided by another insertion material used as
cathode (Figure 5.1A). This "electro-insertion" reaction is basically a
/guest solid state redox reaction involving electrochemical charge
fer coupled with insertion of mobile guest ions (in lithium ion batteries,
e are lithium ions) into the structure of a solid host, which is a mixed
ronic and ionic conductor. The major structural features of the host are
after the insertion of the guests. A common convention in the literature
at "intercalation" is regarded as a special case of "insertion". The term
rcalation" implies the restricting condition that a layered host takes up
ts within its interlayer gaps ("galleries"), which may result in a volume
ge perpendicular to the layers, but which causes no other structural
ges. However, according to this strict definition, even graphite would be
a pure intercalation host, as during Li accomodation the stacking
ence changes by sliding of the graphene layers. Therefore, in this review
erm intercalation will be used where the historical conventions or the
ent practice make its use appropriate, i.e., we will use the term lithium
hite intercalation compounds for lithiated graphites (cf. Refs. 1-16).

hould be noted here, that cation and anion intercalation can also occur into carbon
ials used as conductive electrode additives. At the anode, this cation intercalation is a r
reaction occurring in parallel to intercalation in the active carbonaceous anode ial.
At the cathode, anion intercalation can happen during overcharge of the electrode.
onaceous and Graphitic Anodes 145

Graphite is a redox-amphoteric intercalation host, i.e., it can be


calated by cations and anions yielding so-called donor- and acceptor-
graphite intercalation compounds. 11' 15- 17 All-graphite-based

E ctrolyte

c
2
0 0 0
0 0 0
Electrolyte
0 0 0

Dts.charg•

tr
0 0
0 0
- 0

H 0
0
0
0

0 0
000 0
Discharge
lnMrtion Ho•t
( Or l!lph ile Anodto)
ln1ortlon Ho•l
(Cothodo)
c,.,x c,,x

oo
n
000
000
000

o g Elec trolyte

ooo
0 0 0 + . 980
000
0 0 92 2
M C,
0 "'"""..

c,x c.
+---
Charge g oo
c,x

c, c,
Charge

e 5.1. Rechargeable cells with active graphite intercalation electrodes: (A) graphite as
m cation intercalation host anode (negative electrode) in lithium ion cells, (B) graphite as
(accepting cations M) and cathode (positive electrode, accepting anions X) in dual ite
cells, and (C) hydrogen sulfate ion transfer cell based on graphite anode and cathode
accepting anions X=HS04.), CnX denotes a stage-1, C2nX a stage-11
gensulfate/graphite intercalation compound (cf. Section 5.3.2.2).
argeable batteries have been investigated since decades. In these so d
"dual-graphite" cells, 18 22 - the charge/discharge reaction is the
calation/release of electrolyte cations and anions into graphite (Figure
). As the ion concentration of the electrolyte changes during cycling,
gh electrolyte salt (cations +anions X) must be incorporated in the cell
uarantee the electrolyte conductivity, and enough solvent must be
Chapter 5

ided to leave the electrolyte salt dissolved at any state of charge/


harge.
In contrast with lithium ion cells, where the electrolyte is basically an
transfer medium, this charge/discharge mechanism requires excess of
trolyte salt and solvent at the expense of energy density. Furthermore, as
cell operates at up to 5 V, the electrolyte suffers from strong electrolyte
ction and oxidation.
A very interesting example of an all-graphite-based rechargeable
23
ry has been proposed by Rlidorff and Hofmann as early as 1938. They
constructed an electrochemical cell by combining a graphite cathode,
intercalated with HS04-(H2S04)y (this is a so-called stage I graphite
calation compound, the HS04- guest ion being solvated by sulfuric acid
ecules; cf. Sections 5.3.2.2 and 5.4.2 for explanations) with a plain (not
calated) graphite anode. During charge, the anions are transferred from
cathode to the anode, until both electrodes possess the same guest
entration. During discharge, the guest concentration in the cathode is re
blished by the backwards ion transfer. Using today's terminology, this
trochemical set-up would be named a hydrogen sulfate ion cell. This cell
e first "ancestor" of the lithium ion cell.

HISTORY OF LITHIATED CARBONS

The first occurrence of lithiated carbons formed by reaction of lithium


carbonaceous materials is said to go back to the development of the
monuclear hydrogen bomb in the 1940s, whose enormous energy release
2.4 MeV is based on the strongly exothermal fusion reaction of the
2 4 4
pes 63Li and 1H yielding two molecules of 2He.Z
Nevertheless, the first intended and official synthesis of lithiated
25 26
ons was reported by Herold • in 1955, who prepared a lithium-graphite
calation compound (Li-GIC) from the elements via a chemical synthesis
e. The formation of Li-GICs is in competition with the formation of Li
7 29
des.Z - Therefore, the chemical synthesis has to be carried out at
erate temperatures and lithium vapor pressures. The chemical synthesis e
30 31
GICs of the heavy alkali metals K, Rb, and Cs was reported before, ·
32 33
reas the first Na-GIC's emerged afterwards. • Fully intercalated highly
talline graphites have the stoichiometric formulae of MC 8 (M=K, Rb,
Cs) and LiC6.26 Na hardly intercalates into graphite yielding diluted
11 26
's of the formulae :::NaC24 - NaC 64• ' A higher Na uptake was obtained
34 38
disordered carbons. - An overview about the early works on
mically prepared GICs is given in Ref. 26.
The electrochemical formation of Li-GICs was performed more than
years after the chemical synthesis. As in the case of metals which alloy
onaceous and Graphitic Anodes 147

lithium,39-42 electrochemically prepared lithiated graphites 43-45 emerged


in room temperature lithium cells, when they were used as substrates for
lectrodeposition of metallic lithium from Lt-containing electrolytes. It
a while until the occurring phenomenon was identified to be a
rsible lithium intercalation into graphite.46.47 Not much later, graphite
proposed as reversible anode for nonaqueous electrolyte based
argable lithium batteries48 by adapting the already known concepts of
ro-insertion and electro-intercalation. 1-3
Though the safety problems with the dendritic lithium deposition in
argeable nonaqueous organic electrolyte lithium batteries (cf. reviews
4,49-61) urgently demanded a replacement by an insertion anode, which
ded the use of Li metal, the attempts to introduce a graphitic carbon
e in a rechargeable lithium battery resulted in no practical realization for
46 47
than a decade. These attempts included the use (i) of electrolytes •
h co-intercalate into graphite (cf. Section 5.4.2), (ii) of solid polymer
62
rolytes, '63 and (iii) of a lithiated (charged) graphite anode in molten
64 65 64 66
• or organic electrolytes, ' which is sensitive to air and moisture and
complicates cell assembly.
The first two research reports on carbon anodes with practical
ance for rechargeable lithium batteries by Kanno et al.67 and Mohri et
appeared in 1989. Mohri et al.68 even constructed a complete lithium ion
consisting of a pyrolytic carbon anode and a metal oxide cathode, which
able to deliver several hundreds of cycles at satisfactory efficiencies. In
several japanese companies have investigated and patented the usage of
69
ific carbonaceous anodes before that time. The first announcement of a
mercial application of a carbon insertion host anode in a so-called
m ion cell was done by Sony in 1991.70• 71 Their cell was based on a
dered carbon anode and a LiCo02 cathode, which means the electrode
rials are assembled in the discharged state, the electrode materials being
ery sensitive to moisture and air.
72
The underlying ion transfer concept was proposed and applied with
73 77
native electrode materials - before. However, though lithium ion cells
lithium-aluminum alloy anode73 or an insertion anode based on oxidic
rials74-77 were feasible in principle, they suffered from poor practical
gy densities (oxides) or cycling stabilities (alloys). The superiority of
m ion cells is chiefly connected with the use of carbonaceous anode
rials.
The announcement of Sony induced a run on the research topic lithium
atteries, which in tum produced tens of thousands of papers, patents,
other publications (cf. books and compilations78-82 and reviews
42,54,55,57-59,61,83,84). With regard to carbonaceous anodes, this
publication output is mainly due to the variety of carbon materials
tigated for lithium insertion and the various resulting lithium storage
Chapter 5

hanisms. In addition, the manifold interactions of the carbon material


other battery components, in particular with the electrolyte, have to be
idered. The related issues will be discussed in the following sections.

ELECTROCHEMICAL Li STORAGE IN CARBON


1. Carbonaceous Host Materials and Their Properties
The quality and quantity of sites which are capable of reversible
um accommodation and the type and extent of interaction with the
rolyte depend in a complex manner on the crystallinity, texture, (micro-)
ture, and (micro-) morphology of the carbonaceous host material. The
of carbon determines the current/voltage characteristics of the
rochemical intercalation reaction and also potential side reactions.
onaceous materials suitable for lithium insertion or intercalation are
mercially available in manifold types and qualities (cf. reviews
4,53,57,60,85-94). Many exotic carbons have been specially synthesized
14
laboratory scale by pyrolysis of various precursors. Even fullerene and
95
on nanotubes have been evaluated, however with little practical
ess.
Heteroatoms, i.e., atoms in the carbonaceous material different from
on, can play an important role in the bulk (Section 5.3) and surface
istry (Section 5.4) of carbon and furthermore have strong influence on
haracteristics in the lithium ion cell. The term "carbon alloys" has been
96
ed for structurally and chemically heterogeneous carbons.
It has to be emphasized that the assumed suitability of a carbonaceous
rial for a lithium intercalation host depends strongly on the method of
valuation. Quite a few carbons may have been rejected as anode
rials due to an inadequate evaluation. As a consequence, the
ification of a carbon as "good" or "poor" anode material can be
etimes only preliminary.
Due to the variety of available carbons a classification is inevitable.
t carbonaceous materials which are capable of reversible lithium storage
oughly be classified as graphitic and non-graphitic (disordered).

.1. Graphitic Carbons

Graphitic carbons basically comprise of sp2-hybridized carbon atoms


h are arranged in a planar "honeycomb-like" network, i.e., a "graphene"
is formed97 (Figure 5.2). Van der Waals forces provide a weak
sion of the graphene layers leading to the layered graphite structure.
onaceous and Graphitic Anodes 149

a strictly crystallographic point of view, the term "graphite" is only


icable to carbons having a layered lattice structure with a perfect
king order of graphene layers, either the prevalent AB (hexagonal
hite, 2H-, or a-phase ) or the less common ABC (rhombohedral
hite, 3R-, or -phase). Due to the small energy for transformation of AB
ABC stacking (and viceversa), perfectly stacked graphite crystals are
eadily available. Therefore, the term "graphite" is often used regardless
acking order.
The ratio of hexagonal to rhombohedral contents can be varied by
in processes. Mechanical treatments, especially milling, shearing, or
85 98 99
sonic impact result in a larger extent of the -phase, • • whereas
mal annealing procedures at elevated temperatures convert the material
he thermodynamically more stable a-form. By heat treatment, it is
ible to create a graphite which contains 100% a-phase, whereas this
d not be achieved by mechanical measures for the -form. So far, e
contents up to 30% have been reported. The rhombohedral and
85 98 100
gonal contents of graphites can be estimated from XRD spectra. •
• -
t should be noted here, that in addition to a change of the stacking
ence, the mechanical milling is able to destroy carbon-carbon bonds
104 108
thus to increase the number of structural defects, - the kind and
109 111
nt of defects being dependent on the milling procedure. - On the
rary, heat-treatment does "heal" the graphite structure by reducing the
85 101
ber of defects. ' After long term milling, graphite can develop a fully
110 112
rphous structure. ' Shorter milling times can confine the
101 109 111
rphization to the surface. ' ' Milling is also able to change the
ical (surface) composition of the carbon material, when done under a
113
in atmosphere, as the defects created by milling are highly reactive. -

basal plane surface

outline of
unit cell

e 5.2. Crystal structure of hexagonal graphite showing the AB layer stacking sequence,
it cell, and the subdivision in basal plane and prismatic surfaces.
Chapter 5

The structure of layered graphite gives rise to basically two kinds of


aces, prismatic (edge) surfaces and basal plane surfaces (Figure 5.2). l
(defect- and contaminant-free) basal plane surfaces are homogeneous
"smooth" and consist of carbon atoms. In contrast, the prismatic surfaces
heterogeneous and "rough" and apart from carbon may contain various,
tly (but not only) oxygen-containing, surface groups. The quantity and
ity of surface groups for graphitic and non-graphitic carbonaceous
rials can be changed by mechanical (e.g., milling), thermal (e.g., heat
ment), and chemical measures (e.g., exposure to reagents creating a
in surface chemistry), or a combination of these methods. For further
ils on carbon surface chemistry, cf. 11,117-122. The problems with the
rmination of the surface chemisty of carbons are discussed in Refs.
124.
It is well known that the prismatic and basal plane surfaces of graphite
117 118
a different electrochemical behavior in many respects. •
calation, for example, proceeds via the prismatic and not via the basal e
surfaces. The interaction of graphitic materials with the electrolyte is
dependent on the respective surface and its properties. The information
t the relative and absolute extents of prismatic and basal plane surface
s in a graphite material is essential for understanding and controlling the
ions of the graphite anode in lithium ion cells.
The adsorption of nitrogen at 77 K is a commonly used measurement
2
he determination of the total specific surface area (as m /g) of graphites
other materials through application of the well known Brunauer
ett-Teller (BET) equation. The determination of the BET surface area is
d on the premise that the surface of the solid adsorbent is homogeneous
thus, the whole surface adsorbs the same extent of nitrogen per area,
that the calculation of the nitrogen volume forming a mono-layer on the
rbent allows to determine the surface area. Any surface heterogeneities
ng to different degrees of (multi-layer) nitrogen adsorption at different
ce sites are not accounted for in the BET theory. A more sophisticated
ry than the BET theory has to be applied in order to estimate the total
125 126
ce area of graphitic carbons. ' This theory also allows to
idually estimate the extents of prismatic and basal plane surfaces of a
hitic material, and thus for example may disclose which part of the
hite surface is active for lithium intercalation and which not l 85• 1271•
The actual structure and surface of practical carbonaceous materials
ates more or less from the ideal graphite structure and surface. Even
ly ordered graphites typically have a number of structural defects, such
128 129
slocations, steps, boundaries, point defects, and cracks. • Moreover,
onaceous materials consisting of aggregates of graphite crystallites are
ed graphites as well. For instance, the terms natural, artificial, synthetic,
pyrolytic graphite are commonly used, although the meant materials are
onaceous and Graphitic Anodes 151
130
crystalline. The crystallites may vary considerably in size, ranging
om to (lm. In some carbons, the aggregates are large and relatively free
efects, e.g., in highly oriented pyrolytic graphite (HOPG). Furthermore,
re effects can be observed as the crystallites may be differently oriented
ch other. In addition to essentially graphitic crystallites, carbons may
include crystallites containing carbon layers (or packages of stacked
on layers) with randomly distributed misfits and misorientation angles of
131
stacked segments to each other (turbostratic disorder ) . The latter
der can be identified from a non-uniform and on average increased
130 132
layer spacing compared to graphite; ' the corresponding XRD
rns show relatively broad and quite asymmetric (001) diffraction
133
s.

.2. Non-Graphitic Carbons

hen the structure disorder becomes more dominating among the


allites, the carbonaceous material can be no longer considered graphitic
must be regarded as non-graphitic (disordered). For carbons that contain
characteristic graphitic and non-graphitic structure units, the
ification in graphitic and non-graphitic types can be somehow arbitrary
n many cases only made for the sake of convenience.
In case of non-graphitic carbons most of the carbon atoms are arranged
planar hexagonal network too. The basic structural unit (BSU) contains
ar aromatic structures consisting of several tens of rings, which have
134
rent relative arrangements. Though layered structure segments made
BSUs are probable, there is actually no far-reaching crystallographic
r inc direction. This is typical of the BSUs form carbon structures which
haracterized by amorphous areas embedding and partially crosslinking
135 137
graphitic-type (layered) structure segments. - The number and size
ese areas vary and depend both on the precursor material and on the
ufacturing process, e.g., manufacturing temperature and pressure. The
of the BSUs and of the structure segments made from the BSUs can be
l, so that many internal edges with internal heteroatoms or unpaired
117
rons are possible. Most non-graphitic carbons are prepared by
lysis of organic polymer or hydrocarbon precursors at temperatures
w -1500°C. Further heat treatment at temperatures from -1500 to
0°C allows to distinguish between two different types of carbons.
Graphitizing carbons develop the graphite structure continuously
g the heating process. The structure segments are mobile enough to
graphite-like crystallites as crosslinking between them is weak.
hitization of these carbons is simply the disorder order transformation
all but disorderedly stacked carbon layers and graphite crystallites into
ordered (more graphitic) arrangements.
Chapter 5

Non-graphitizing carbons exhibit no true development of the graphite


ture, even at high temperatures (2500-3000°C), since the carbon layers
mmobilized by strong crosslinking. In order to increase the number of
slinks, organic precursors which tend to crosslink, or crosslinking agents
138
as oxygen can be applied. Since non-graphitizing carbons are
hanically harder than graphitizing ones, it is common to divide the non
hitic carbons into soft and hard carbons.135 The precursors, the
aration, and assumed structures of hard carbons resemble those of glassy
139 140
on. • The inter-layer and intra-layer disorder in hard carbons is so
ng that the carbon layer fragments building up the carbonaceous material
sizes of only z1 nm. 141' 142
Franklin 135 reported that, compared to graphitizing carbons, non
hitizing carbons exhibit a considerably larger fine-structure micro- and
143
-porosity. The size of the pores is in the range of 1 nm. 141•
The different structural features (graphitic order, disorder, and
pores) of graphite, soft carbons, and hard carbons result in different
53 85
um storage mechanisms (see below). Dahn and colleagues • and
umi and colleagues144 '145 have proposed theories based on the Franklin
el, which allows to correlate the complex XRD patterns of non-graphitic
ons with the relative amounts of unorganized (randomly oriented and
rphous) and organized (layered) areas. As a result, the lithium storage
city of a specific carbon material can be approximately predicted.
146 147
Azuma and colleagues ' have developed a novel model of the
ture of soft and hard carbons. The model is based on the analysis of the
layer distances, true densities, and nearest-neighbor-interactions of
le carbon layers in a carbonaceous material and allowed them to predict
tural characteristics beneficial for high lithium storage capabilities. The
difference to the Franklin model is that the model considers each single
on layer, whereas the Franklin model considers small crystallites, each
aining two or three carbon layers, with equidistant interlayer distances
equal orientation to each other.
For graphitizing carbons, Mering and colleagues 148 has proposed a
el which assumes that each single carbon layer is disordered.
hitization is primarily considered as an ordering of this intra-layer
rder. The development of inter-layer ordered graphite structure is a
ndary effect, resulting from the intra-layer ordering process. The
ication of this model to the lithium intercalation behavior is reported in
. 85,149.
The mobility of the carbon structure units, i.e., depending on the
el, the mobility (i) of small graphite crystallites, (ii) of single carbon
rs (or BSUs), or (iii) within the single layers, determines the degree of
ostructural ordering as well as the texture of the carbonaceous material.
pends on the state of aggregation of the intermediate phase during
137
lysis, which can be solid, liquid, or gaseous. Non-graphitizing carbons
onaceous and Graphitic Anodes 153

usually products of solid-phase pyrolysis, whereas graphitizing carbons


commonly produced by liquid- or gas-phase pyrolysis. Examples of
ucts of solid-phase pyrolysis are chars and glassy (vitreous) carbon.
use of the small crystal size and high structural disorder of the precursor
mers and the presence of crosslinkings, the ability of these carbons to
hitize is low. Pyrolysis of thermally stabilized polyacrylonitrile or pitch,
h are the precursors for carbon fibers, yields also solid intermediate
es, but stretching of the fibrous material during the manufacturing
137
ess produces an ordered microstructure. The synthesis of petroleum
, which is the most important precursor for the manufacture of carbons
graphites, is an example of liquid-phase pyrolysis. Petroleum coke is
uced by the pyrolysis of petroleum pitch, which is the residue from the
llation of petroleum fractions. Cokes are also products from pyrolysis of
tar pitch and aromatic hydrocarbons at 300-500°C. Carbon black,
carbon, and carbon films are examples of gas-phase pyrolysis products,
products of thermal cracking of gaseous hydrocarbon compounds which
130 137
eposited as carbon on a substrate. •
The ability to graphitize also depends on the pre-ordering and pre
re of the respective precursor. For example, the graphitization ability
in the carbon layer should be higher (i) when the precursor material
prises highly condensed aromatic hydrocarbons, which can be
idered to have a graphene-like structure and (ii) when neighboring
s, graphene layers or graphitic crystallites are suitably orientated to each
r.
Apart from manifold structures, carbons can have various shapes,
s, and textures including powders with different particle size
91 150152
ibutions, foams, whiskers, foils, felts, papers, fibers, • spherical
150 153 87 154160
cles ' such as mesophase carbon microbeads (MCMB), ' etc.
erent shapes, forms, and textures do not only influence the lithium
calation behavior and the interactions with the electrolyte, but also may
91
rucial for electrode construction. 90 ' Comprehensive overviews on
on properties are given e.g., in Refs. 130,136,137. Further information
arbonaceous materials can be found in Refs. 130,135,137,161-164.

2. Electrochemical Li Storage in Graphitic Carbons


The electro-insertion of Lt cations into carbon proceeds according to:
discharge

charge
Chapter 5

During electrochemical reduction (charge) of the carbon host, Li


ons penetrate into the carbon and form a lithiated carbon LixCn. Li cation
ase during carbon oxidation is the anode discharge reaction.

2.1. In-Plane Ordering

In general, a maximum lithium content of one Li guest atom per 6


on host atoms can be reached for lithium intercalation into highly
red, highly crystalline graphite (n6 in LiCn or1 in LixC6) at ambient
sure. Higher lithium storage capacities into carbon can be reached with
in non-graphitic carbons and specifically treated graphites (see below).
The intercalation reaction proceeds via the prismatic surfaces (Figure
. Through the basal planes, intercalation is possible at defect sites only.
ng intercalation the stacking order of the graphene layers shifts to AA.
s, two neighboring graphene layers in LiC6 directly face each other
ure 5.3A). The energetically favored AA stacking sequence of LiC6 has
1165 1661
proven by quantum mechanical calculations. · Due to the hosted
um the interlayer distance between the 16graphene 167 168 layers increases
erately (10.3% has been calculated for LiC6 · · ). The stacking order
he lithium interlayers is aa (a Li-C6-Li-C6-Li chain exists along the c
16'169). In LiC6 the lithium is distributed in-plane in such a manner that

r:
37 0

·l!::;;:

$
ccupation of nearest neighbor sites is avoided (Figure 5.3B).

A Li layer B C

A
-1§ ij@@ . 0 0

cl
"""'

0· "<?'t:>
0.430 nm grap hene Iayer I} "<'fao
e 5.3. AA layer stacking sequence and the aa interlayer ordering of the intercalated
m in LiC6 (A). In-plane structures of LiC6 (B) and LiC2 (C).
A higher lithium in-plane density by occupation of nearest neighbor
is obtained in the phases LiC2 - LiC4, i.e., x in LixC6 = 2-3, which are
ared chemically from graphitic carbon under high pressure (-60 kbar)
89 173
high temperature (-300°C) conditions. • 170 - The close Li-Li distance
C2 (Figure 5.3C) results in a higher chemical activity 174
of lithium than that
thium metal (Li-Li bond length (20°C) = 0.304 nm ). Under ambient
itions LiC2 decomposes slowly via various metastable intermediate Li/C
89 172
es to LiC6 and metallic lithium. ' A study of the electrochemical
onaceous and Graphitic Anodes 155

vior of LiC 2 can be found in Ref. 89. For more details on the chemical
hesis of LixC6, see Refs. 26,88,89,175,176.

2.2. Stage Formation

A general feature of intercalation into graphite is the formation of a


dic array of unoccupied layer gaps (galleries) at low concentrations of
25 26 177 180
11 15 16 23
t species, called stage formation. ' • • - This stepwise process
' ' '
be described by the stage index "s" which is equal to the number of
hene layers between two nearest guest layers. Staging is a
modynamic phenomenon related with the energy required to "open" the
der Waals gap between two graphene layers for the guests entering the
. The repulsive coulombic interactions between the guest ions are less
tive. As a consequence, few but highly occupied van der Waals gaps are
getically favored over a random distribution of guests.
Staging phenomena as well as the degree of intercalation can be easily

A
-
- -" Li
0.3
B

·m
3

S
== tag e II
la yer
Is> IV (1' Li)
1
IV]

stage I
I
I

.2 S> IV 0.2 liV III


(1" Li)
+
IV > III IIL
II L ll
(ij

0.1
IV II L
+ +
I
+ & (Reduction)
Ill :II L: II
I I
II+ I
t
0 0 '-'------+
t (i = const.)
I
-0.2 0.34 0.5 1 xin Li,C.
-30 18 12 6 n in LiC,
Ill II L II I Stage
e 5.4. Stage formation during electrochemical lithiation of graphite. A: Schematic
nt current charge curve. B: Schematic voltarnmetric curve.
Chapter 5

rved during the electrochemical reduction of carbons in Lt containing


rolytes. Figure 5.4A shows a schematic potential/composition curve for
onstant current reduction (charge) of graphite to LiC6 corresponding to a
um storage capacity of 372 Ahlkg with respect to the graphite mass. The
ntial plateaus in the curve arising during reduction indicate two-phase
ons (coexistence of two phases). Under potentiodynamic control (linear
ntial sweep voltammetry) the two-phase regions are indicated by current
s (Figure 5.4B).
Only within the small one-phase regions, the Li+ transport is a
sion process. Within the two phase regions, the stage transformation
eeds by nucleation of lithium and following phase boundary movement, a
181 183
reaction front propagates through the graphite. - The reaction front a
narrow width of <5 p,m and a rate of 5-10 mm/min. 183
Apart from the stage s = I, other binary phases corresponding to the
es s =IV, III, II L, and II (which can be also obtained by chemical
hesis12• 14• 25•26 ' 177' 179' 184) were identified and confirmed by X-ray
action 12' 14' 184- 188 and Raman spectroscopy. 189• 190 The splitting of stage II
two, s = II (x=0.5 in LixC6) and s = II L (x=0.33 in LixC6), is due to
rent lithium packing densities. The term II L indicates a liquid like
ture, which has no in-plane ordering [ 1911. A phase diagram of LixC 6 was
tructed from chemical184 and electrochemical188 data. There are different
rts in the literature about what happens at the beginning of intercalation,
how the "181 lithium" is accommodated in graphite, before the stage IV
pound is formed. It is reported, that the 1st lithium forms stages higher
189 192
s = IV. ' In contrast, it is said that the 1st lithium is randomly
ibuted in the graphite.188'193' 194 The discrepancies about staging are
ussed in Ref. 90.

.3. Nature of the Bond in Li-Graphite Intercalation Compounds

In 1934-1938 Hofmann and co-workers23'195 have proposed that the


in graphite intercalation compounds is of electrostatic nature, which led
to the term "graphite salts". Based on this proposal, Hennig and
34 196
agues ' and Ubbelohde and colleagues 197' 198 have developed the
ic model", e.g., lithium is stored in cationic form in graphite, whereas the
hite host takes over the correponding negative charge. Today, this model
ill in use and may be the basis for the term "lithium ion battery". In
ral, GICs show a larger electronic conductivity than pure graphite
efore GICs are called "synthetic metals"), which is an indicator for the
up of electrons by graphite. Moreover, the electrons are not
ogeneously, but locally distributed over the graphene planes, the
ron density being particularly high near the intercalated cationic
onaceous and Graphitic Anodes 157
7 143 146 199 202
tsY Li NMR spectroscopy ' ' - as well as quantum mechanical
ulations203 confirm the mostly ionic state of lithium in Li-GICs.
However, there is considerable criticism on the purely ionic model.
cially the Li-graphite bond in LiC 6 seems to be partially metallic (or
lent). Due to the aa stacking of the lithium guest layers, the Li-Li
nce along the c axis is smaller than the in-plane Li-Li distance (Figure
). On the other hand, the small increase in volume due to Li
calation can be better explained by assuming that the lithium is stored as
204
all size guest, i.e., in ionic form. Recently, Hightower et al. attributed
utral character to the Li in stage-!LiC 6 by using transmission electron
gy loss spectroscopy. Indeed, the potential of the stage-! compound
ure 5.4A) is very close (but is not the same!) to metallic lithium, whereas
higher stage compounds and the diluted stage-!compound show more
tive potentials. It is reasonable to presume that at the beginning of
calation the lithium is accommodated into graphite in a more ionic form.
is also in agreement with the possibility of formation of solvated Li
s (cf. Section 5.4.2). During further reduction, the intercalated lithium
ually becomes more neutral. However, as there is still a small potential
between the potential of metallic Li and that of LiC6, the Li in LiC6 still
ld be partly ionic. Even the lithium which is stored in hard carbons at
ntials of only 5 mV vs. LilLi+ is not in a fully metallic state (cf. Section
). Finally, also the regular in-plane order of guests in LiC6 (Figure 5.3B)
be better explained if the Li contains still some ionic charge which is
iding repulsive coulombic interactions with its near lithium neighbors.

.4. Reversible and Irreversible Capacity

Constant current charge/discharge curves for u+ intercalation/de


calation into/out of graphite clearly prove the staging phenomenon
ure 5.5A). Nevertheless, there are no sharp discontinuities between the
phase regions because (i) the packing density of LixC 6 slightly varies (a
e width exists), 12• 14 (ii) various types of overpotentials cause plateau
ing in galvanostatic measurements (and peak broadening in
12
mmetric measurements, respectively), '14 and (iii) in practical cases
um intercalation does not proceed homogeneously over the electrode.
retically, the Li+ intercalation into carbons is fully reversible. In the
tical charge/discharge curve, however, the charge consumed in the first e
significantly exceeds the theoretical specific charge for the first stage of
372 Ah/kg. The subsequent discharge recovers only -80-95% of this ge.
In the second and subsequent cycles the charge capacity is lower and
harge recovery is close to 100%. The excess charge consumed in the
cycle is generally ascribed to irreversible reactions (i) of Lt with
hite and (ii) of the (lithiated) graphite with the electrolyte.
Chapter 5

The first reasoning is only to a minor part responsible for the excess
ge. It is believed that reduction of impurities like H20 or 02 present on
arbon surface, reduction of surface groups at the prismatic surfaces, and
ersible lithium incorporation into the carbon matrix ("formation of
205 207
ue compounds" - ), e.g., by reduction of heteroatom-groups located
rbon layer edges in polycrystalline carbons, take place.
The main part of the irreversible charge loss, however, is due to
tions with the electrolyte, which typically consists of a mixture of
nic solvents and a highly soluble lithium salt. The strong reducing
er of graphite (and other carbon anodes), at potentials where lithium
53 208 211
calation proceeds, leads to reductive electrolyte decomposition. • -
suitable nonaqueous electrolytes, however, "passivating" films of

2.00
0
8 A
:::. 1.60
c
6 _J

4 .; 1.20
Discharge > Discharge
2
>
0 0.80
"iii
8 'E
Q)
6 0.40
0
4 a..
2 0.00
0
Charge 0 200 400 600 800
200 400 Capacity I Ah kg·'
Capacity I Ah kg·' 2.00
8
0 ·- +
::J
:::. D
6
B _J 1.60
ui
.4- > 1.20
2 >
0 Iii 0.80
8 .. 'E
6 ..
4 ..
a
a.. 0.40
2
0 0.00
100 200 0 200 400 600 800
Capacity I Ah kg·' Capacity I Ah kg·'

e 5.5. Typical schematic I" cycle charge/discharge curve of (A) graphite, (B) soft
n (coke), (C) soft carbon (low temperature, hydrogen containing), (D) hard carbon.

containing electrolyte decomposition products protect the carbon


ces and the electrolyte against further reactions with each other. These
s are considered to act as a "sieve" being selectively permeable to the
rochemically active charge carrier, the Lt cation, but impermeable to
other electrolyte component that would react with lithium, i.e., they are
onaceous and Graphitic Anodes 159

idered to behave as a electronically insulating solid electrolyte


212 213
phase (SEI). '
Since the reactions of lithium with carbon and surface impurities as
as the film formation on LixC6 are associated with the irreversible
umption of material (lithium and electrolyte), the corresponding charge
is frequently called "irreversible specific charge" or "irreversible
city". The reversible lithium intercalation, on the other hand, is called
ersible specific charge" or "reversible capacity". The losses have to be
mized because the charge and lithium losses are detrimental to the
ific energy of the whole cell and, moreover, increase the material
nses due to the necessary excess of costly cathode material, which is the
um source in a lithium ion cell after cell assembly.
The extent of the irreversible charge losses due to SEI formation
nds to a first approximation on the surface area of the lithiated carbon
109 208
h is wetted by the electrolyte. ' '211'214-222 However, detailed
223
stigations proved that the particle-size, ·224 -shape (fiber, flake, bead, or
225 226
to shapes, etc.), ' -thickness 211 '227 '228 and -morphologl29 -232 also
ence the performance.
A third contribution to the irreversible capacity is rather related with
roperties of the electrode than the properties of the active material. The
rate capability of a carbon electrode may be achieved by thin layer
posite electrodes that are made up from small particle size carbons, with
in the Jl.m range, that are mechanically bound together by an usually
58
nic binder material '215 '218 '233 -236 which supports the compactness of the
rode. Usually, the binder amount is in the range of a few wt%. The
er/carbon composite is attached to a thin copper foil functioning as
nt collector.
2
The presence of these "inactive" components makes the relation of
rial and electrode parameters with reversible and irreversible capacities
complex. For example, the binder in the electrode on the one hand
y coats the electrochemically active surface area, so that SEI formation
218 237
solvent co-intercalation reactions are reduced. • ' 238 On the other
, the rate capability is decreased because of the covered surface areas. In
ion, it has to be considered that the binder reduces also the capacity
use of the extra inactive mass.
Another influence of the inactive electrode components is due to the
that they experience the same potential as the active material. On all
ronically conductive electrode components (active material, conductive
ive and current collector) in contact with the electrolyte, SEI formation
place. In some cases, the binder also reacts in an irreversible reaction.

ductive additives like carbon blacks, which reversibly take up lithium, can not be
ered as inactive.
Chapter 5

rominent example for the latter effect are fluorinated binders like
(tetrafluoro ethylene) (PTFE; "teflon", (-CF2-CF2-)n) and several
239
(vinylidene fluoride) (PVdF, (CHrCFr)n)· Kavan has disclosed that
rinated polymers can be electrochemically reduced ("electrochemical
onization") at the conditions a graphite anode experiences in contact
an organic electrolyte in a lithium ion cell during charge. In general,
alogenated polymers react with lithium very easily. The dehalogenation
ds LiHal (LiF, LiCl...) and elemental carbon. The reduction of PTFE by
um is well investigated as PTFE was suggested by Gabano and
240
eagues as cathode for lithium primary cells. PTFE can be completely
241
erted into carbon by electrochemical reduction, therefore increases
42
irreversible capacitl and consequently should be avoided as binder
carbon anodes. The reaction of Li with halogenated polymers
aining vicinal halogen atoms is facilitated due to the formation of
getically favored products, i.e., conjugated C=C double bonds and LiF.
ially halogenated polymers which contain no vicinal halogen atoms, such
VdF and poly(vinyl chloride) (PVC) usually do not react, because the C
ond is more resistive against reaction with Li, which blocks the
239
ation of a conjugated carbon-carbon bond system. In contrast,
2431
san et al. [ have observed a highly exothermal reaction of PVdF with
ated graphite at elevated temperatures. It is likely that the presence of
cts or irregularities in the monomer sequence, which locally lead to
al halogen atoms in the partially halogenated polymer, may alleviate the
rochemical reduction by lithium.

3. Electrochemical Li Storage in Non-Graphitic


Carbons

Compared to graphite, non-graphitic (disordered) carbons offer a


r variety of structures and thus of sites available to lithium storage (cf.
ion 5.3.1.2). This leads to different constant current charge/discharge
ntial profiles [Figure 5.5(B-D)]. In analogy to graphite, however, there is
reversible part in the charge/discharge potential profile of these carbons, h
again can be attributed to reactions with the electrolyte and SEI
ation and to irreversible reactions of lithium with the carbon host.
It should be noted again that the use of the term intercalation is
icted to processes which involve the lithium accommodation within the
layer gaps of a layered host like graphite. Any other Li storage process
arbons without significant layered structure is considered as insertion
ess.
Depending on the precursor and the heat-treatment temperature the
onaceous materials discussed in this chapter contain heteroatoms in
onaceous and Graphitic Anodes 161

tion to the prevailing carbon atoms. In particular, carbons prepared at


eratures below 1000°C do not consist of pure carbon and can contain
tantial amounts of heteroatoms. Even highly crystalline graphite is
ated with heteroatoms at dislocations in the crystallites and at edges of
graphene layers (prismatic surfaces), which are supposed to affect the
ation of residue compounds and the (electro-)chemistry at the
rode/electrolyte interface. From this point of view, the influence of
-carbonaceous" elements which have been particularly added to the
on precursor material is of great interest. If the non-carbon atoms are
duced in the carbon lattice by intention, the term "doped carbons" is
. This definition is in contrast with carbons made from "carbon
usors" which contain heteroatoms by chance.

.1. Non-Graphitic Carbons Made from "Carbon Precursors"

Non-graphitic carbons can offer additional or simply more sites for


m accommodation than graphites. As a result, they show a higher
bility of reversible lithium storage than graphites. These so-called "high
ific charge" or "high capacity" carbons are usually synthesized at rather
temperatures of -500 to -1000°C and can exhibit reversible capacities
400 to -2000 Ah/kg, depending on the heat treatment, the organic
ursor, and the electrolyte used. When lithium is stored in the bulk of
graphitic (soft and hard) carbons, one can suppose that a higher specific
ge (in Ah/kg) requires a correspondingly higher volume (lower density)
e carbonaceous matrix to accommodate the lithium. The calculated X
ensities and average carbon layer distances of soft and hard carbons
te from that of graphite as follows: graphite: 2.26 g/cm 3 & 335.4 pm;
3 3
carbon: ""2.0 g/cm & 375 pm; hard carbon: 1.4-1.8 g/cm & 380-
85 43 146
pm. .1 • As a consequence, the charge densities (in Ah/1, these
metric values are important for small portable applications) of these
ons should be comparable to those of graphite.
The variety of precursor materials and of manufacture processes leads
rbonaceous host materials with various structures and compositions.
might explain the numerous models which have been suggested to
88 244
in the high capacity. Yazami et al. ' - 248 proposed the formation of
dendritic metallic lithium multilayers on external graphene sheets and
249 250
ces. Sato et al. " suggested that Lh covalent molecules occupy
st neighbor sites in intercalated carbons, i.e., they assume a higher in
density of lithium guests. Yata's and Yamabe's groups discussed the
bility of lithium bilayer accommodation within the graphitic galleries of
ns with high interlayer spacing of -0.400 nm.251- 256 Peled et al.213• 257•258
ested that the extra charge gained by mild oxidation of graphite is
uted to the accommodation of lithium at the prismatic faces between
Chapter 5

adjacent crystallites and in the vicinity of defects (cf. Section 5.4.2.3). In


. 259-264 it is assumed that small particle size carbons can store a
iderable amount of lithium at graphite edges and surfaces in addition to
lithium located between the graphene layers. The existence of different
265
torage sites is discussed by many other authors, -271 mostly however on
basis of different models. Other groups proposed that additional lithium
be accommodated in nano-cavities87'154 '156 -158 or pores,272• 273 which are
ent in the carbon at temperatures below -800°C and which the
272
trolyte can not enter. Alternative comparisons of the models can be
d in the reviews 12,14,60,85,87,90,91. The significance of the models is
er controversially discussed.267 -278
For a systematic correlation of the lithium storage capacity with the
cture of the parent carbonaceous material, we will use the considerations
Dahn's group,277-281 which are supported by work of Fischer and
eagues 141' 142' 282' 283(cf. also their recent reviews 282' 284).
Their understanding is based on the structural model of graphitizing
t) and non-graphitizing (hard) carbons proposed by Franklin (cf. Section
1.2 for the Franklin model and other related information). If soft and hard
ons are prepared at temperatures of "'650 to 900°C, they show very high
cities, which are especially high at very low temrceratures.274• 285 In
278 2 0 281
252 277
tion, they exhibit a potential hysteresis: • • • the lithium
'
rtion occurs close to 0 V vs. LilLi+ whereas the lithium de-insertion
rs at much more positive potentials (Figure 5.5C). The hysteresis is due
netic hindrances,281 as the insertion/release of Li into/from these carbons
sociated with large exothermal heats.286
These low-temperature carbons can be considered as an intermediate
rial between the organic precursor compounds and carbon, as
287
iderable hydrogen is still contained in their structure. The extent of
um storage capacity and of potential hysteresis is assumed to be
ortional to the hydrogen content in the carbon.274' 278' 288 The hydrogen is
ed at the periphery of aromatic molecules constituting the basic
ture units. The ratio of hydrogen to carbon (H/C ratio) in the material is
when a substantial amount of hydrogen is present during manufacture,
r because hydrogen is already incorporated in the precursor material
or by manufacture under H2 atmosphere. It has been suggested that
um is bound near single proton terminated edge carbons which induces a
3
al bond change at the carbon from sp2- to sp -hybridization.281• 282 The
change requires activation energy for both the lithium insertion and
oval process leading to the observed potential hysteresis. Alternatively, a
kage-recovery model of weak C-H bonds has been suggested in Refs.
290. Other ideas for the lithium storage mechanism are discussed in
. 291-293.
With increasing temperature the electrical conductivity of the material
294
ases by several orders of magnitude and hydrogen is removed.
onaceous and Graphitic Anodes 163
295
lly, all hydrogen is lost at temperatures of 1000°C, whereas oxygen
296 297
nitrogen (1500°C) and sulfur (2000°C) are lost at higher
eratures and thus may still have an effect on the lithium storage
vior. The specific charges achieved after the removal of hydrogen
nd on the structure of the carbonaceous material, whether it is a soft
phitizing) or a hard (non-graphitizing) carbon.J57,159,202,278,281,298-30J
At temperatures -1000°C the graphitizing (soft) carbons develop a
rdered structure, which offers a lower number of sites for lithium
12 14 53 85
calation as compared to graphite. ' ' " In addition, cross-linking of
on layers in disordered carbons hampers the shift to AA stacking, which
cessary for the accommodation of a higher lithium amount into graphitic
02 304
? - Correspondingly, rather low capacities of ::::150-200 Ah/kg are
rved in soft carbons like turbostratic carbons, and more disordered
ons like cokes and certain carbon blacks. The potential profile of the 1st
ntercalation/de-intercalation cycle of a coke electrode differs from that
raphite, in the sense that the reversible intercalation of Lt begins at a
ntial >1 V vs. Li!Lt, and the curve slopes without distinguishable
aus (Figure 5.4B). This behavior is a consequence of the disordered
ture providing electronically and geometrically non-equivalent sites,
eas for a particular intercalation
3 stage in highly crystalline graphite the
are basically equivalent.5
With increasing treatment temperature soft carbons develop more
hitic structure segments. The sites for lithium storage which were
erly determined by the disordered structure (see above) change to
hitic sites, where lithium resides in the Van der Waals gaps between
red graphene layers. Finally, at -3000°C the structure 12of14graphite with
ready reported electrochemical performance is achieved. '
In contrast to soft carbons, many non-graphitizing (hard) carbons
ned at temperatures of -1000°C show a high specific charge with little
resis. This high specific charge of several hundreds Ah/kg can be
ed only at a very low potential of a few mV vs. Li!Lt (Figure 5.5D).
paring with graphitic carbons and cokes which show volume expansions
contractions in the range of -10% during cycling, the hard carbons are
ed not to be subject to dimensional changes during lithium uptake and
val due to the high distance of >-0.380 nm between two neighboring
143
on layers. In order to explain the high capability of lithium storage in
277 279 305 308
graphitizing carbons, Dahn et al. ' · - suggested that lithium is
orbed" on both sides 305 of single graphene la1ter
06 sheets which are arranged
a "house of cards" or like "falling cards" (Figure 5.6A). The "falling
" model is the advanced form of the "house of cards" model and takes
into account the storage of lithium in micropores. Both the pore size and
ore openings should be small to avoid the reaction of stored lithium
the electrolyte. '279" 305' 309 Recent studies on a hard carbon prepared at
278

°C reveal that the size of the single layers as well as the size of the
Chapter 5

141 142 282


s are in the range of 1 nm. ' • In conclusion, a large fraction of
le layer sheets and nanopores is beneficial for the lithium storage
bilities of hard carbons.
On the other hand, heat treatment higher than 1oooac leads to
159 310
tically reduced capacities of hard carbons. ' This may be related to
279 284
bum-off of material or to a slight mobility of single carbon layers,
ch causes the opening of the nanopores. Electrolyte can penetrate in, and
ites in the pore are no longer available for lithium storage (Figure 5.6B).
sensitiveness of nanoporous hard carbons might be a difficulty for
ace treatment processes involving higher temperatures.
The existence of different lithium storage sites in these carbons have
7 143 146 311
also monitored by Li NMR spectroscopy. In conclusion, the
• •
um stored in soft carbons is considered as almost fully ionic, whereas the
um in hard carbons is present in two different states, (i) a pseudo
llic (but not metallic!) state of the lithium, which is stored at potentials
e to the lithium metal potential, and (ii) an ionic state of the lithium
ed at higher carbon electrode potentials. The pseudo-metallic character
thus the- compared to ionic lithium- reduced repulsive coulombic

e 5.6. A) Mechanism of lithium storage in hard (non-graphitizing) carbons;


ectrolyte penetration in the pores after pore opening.

action between neighboring lithium is an explanation for the higher


um packing density in pores and at the single carbon layers.
Finally, it should be emphasized that the above proposed models for
um storage in non-graphitic carbons are based on a limited number of
riments made with a limited number of carbonaceous materials (for the
precursors, cf. Refs. 85,94). This means that carbons may be
hesized which do not belong to any of the above categories. For
ple, it cannot be excluded that lithium storage in nanopores and near
ogen terminated edge carbons proceeds in parallel. For another example,
s reported that milling of hard carbons alters the charge/discharge curve
3121
pletely, as hysteresis is observed. This may be explained with a
onaceous and Graphitic Anodes 165

um storage mechanism near oxygen surface groups, as carbon-carbon


cleavages due to milling create unpaired electrons which react with
en from air thus creating the surface groups.
Tarascon and colleagues found that also milling of highly graphitic
ons resulted in graphites with very high reversible and irreversible
109
cities. - 111 As the milling creates structural disorder, an
rochemistry-structure relation may be indeed valid also in this case.
ever, the milling creates also a large number of broken bonds and
fore unpaired electrons, which react with hydrogen or oxygen present in
tmosphere during the milling process; some contribution of heteroatoms
e capacity may be taken into account, too.- 113• 116
282

Despite the fact that the high specific charge carbons show a multiple
e specific charge of graphite, there are still some problems to solve.
In many cases extremely high irreversible specific charges were
rved,157• 253• 265'277- 279• 284• 313- 315 occasionally also at higher cycle
bers.265•278•313 •314•316 •317 The' irreversible capacities can be correlated with
formation of the SEI. 157 278279 '
313 317
' ' However, an "irreversible lithium
265 317 320
rporation" into the carbon is discussed, too. • - Apart from an
ersible trapping of lithium in the pore volume of disordered carbons, 320
arge fraction of (internal and external) heteroatorns in the non-graphitic
ons, such as hydrogen and oxygen, can irreversibly bind a considerable
unt of lithium during reduction of the carbon.Z65• 284·317 -319 In addition, the
amount of polar surface groups adsorbs large amounts of impurities
air, which can irreversibly react with lithium and thus have to be
321
ved.93•312• All of the above charge losses have to be compensated by
xcess of cathode material as lithium ion cells are assembled in the
arged state. As, in contrast to hydrogen-containing carbons, hard carbon
electrochemical properties suitable for application in lithium ion
143
ries, there are attempts to reduce the irreversible capacity of hard
312 315 318
ons by changing the surface properties.284 • • •
3221
With one exception r , carbons exhibiting hysteresis show a low
iency and poor cycling performance. Furthermore, they can be
251
arged only over a broad potential region of about 1-2 V.87• 157 158 -
• •
7-279'305'308'313 As a result the practical energy efficiency of a lithium ion
s reduced.
The end of charge potential of non-graphitic carbons must be chosen
close to 0 V vs. LilLi+ in order to obtain the available capacity. The
w "safety gap" separating from the potential where metallic lithium is
sited on the carbon surface might give rise to some safety problems of
carbons. In particular, if fast charging is applied, there is a high risk of
m plating at the end of charge. In some cases 278 •279305

308
• the hard carbon
rode was indeed charged below 0 V vs. Li/Lt and dendritic323 lithium
sition on such carbons was observed. In contrast, there is a difference of
Chapter 5

oximately 0.1 V between the potential of LiC6 and the potential of


um deposition (Figures 5.3A and 5.5A).
At a very low temperature, -30°C, a high polarization of the carbon
trode is observed, which is equivalent to a high overpotential. As the
potential shifts the lithium insertion potential downwards beyond the
um deposition potential, parts of the lithium storage capacity are not
lable anymore. Even the lithium intercalation capacity of graphite is very h
24
reduced in this case? Cokes might benefit from their smooth change
324
thium storage capacity as a function of the potential (Figure 5.5C).
effects of low temperature on the lithium storage capacity of hard
ons at 5 mV vs. LilLi+ (Figure 5.5D), however, must be dramatic.
The reported limitations of non-graphitic carbons seem to favor the
of graphitic anode materials at present. On the other hand, the
ge/discharge profile of hard carbons gradually changes with time, which
vantageous for estimation of the capacity of a lithium ion cell. Hybrids
raphitic and non-graphitic carbons may be a reasonable compromise (cf.
ion 5.4.2.3).

.2. Non-Graphitic Carbons with Heteroatoms ("Doped Carbons")

The reaction of precursor materials (i) containing carbon atoms


ther with (various) heteroatoms or (ii) combining a "carbon precursor"
"heteroatom precursors" can result in a variety of doped carbons
rials with interesting physical and (electro-)chemical properties. The
bination" of carbon and heteroatoms is done by the following methods:
hanical milling, chemical treatment of carbons with the dopant atom
aining precursor at elevated temperatures, chemical vapor co-deposition,
co-pyrolysis. Doping of carbons has been originally applied in order (i)
hange the chemical composition in the bulk and/or the surface, (ii) to
ge the electron distribution, and (iii) to enhance (catalyze) or slow the
325 327
hitization process. - The dopant can be substituted for carbon or is
tionally incorporated in the carbon. For further details, in particular
rding the synthesis and preparation of the materials, see Refs.
5,328,329. For the application in lithium ion cells, B, N, S, Si, and P
been preferably used as dopants.
Boron is assumed to act as an electron acceptor in a carbon host and
to cause a shift of the intercalation potential to more positive values and
53 85 330 335
crease of the reversible capacity due to more electronic sites.
• • -
can enable a more rapid charging process. For HOPG it has been found
336
B substitution results in a more disordered structure. This might be the
n for the compatibility of B-doped graphites with electrolytes which are
compatible with undoped graphites. B-doped graphitized carbon
327 334 337 338 339 340
s ' ' ' are used by Toshiba. •
onaceous and Graphitic Anodes 167

Nitrogen can be incorporated substitutionally into carbon, and a co


ng with B is also possible. N presumably functions as an electron donor
should therefore have the opposite effect on the reversible capacity and
nsertion potential.53 "341 Contrarily, others342 "343 report that N-containing
ons can provide high specific charges of -500 Ah/kg. Whereas the
er lithium storage capability of the above B- and N-containing anode
rials is mainly explained by different electronic properties of the
53 331
• the high specific charge of phosphorous-doped carbons, 344.349
dy observed in 1991,350 is discussed on the basis of steric effects.344
r substituted carbons, such as layered B/C/N materials351 -357 and
42 358
• have been evaluated, too.
High capacity lithium storage materials derived by pyrolysis from
on-containing precursors like silicon-containing polymers or epoxy e
composites have been the subject of investigations, too.359 -368 In
tion to silicon and carbon, these materials can contain a substantial
unt of hydrogen and oxygen, which can lead to a large variety of
361
positions?60 • Apart from high reversible capacities of up to 770 Ah/kg,
h seem to depend on the Si content in the matrix, 361" 362 these materials
lly exhibit strong potential hysteresis and large irreversible capacities
0 Ah/kg). The interactions of the various heteroatorns with each other
with the carbon atom neighbors and their influence on reversible and
ersible lithium storage seem to be quite complex and have not been
ely clarified yet. Also, the nature of the lithium insertion mechanism is
366 367
uncertain. In some reports, • it was proposed that carbon/silicon
posite materials were prepared by above synthesis procedures. The high
sible capacities can be explained by the high Li alloying capacity of
on in addition to the lithium incorporation in disordered carbon regions
eeding independently?68 "369 If true, the insertion mechanism of a Si
l/carbon composite would be different from that of Si-doped carbon.
For all doped carbons based on non-graphitic low temperature
ons, there is some uncertainty about the effect of doping. In particular, in
e cases it is not clear whether the structure, the chemical composition, or
are responsible for the observed lithium storage behavior.

REACTIONS OF LITHIATED CARBONS WITH


THE ELECTROLYTE

The solid electrolyte interphase (SEI) concept (cf. Section 5.3.2.4)


ribes the filming behavior observed on the LixC6 anode in a very basic
general way. In fact, SEI formation is a complex process and the formed
do obviously not have the properties of a true solid electrolyte for
m cations with a transference number tu+ = 1. Nevertheless, the SEI
Chapter 5

ept has been quite generally accepted due to its simplicity.


The first note on the solid electrolyte character of the film formed on
370 213 371 372
llic Li in organic electrolytes was made by Dey. Peled • • has
ussed the reaction of Li and other reactive metals with organic and
ganic electrolytes in detail and has proposed the term SEI for the unique
the term being in use until today. It should be emphasized that the
nal work of Peled considers the SEI as a new phase formed between
e phase and electrolyte phase at the electrode/electrolyte interface, i.e.,
an "interphase", not an "interface". Depending on the electrolyte, other
mposition products may be liquid and dissolve or accumulate in the
43
rolyte or are gaseous, ' - the latter increasing the cell pressure.
373 378

1. Interphase Formation- Metallic Li Anode vs. LixC 6


Anode and Oxide Cathode

Though
• the SEI concept has been basically adapted for carbonaceous
08 210 212 213
es/ • ' there are significant differences between film formation
esses on metallic lithium and lithiated carbon. Film formation on
llic Li takes place upon contact with the electrolyte. The electrolyte,
h consists of various electrolyte components (solvent(s), electrolyte
ives, electrolyte salt, impurities) decomposes spontaneously with low
14
tivity, and some of the decomposition products form the film. On the
ary, film formation on the surface of carbonaceous hosts takes place as
arge consuming side reaction in the first few Lt intercalation/de
calation cycles, especially during the first reduction of the carbon host
rial, leading to the so-called "irreversible capacity". In this case, the
rolyte components which are least stable towards reduction selectively
first. The chemical composition of the SEI on lithiated carbon varies
14
gh the depth of the film. In addition, the film composition and
hology is also laterally non-homogeneously distributed over the carbon e
79
surface? As a consequence of the difference in the reduction
vior to metallic lithium, dissimilar intermediate reduction products and
rent decomposition mechanisms of the electrolyte may occur in the
nce of lithiated carbon.
Finally, the behavior of metallic lithium and of lithiated carbon,
ctively, during battery charge and its influence on the SEI has to be
ssed. Upon recharge of the Li anode, lithium plating occurs
ltaneously to lithium corrosion and "passivation" (formation of SEI).
, lithium deposits as highly disperse, highly reactive metal particles.
e dendrites are covered with SEI films, which in some cases
ronically insulate them from the rest of the Li. Thus, the dendrites are
onaceous and Graphitic Anodes 169

ally electrochemically inactive. This reduces the efficiency of the


um dissolution/deposition process. Moreover, the dendrites grow to
ents upon cycling, which may short-circuit and locally overheat the cell
cause a disastrous thermal runaway due to the low melting point of
ly reactive Li (-180°C) and reaction with the organic electrolyte. The
e reactions imply that the surface of a metallic lithium electrode is
dically renewed during cycling, i.e., a "new" SEI is formed in each e.
Unless the Li electrode becomes inactive due to full passivation, this
ess can be repeated 12 49 59until the Li anode and/or the electrolyte are
61
pletely consumed. ' - '
At difference, the surface of the lithiated carbon electrode is all the
passivated by the SEI during cycling and no dendrites are formed as
um is inserted into carbon. The film formation on lithiated carbons
eeds in several subsequent steps. These are of course influenced by the
ions taking place in parallel at the carbon anode, e.g., reduction of
on surface groups and surface impurities, unsolvated and solvated
m insertion and self-discharge reactions. For ester-based electrolytes
ollowing reaction sequence can be assumed: (i) electron transfer from
380 382
cathodically polarized electrode in the electrolyte solution - and
381 382
ation of a solvated radical anion · (and possible intermediate
213 383
ence of solvated electrons ' ), (ii) chain reaction of the radical with
hboring electrolyte species (e.g. further electron transfer) leading to
381 382
uble products " (iii) precipitation of these products on the carbon
384
e surface by nucleation and crystal growth, (iv) further precipitation
385 387
a dense, but also thicker film is formed, - as well as further
ction of the film products deposited near the carbon anode which is
ming gradually more reductive. In contact with the highly reductive
lithiated carbon anode only fully reduced (inorganic) species, such as
LiCl, LizO, or LizC03 can exist. Partially reduced (organic) species can
"survive" in SEI regions far 12 14away
213 from the reductive carbon anode
ce near the electrolyte side. ' ' The inorganic part may be as thin as
388
389 390
The film thickness and resistance increase during charge · and
390
arge. The increase seems to be a discontinuous process proceeding in
385 386 389391
al steps. · · · The film formed in the first cycle has a thickness of
08 378 385 387
al tens of nm.Z ' ' - The thickness of the SEI increases to several
·14·388 durm. g eye1"mg or storage
h . .
t e rest stance creases m
and .
m
392 399 400
lel. - This process contributes to "cell aging". The increase of the
resistance and thus the higher overpotentials or even the electronic
ation of carbon particles by the SEI are considered as main reason for
96 398 401
city fade of carbon electrodes during cycling? · · .4°2 In parallel, SEI
ucts may dissolve in the electrolyte, which is a major factor for the self
403 405
arge of lithiated carbons. - SEI formation and dissolution are in a
Chapter 5

amic equilibrium.405 Peled406 accounts the breaking of the SEI due to


hite expansion/contraction during lithium uptake/release for the self
harge phenomenon. A list of factors contributing to self-discharge is n
in Ref. 405. Especially in the first cycles, self-discharge is a serious
lem as the SEI is not fully developed and thus sufficiently protective.
surements of self-discharge of sufficiently filmed lithium carbon
trodes show a linear lithium loss with storage time during -40 d of
age. Thereafter, the reaction rate decreases, but self-discharge is still
407 408
tent after even -170 d. ' The self-discharge rate of the carbon anode
409 410
eases with temperature, ' which may be associated with the
easing rate for SEI dissolution or breakdown.409•4 u.412 Broussely et
0·410 concluded that the electronic conductivity of the SEI is the main
ributor to the self-discharge of a graphite electrode. This assumption
ies that the SEI is not a true solid electrolyte.
Also at the cathode an interphase consisting of reaction products of
ode material and electrolyte is formed, 12.413.415 which shows "SEI-like"
erties. The electrolyte decomposition products at the cathode are,
ever, formed by oxidation. Due to the fact that various cathodes, e.g.,
o02, LiNi02, LiMn204, LiFeP04 and derivatives are used, the interphase
positions and formation mechanisms may vary more than for
onaceous anodes, which all basically consist of carbon. It has been
419
rted,392·416- that the cathode interphase contributes more to the overall
resistance than the anode interphase (SEI).
It is furthermore assumed that SEI components can migrate between
anode and cathode, which would correspond to a shuttle mechanism
420
ting self-discharge. As the transition metal oxides used for the cathode
thium ion cells partially dissolve in the electrolyte,409·421-423 and then are
sited in metallic form on the carbon 424 surface or are accumulated in the
e-SEI, Komaba and co-authors have studied the influence of
ganese, cobalt, and nickel ions on the SEI formation process. They
d detrimental effects both on capacity and on rechargeability. A general
conclusion to be drawn is that reactions at the cathode and anode and
interactive behavior should be considered in parallel.
The chemical composition and the properties of the films formed on
hite and the mechanisms involved with their formation have been
yzed by various sophisticated in situ and ex situ analytical tools. For
e reasons, in this chapter we may only mention the works of Aurbach's
p,413-415.425·426 Novak's group 216'217'375-378 and Peled's and Golodnitzky's
_212,213,379
The obtained information, however, has to be carefully considered.
ral reports had to be withdrawn because later they were disproved by a
sophisticated method. A general limitation is also that a certain
ytical method is only providing a piece of information, but does not give
onaceous and Graphitic Anodes 171

omplete set of facts. Therefore, a certain property or property change of


ilm, which has been detected by a particular method may, but not
tably, be related to a corresponding (change of) electrochemical
ormance. Furthermore, the electrolyte decomposition products are highly
tive to reaction with moisture and other atmospheric species, which s
the meaning of ex situ results. On the other hand, using in situ or on
methods, the relevant information may be so complex that it is not easy
xtract the relevant information. The situation is getting even more
plex, due to the large number of electrolyte components and their
ures as well as due to the fact that the formed film and the other
rolyte decomposition products contain various species. Moreover,
rent charge/discharge regimes under various conditions, such as
erature, result in SEI films with different properties. For instance,
er charging currents result in low irreversible capacity and low SEI
406 409
tance. • Finally, also the effect of impurities in/on the electrode and
427
e electrolyte, .428 such as water,378 •409 .429 -432 always has to be considered.
large number of effects may be the reason for the quite often
nsistent reports on the SEI film.

2. Unsolvated and Solvated Lithium Intercalation


Apart from reactions with the electrolyte at the carbon surface, the
ersible capacity is furthermore strongly affected by the possible co
calation of polar solvent molecules between the graphene layers of
y graphitic matrices. This so-called solvated intercalation reaction
nds (i) on the composition of the electrolyte and (ii) on the crystallinity
morphology of the parent carbonaceous material.

.1. Effects of the Electrolyte on Co-Intercalation and SEI


Formation

In general, the intercalation of Li+ from electrolytes with organic


r solvents into fairly crystalline graphitic carbons quite often yields
ted (ternary) lithium-graphite
• intercalation compounds, Lix(solv)yCn
433 12 14 6 7 59 60 208
re 5.7B). ' .4 .4 • • • The co-intercalation of the large solvent
cules is associated with extreme expansion of the graphite matrix
cally >100%), frequently leading to graphite exfoliation (shedding of
e graphene layers or packages of graphene layers), and mechanical
tegration of the electrode. This large expansion is possible as the
tive interaction of the donor solvent shell with the Li+ cation is much
ger than the Van der Waals forces between the graphene layers of
Chapter 5

hite. In the "best" case reduced charge storage capabilities, in the worst
complete electrode destruction are the results of this reaction.
As long as the content of lithium in the graphitic carbon is low (
in LixC6), the ternary lithium-graphite intercalation compounds are
modynamically favored over the unsolvated binary compounds, LixC 6
ure 5.7A). Hence, the potentials of their electrochemical formation are
e positive than those for the formation of the corresponding compound
6. At this stage of Lt intercalation the coulombic interaction between
lithium guest layer (Ln and the balancing negative charge distributed
the graphene layers (Cn) is weak, and space to accommodate large
12 14 59 60 34 435
ent molecules is still available. • • • .4 •
The solvated GICs are thermodynamically unstable with respect to the
12 14 59 60
ction of the co-intercalated solvent molecules. The kinetically
• · •
rolled reduction depends on the type of co-intercalated solvent. It is slow
e.g., dimethyl sulfoxide, where even staging of solvated GICs can be
.4 6.4 46
where the
' -
11 3 37 43 438 441
rved, but very much faster for, e.g., PC, '
trochemical intercalation followed by fast decomposition of the
calated Lt(solv)y can be misunderstood as simple electrolyte
mposition. The reduction of Li\solv)y inside the graphite is associated
extra irreversible capacity.
Both effects resulting from solvent co-intercalation, the mechanical
ruction and the higher irreversible capacities, seriously complicate the
ation of graphitic anode materials. Due to the fact that ternary lithiated
ons are thermodynamically favored at low lithium concentrations in the
hite, i.e., at the beginning of intercalation, kinetic measures have to be
ied to diminish or even to completely suppress solvent co-intercalation.

Binary (unsolvated)
A lithium-graphite
intercalation compound

00000000
00000000

Ternary (solvated)

B lithium-graphite
intercalation compound

-graphene layer o
lithium
0 solvent

e 5.7. Schematic drawing (A) of binary and (B) of ternary lithium-graphite intercalation
ounds, as well as (C) of the SEI formed on/in graphite via electrochemically formed
ted lithium/graphite intercalation compounds.
onaceous and Graphitic Anodes 173

This can be accomplished by using electrolyte components that form


tively protecting SEI films, which are only permeable for unsolvated
208
um cations. The first effective solvent in this respect was ethylene
433 42 446
onate (EC). .4 - Since the viscosity of electrolytes using pure EC is
r high, mixtures of EC with low viscosity solvents such as dimethyl
onate (DMC), diethyl carbonate (DEC), ethyl methyl carbonate (EMC)
widely used.447-453
Although the formation of binary lithium-graphite intercalation
pounds prevails in EC-based electrolytes, many examinations point at a
formation mechanism, where also solvated lithiated graphites
cipate. Film formation in the first cycle during the first reduction of the
material is not a simple surface reaction but a rather complex three
nsional process, taking basically place at a potential of -1 - -0.6 V vs.
445 454 455 189
t (Figure 5.5A). In situ dilatometric, STM, • and Raman
ods indicate a (partially) large expansion of the graphite host
sponding to the (intermediate) formation of Lix(solv)yCn at those
ntials. The reduction of Lix(solv)y on parts of the internal surfaces
een the graphene layers results in an "extra" film, which penetrates into
bulk of the graphite host (Figure 5.7C). Correspondingly "extra"
445
ersible charge losses are observed. The penetration depth of the film
the graphite depends on how deep the reaction front of solvated lithium
can propagate into the graphite, before the solvated lithium is
ctively decomposed inside the graphite. Several investigations indicate
the film formation and solvent co-intercalation
192 385 386 389 454 processes
456 on/into
hite can be even more complex. · · · ' - Solvent co-
intercalation
C-based electrolytes depends on the kind of the low viscosity co
458 459
nt457 and the kind and concentration of the electrolyte salt.
The structures of EC and PC are very similar 217 and both solvents evolve
216 217
s, ethylene (EC) ' .460 or propylene (PC)43 ' during reduction, but
tendency to exfoliation of graphite is dramatically different. Therefore,
is controversy about the reactions occurring in EC- and PC-based
rolytes.
461
Ross and colleagues have observed a significant kinetic hindrance
462
C reduction. Chung et al. .463 have proposed a strong dependence of
olvent co-intercalation behavior on structure of the solvent, by using
rently methyl-substituted PC molecules: cis- (c-BC) and trans-butylene
onate (t-BC). c-BC does, t-BC does not co-intercalate into graphite,
h is explained by steric hindrances.
425 464
Aurbach and colleagues ' attribute the exfoliation of graphite in PC
rolytes to the penetration of graphite openings such as pores and fissures
lvent molecules. Due to the fact that the graphite is only insufficiently
vated by the SEI in PC electrolytes, PC decomposes inside these
ings to propylene gas, which pressure induces cracking of the graphite.
formed cracks allow massive penetration of PC molecules inside the
Chapter 5

hite matrix, where they are reduced. Again gas is produced, which leads
rther cracking and so on. This reaction mechanism involves no PC co
calation step. This behavior seems to be only typical for PC electrolytes,
or electrochemical reduction or oxidation of other nonaqueous and
ous electrolytes, which results into strong gas evolution; a similar and
rapid mechanical destruction mechanism has not been reported so far.
465
Takamura and colleagues investigated highly graphitized carbon
rs in PC based electrolytes. They found a dependence of the extent of
liation on the number of used carbon fibers and their relative orientation
ach other. With a single fiber no exfoliation and very low irreversible
city could be observed. With a bundle of five fibers in which the fibers
been irregularly oriented to each other, strong exfoliation takes place;
irreversible capacity is high. However, if the fibers in the bundle are
nged in parallel to each other, the extent of the exfoliation reaction is
much reduced. They attributed the exfoliation to an inhomogeneous
ent distribution in the bundle, which does not occur with a single carbon
r. One might, however, also speculate that the irreversible capacity in
case is also reduced, when the current density is high and furthermore is
orm for the total surface area of the anode material.
466
The authors have investigated the reactions of graphite vs. PC by in
electrochemical dilatometry. Strong macroscopic expansions of graphite
r, which can be partially reversible under certain conditions. The results
est that PC co-intercalation into graphite is the initial step, which opens
ssures and pores in the graphite. The second step is physical penetration
C electrolyte into these openings of graphite, then gas evolution inside
hite, which causes strong mechanical stress and graphite destruction.
462 63 67
subsequent reaction process is also supported by Chung et al. .4 .4

2.2. Film Forming Electrolyte Additives and Electrolyte


Components

The choice of solvents or solvent mixtures for a certain lithium ion


ry application is usually a compromise between the desired physical
, electrolyte conductivity, volatility, flammability, wetting ability, etc.)
electrochemical properties (reduction and oxidation at the respective
rode/electrolyte interfaces, solid electrolyte interphase (SEI) formation
v1. 0r, etc.).468·469 A n elegant way to overcome the m· evt·tabl e
1t·mt·tatt·ons is compromise is the use of electrolyte components, which
even in small unts ("additive amounts") improve the electrolyte
properties in the
468
ed direction. The technical realization of this concept is quite simple,
e electrolyte additive can be just added to the base electrolyte. Among
y additive applications, such as safety improvement and overcharge
ction, electrolyte components for improved film formation processes at
onaceous and Graphitic Anodes 175

e and cathode have found particular interest. Beside EC, significant


ovements have been achieved at the anode with a large number of film
ing components.
The first
ponents such as reports deal with gaseous
co2 ,390.403.433,446,470-474 electrolyte
Nz0,390,474 additives and
and 502_445,474-476
Some other prominent examples are derivatives or analogous
pounds of the cyclic carbonates ethylene carbonate (EC) and propylene
477 481
onate (PC), e.g., chloro ethylene carbonate - (which evolves C02
460 482 483
ng reduction ' ), 4,5-dichloroethylene carbonate, fluoro ethylene
484 477 481 485
onate, trifluoro propylene carbonate, ' ' vinylene carbonate
486 491 492 468 493 494
), - catechol carbonate, ethylene sulfite ' ' and propylene
495
te.
390 474 96 497 498
Other sulfur additives are: S/, ' .4 ' sulfites ( and cf. above),
499 500 501 493
ane sultone, ' S02 (above), sulfates, etc.
Also derivatives or analogous compounds of the linear carbonates,
yl carbonate (DEC) and dimethyl carbonate (DMC), e.g. dimethyl
493 502 503
te and diethyl sulfite, • S,S-dialkyl dithiocarbonates, 2-
504 505 506
oxyethyl (methyl) carbonate, dimethyl pyrocarbonate (DMPC), ·
506 182 507
tyl pyrocarbonate, ethyl propyl carbonate, ' ethyl methyl
508 509 510 511
onate · and other asymmetric alkyl methyl carbonates, · 1-
512
oroethylmethyl carbonate, and other partially fluorinated linear
513 406 514 515
onates have been proven to be useful. Even LizC03 ' ' is an
tive electrolyte additive.
A third family of compounds include partially halogenated organic
pounds such as bromo butyrolactone,516 chloro and fluoro ethylene
onate (see above), trifluoro propylene carbonate (see above), fluorinated
517 518 519
yclic compounds as glycol ethers and other ethers, urethanes,
520 521 522
ol esters, N,N-dimethylamino trifluoro acetamide, • trifluoro
methyl carbonate and other partially fluorinated linear carbonates (see
516
e), and methyl chloroformate. An overview on fluorinated solvents,
beneficial low-temperature and safety behavior, how they operate in the
etc., is given in Refs. 523,524.
A novel class of additives incorporates polymerizable unsaturated
s. These include vinylene compounds, such as vinylene carbonate (VC,
522 525 527 528
above), acrylic acid nitrile, ' - ethyl cinnamate, and vinylene
529 526 527
te. The reaction ' is proceeding according to:

=/X
+e· .. =/X
=--'X
•e

" -X" being an electron-withdrawing group (see also below).


In general, the films
390 505formed in the presence
489 of electrolyte additives
it a low resistance • and are very thin.
Chapter 5

Many of the above film forming compounds take advantage from the
that they are usually reduced at quite positive graphite electrode
ntials, i.e., at the early stages of the first reduction of the graphite
trode, before detrimental side reactions such as solvent co-intercalation
eed. The formed films have SEI properties. Solvent co-intercalation n
as a side reaction) is suppressed. This sensitiveness towards reduction
be explained (i) by the electron-withdrawing effect of chlorine- or
rine-groups introducing partial positive charge on the molecule
orinated and fluorinated solvents) or (ii) by the presence of atoms or
ps in the molecule which have a high electron affinity, e.g., sulfur in the
ation state +IV (sulfites) or double bonds (vinylene compounds). The
ction behavior and the reduction potentials of film forming components
461
be also calculated, '486 though the dependence on the chosen
rimental conditions (type of electrode and co-electrolyte components,
ge regime, kinetics, etc.) will inevitably make a practical test necessary.
In many cases, electrolyte additives not only improve typical lithium
battery electrolytes, but also allow the use of PC-based electrolytes and
r electrolytes not compatible with graphitic anodes. Especially, the use
C instead of EC in a lithium ion battery electrolyte is highly desired, as
as a large liquid range from -49°C to +240°C, whereas EC is a solid at
temperature. Thus, PC-based electrolytes usually show a low
erature performance desired for use in lithium ion cells. The low
osity of the PC at lower temperatures is counteracted by the still high
uctivity of the SEI film formed in the presence of PC.530
There is no universally applicable electrolyte additive or electrolyte
ent available and therefore additive/solvent mixtures are used at the
ent. However, the cross-interaction of the various electrolyte
ponents contributing to SEI formation is an issue of concern. For
ple, in electrolytes designed for good low temperature performance, not
still comparatively high electrolyte conductivity, but the low ionic
uctivity • of lithium within the SEI formed in these
rolytes,324 506' 531' 532and especially the low conductivity within the carbon
24
riae •506• 533 at these temperatures, limit the low temperature
ormance. Similar observations were made with flame retardant or other
y-relevant electrolyte additives which may deteriorate,534• 535 but also
improve536 '537 the SEI formation process. Finally, electrolyte additives
esired, which are in parallel beneficial for the interphase formation at
e and cathode.

.3. Effects of the Carbon on Co-Intercalation and SEI formation

Disordered soft and hard carbons are much less sensitive to solvent co-
onaceous and Graphitic Anodes 177

calation than highly crystalline graphites. The crosslinking between the


3
hene layers and graphite crystallites by sp -hybridized carbon atoms
hanically suppresses the formation of solvated lithiated
12 14 53 59 60 85 208
hites. • • • • • • As a result the gap between the layers cannot
nd very much and thus there is not enough space for the solvent to co
calate. Furthermore, due to the presence of defects (pores, etc.) in the
ture, the transport of solvated lithium ions inside the graphite particle by
nsertion mechanism is hindered. Therefore, these carbons have the
ntage that they can operate in electrolytes which are free of typical film
ing electrolyte components.
Using thermally treated graphites with a low number of defects (and a
hexagonal phase content), i.e., graphites with extremely high
allinity, even the use of EC-based electrolytes results in a solvent co
85 538
calation, exfoliation and corresponding irreversible capacities. ' On
ther hand, strongly milled or otherwise mechanically treated graphites
a low number of defects (and a higher rhombohedral phase content) do
85 538
how exfoliation at all. ' -541 The tendency to solvent co-intercalation is
arily dependent on the defect concentration and not on the relative ratio
541
xagonal to rhombohedral phase.
Composite carbonaceous materials, comprising a "core" of graphite
a thin protective "shell" of non-graphitic carbon, combine the beneficial
erties of graphite (stable lithium storage potential plateau, larger gap to
metallic lithium deposition potential, high reliability of manufacturing,
cost, etc.), with the high tolerance of non-graphitic carbons to electrolyte
201
ms not compatible with graphite. ' 542- 551 These carbons also show a
r extent of irreversible capacity with solvents having low tendency to
tercalation, obviously due to an improved SEI formation process.
Graphitic materials with a crystalline core, but with more disordered
-surface structure" (i.e., thin part of graphite bulk material next to the
101 467
ce) yield similar results as the above composites. • •552 -555 Such
hite surface and sub-surface structures can be created by mechanical
101 554 555
ng and by high temperature gas treatment. • •
556 557 545 558 562
Polymer-coated, ' and metal-coated ' - carbons exhibit several
ovements compared to the uncoated material. In addition to impacts on
formation and solvent co-intercalation behavior, the metal-coated
hites benefit from better electronic conductivities and higher Li storage
cities. The latter are particularly observed when the coating consists of
ls which alloy with lithium, as lithiated metals and alloys show much
42
er lithium storage capacities than graphite (cf. Refs. 544,563-572 and
on 5.3.4.2 for C/Si composites).
In general, surface modification has been proven to be a tool for
er improvements of the carbonaceous anode materials, in particular in
of improved SEI formation. Coatings and surface modifications of hard
ns have already been discussed in Section 5.3.4.1. Takamura and his
Chapter 5

gues93,32I,465,558,562,573-575 started work on the topic "surface


ification" very early. The basic intention is to control irreversible
tions with the electrolyte, such as solvent co-intercalation and SEI
osition, as well as to remove or introduce carbon surface properties (e.g.,
ain morphologies and chemical compositions) detrimental or beneficial
performance. The interaction of anode surface properties, surface
ings and surface modifications with the electrolyte can be easily
rstood, when SEI formation on the carbon surface is compared with a
576 578
sition process (Figure 5.8). -
Apart from surface coatings, chemical treatments such as surface
524 579 580
rination, surface oxidation, surface reduction ' or heat treatment
573
r inert atmosphere ("outgassing"), as well as chemical bonding of
558 576
in substances to carbon surface groups and surface impurities, · and
3 6
ng under certain gas atmosphereli -II have been investigated. Oxidation
e most commonly applied method of surface modification. It has been
ormed by gas (air, 02, C02, 03) treatments2I3,257,258,384,554,555,577-58I and by
582 584
chemical measures. - A most interesting phenomenon is that in
e, but not all of the cases, the reversible capacity of oxidized graphites
exceed the theoretical value of the first stage compound LiC6 by more
213 257 258 582
10%. • · · A problem remains the interpretation of the results, as
basically equal treatment procedures the results vary considerably. The

A B
SEI Products
SEI Products Nuc

Substrate Substrate
(Carbon Surface) (Carbon Surface)

e 5.8. Deposition (plating") of SEI film products. Composition and morphology of the
eposit are controlled by the "plating conditions", i.e., by (i) the electrolyte composition, e
pretreatment (coating or modification) of the carbon surface ("substrate"), and (iii) the g
conditions (constant current or pulse plating, etc.): A) Plating conditions favoring
ation result in a compact and dense SEI. B) Plating conditions which facilitate the crystal
h of the initially formed nuclei induce the formation of a rough SEI deposit, which
es more SEI products to get pin-hole-free, i.e., consumes more irreversible capacity.
considerations can be applied to other anode and cathode materials, too.

ty of graphites and their various properties again makes the matter


plex and obviously not reproducible. Generally speaking, morphology
ges213' 257' 258' 384' 577 as well as surface chemistry changes 213·257·258· 384· 582
onaceous and Graphitic Anodes 179

treatment are accounted for the obtained results. In addition, the


-off of reactive carbon sites or complete reactive particles, which
d contribute to the irreversible capacity to a large proportion, may also
nsidered.
Though a comprehensive interpretation of the above effects of surface
ifications is still missing, the reports have elucidated the importance of
ce properties for the performance of carbon anodes.
A most critical issue is still the influence of carbon surface
ogeneities on performance. Both unsolvated and solvated intercalation
place via the prismatic surfaces. In addition, the prismatic surface and
plane surface are different both from the viewpoint of morphology and
istry, i.e., they are very different foundations for SEI deposition (cf.
re 5.8). Thus, not the total external surface area but rather the ratio of
prismatic and basal plane surfaces will affect the irreversible
120 127
city • as well as the rate capabilities of graphites. The reports of
d and colleagues213'379 ·585 are in line with this idea, as they have detected
pletely different SEI compositions at the edge and basal plane surfaces
OPG. The existence of different surface sites and their influence on
ersible capacities is discussed also in Refs. 224,515,586,587. The
rage and/or removal of detrimental or sensitive surface sites may be the
motivation for surface coatings and modifications.

WHAT IS SPECIAL ABOUT LITHIATED


CARBONS?

Carbons have been and still are considered to be the anode material for
rgeable high energy density lithium batteries, due to a synergetic
ination of properties beneficial for performance and production. These
erties include: high lithium storage capacities, negative redox potentials
he cathode, long term cycling performance, low costs and large
dance. Any other anode material discussed in this book may possess
al, but not all of these properties. Nevertheless, as (surface)
fications or the use in composites seem to be the perspective for future
n anode materials, the same might be true for other anode materials,
e in a composite together with carbon.
Two "wonders" are associated with the story of success of carbon
es. The first wonder is strongly related with the properties of metallic
m. Apart from having the highest capacity, among the light metals M =
a, and Mg, solely metallic Li shows a chemical and electrochemical
vior which favors its use in high energy density batteries, because
ce films with the unique SEI properties are formed. In contrast,
cts of electrolyte decomposition of alkali metals other than Li are
Chapter 5

cally partially soluble and therefore do not form similarly protective


12 588
s. Films formed on Mg are typically highly passivating. Mg can be
used in combination with electrolytes which do not form films on the
589
l surface. The resulting cell, however, by far can not reach the energy
590
ities of lithium ion batteries. The excellent protective properties of the
s formed on lithiated carbons can be directly related to the extraordinary
s formed on metallic lithium.
The second wonder is the obviously "perfect accommodation" of
um cations inside carbon. There is no other cationic guest species, that
be inserted into carbons at such high concentrations, with such high rates
at a such low potential vs. a cathode material. The alkali metals M = K,
Cs form 1st stage GICs MC8 (cf. LiC6) and the increase in interlayer
ing due to intercalation of the large M cations is large. As a result, the
ge storage capacity is poor. Sodium can hardly be intercalated into
hitic materials, but in disordered soft and hard carbons (cf. Section 5.2).
ever, also in this case the sodium storage capacities are significantly
r than the Li storage capacities in the same material, and the
rsibility is poor, which may be related with insufficiently protective
ace films.
It is a most lucky case in battery science and technology, that lithiated
ons combine all the properties necessary for an outstanding anode
rial. The final questions are: What comes after lithiated carbon? Will
be a third wonder in the future?

KNOWLEDGEMENT

We acknowledge the long term support of the Austrian Science Funds


F) for our work on carbon anodes and other lithium battery materials.

FERENCES
M. B. Armand, in: Fast Ion Transport in Solids, W. van Gool, Ed., Elsevier, Amsterdam,
1973,665.
B. C. H. Steele, in: Fast Ion Transport in Solids, W. van Gool, Ed., Elsevier, Amsterdam,
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ter 6

RAPHITE-ELECTROLYTE INTERFACE IN
LITHIUM-ION BATTERIES

1 2 2
M.Nazri , B.Yebka and G.-A. Nazri

iversity of Windsor, Department of Chemistry, Windsor, Ontario N9B 3P4, Canada


2. GM Research and Development Center, Warren, Michigan 48090, U.S.A.

INTRODUCTION
The recent commercialization of advanced lithium batteries is mainly
the breakthrough in the stabilization of the anode-electrolyte interface.
gh metallic lithium has an energy density (3860 mAhlg) higher than
other alternative anodes, its poor performance and safety issues
to the low melting point of lithium (180 OC), dendritic growth during
deposition (charge), and high reactivity toward the electrolytes have
ed the commercialization of rechargeable lithium-anode batteries.
There have been several approaches to solve the problem of lithium
The development of lithium alloys, particularly the binary and ternary
has received considerable attention (see Chapter 9 of this book).
er, the performance of these alloys is unsatisfactory mainly due to the
olume change (100-200%) during lithiation and delithiation processes.
xpansion and contraction processes may cause the alloy particles to
nd lose contact with the electrode substrate. In addition, the lithium
with high concentration of lithium are very reactive toward the
lytes and cause decomposition. Therefore a problem similar to that of
tallic lithium also exists for Li-alloy anodes. Recently, some success
en made using intermetallic alloys such as Cu 6Sn5 that insert lithium
tically over a wide composition range LixCu 6Sn5 (0<x<l3).1 Despite
d volumetric energy density of these alloys, their gravimetric energy
is poor and there is a significant capacity loss during multiple
.
The early transition metal oxide anodes have also been proposed for
tion in rechargeable lithium batteries -in particular, the use of lithium
lated titanium oxide.2 -7 The lithium titanium oxide anode is described
Chapter6

ero-strain insertion anode owing to negligible volume change during


hium insertion/extraction process. In addition, titanium oxide does not
pose the organic electrolytes, hence it can be considered as a safe
for rechargeable lithium batteries. The drawback of the lithiated
8
m oxide is its high redox potential (1.5 V vs. Li). Ohzuku et a/. have
very good reversibility and electrochemical performance for
012.
Lithium transition metal nitrides and phosphides also have been
9 15
ered as anodes for rechargeable lithium batteries. - The voltage
s of nitrides and phosphides during charge-discharge are between 0 to
vs. Li. There is also a large voltage hysteresis between the charge and
rge of nitrides and phosphides. The principal mechanism is believed to e
formation of lithium nitride and phosphide during reduction of ion
metal ions to the metallic state. The nano-scale transition metal rs
formed in this process are catalytically active, and during lithium
tion reaction they tend to form the original compound. The slow
cs and large hysterises between charge and discharge is a major
ack for the nitride and phosphide anodes.
In early 1990, a breakthrough was announced by researchers from
Energytech: an anode based on lithium intercalated carbon or graphite
hargeable lithium battery was used. 16 The volume change during full
m intercalation in graphite (LiC6) is less than 9% according to the in
-ray diffraction study. The specific capacity of the lithiated graphite is
iC6 (370 mAh/g), much lower than that of metallic lithium. In spite of
wer energy density, the current rechargeable lithium battery (Li-ion
) technology uses a lithiated carbonaceous anode. 17 -21 The success of
C6 anode is mainly due to the fast stabilization of the anode/electrolyte
ce and the high electrochemical reversibility of lithium
lation/deintercalation process. The LiC6 anodes have been charged and
rged over 1000 times without an appreciable capacity loss. The Li-ion
is currently replacing all other battery types in the market, particularly
field of electronics, computers, and communications. In recent years,
plication of the Li-ion batteries for more power demanding applications
as power tools, stationary, and transportation has started. The
tion of Li-ion batteries in 2002 has exceeded 500 million cells, with
as the main producer (over 70%).
Lithium intercalation in graphite is not new and has been fully studied
ysicists in search of high Tc superconductors during the last 50
2 23
• The hexagonal structure of graphite in ABAB arrangement is
in Figure 6.1. The layer B is shifted with respect to the A layer, but
nd BB layers are on exact registry with each other. When lithium
lates between the layers, the layer B glides to make an exact AAAA
re.
e-Electrolyte Interface in Lithium-Ion Batteries 197

Graphite has an ideal layered structure with weak van der Waals
g between the graphene layers. Thus, Li can be inserted between the
6 7
of graphite. According to recent Li- and Li- NMR studies, the nature
um in graphite is partly ionic. There is partial charge transfer from
to the n-orbitals of the graphene planes. The lithium in the graphite
so a high mobility, which is ideal for applications in high-power
s. In addition, the graphite has very high electronic conductivity,
electrode resistance is very low. Natural graphite is abundant, and
tic graphite also can be made from a variety of precursors. Heat
nt of various organic polymers, particularly those with conjugated
e rings, goes through a carbonization process around 1200-1500 OC
aphitization around 2300-3000 OC. During graphitization, the rate of
in a and c directions is strongly temperature dependent. Therefore,
e flakes with extended a or spherical with extended c directions can
de for different applications. The ideal graphite structure consists of

I. Schematic of graphite and lithium intercalated graphite.

of carbon atoms arranged in hexagonal rings that are stacked in an


sequence (Figure 6.1). The graphite comprises planar hexagonal
ks of carbon atoms (honeycombs) with two different crystalline forms,
nal (2H) and rhombohedral (3R). The 2H graphite structure is the
ommon and the carbon layers are arranged in the ABAB sequence,
Chapter6

the B layers are shifted to a registered position with respect to the A


. In the 3R (rhombohedral) structure, the stacking sequence is
BC, where the C layers are also shifted by the same distance with
t to the B layers, as the B layers are shifted with respect to the A
24
.
The separation of the layers in well-graphitized sample is 3.35 A, and
are held together with weak van der Waals bonds. The softness and the
ty of graphite can be attributed to the easy glide of these layers over
nother. Within each graphene layer only three carbon atoms surround
carbon atom. After forming one cr bond with each neighbor, each
atom would still have one electron and these are paired up into a
25
of 1t bonds.

EXPERIMENTAL SET UP TO EVALUATE


SURFACE REACTIONS OF GRAPHITE ANODES

Graphite Types
Several natural and synthetic graphite samples commercially available
4, BG-35, CPC, CN-39, CN-39A, SFG-15) with different morphology,

.2. SEM morphology of natural graphites BG34, BG35, KS44, and synthetic graphite
CPC, CN-39, CN39A, and SFG-15.
-Electrolyte Interface in Lithium-Ion Batteries 199

size, and surface area have been examined. Figure 6.2 shows the
ology of these graphite samples.

1. Surface area of various commercial graphite samples.

raphite 2
ace area (m )

The surface area of the graphites is listed in Table 6.1. These samples
ow surface area and, so, may be suitable for battery applications.
e of the high reactivity of lithiated graphite, lower surface area
s are preferred.
The X-ray diffractions of the graphite samples listed above are shown
re 6.3. The high and narrow 002 peak is an indication of the good
nity of the samples.

/ 0
0
N

0
......
......

MCMB.10
l 1L ± A
BG·34 A
/ SFG-15 Jl /
L KS·44 A /
L N·39A A /
/ CN·39 A /
/ CPC J\. /
/ BG·3S A /
/
10 20 30 40 so 60 70 80
2 Teta (degree)

.3. X-ray diffractions of various graphite samples.


Chapter 6

A General Procedure to Fabricate Carbon Anodes


and their Evaluation
The graphite samples need to be heated in vacuum between 700-900
remove moisture and attached functional groups, which usually exist at
ge of graphene sheets. It is very important to remove the water
ules trapped in graphite before using it in a lithium battery. Previous
rature program desorption (TPD) study has shown that almost all
e functional groups can be removed at 700-900 °C. The heat treated
te is then mixed with 8-10 wt% conductive diluent carbon, and to this
e 4-5 wt% EPDM binder (in xylene) is added to make a slurry. The
e of graphite sample, diluent carbon, and binder is ball milled using a
ercial micronizer. The slurry is spread on the surface of a copper foil
ried to remove xylene. To improve the adhesion of the sample to
, the sample is hot pressed inside of a dry box at lOOOC. The coating
s to make an electrode for lithium cells is shown in Figure 6.4.

rbon
EPDM Sam pie
ack binder Carbon
powder

.1 .
Mixture

Micronizer

..
. 4.

Coa t ing
Electrode

.4. Coating process to make electrodes for lithium cells. Anode is metallic lithium, the
is the graphite electrode, and reference electrode is lithium wire
in the cell between two layers of porous separator.
e-Electrolyte Interface in Lithium-Ion Batteries 201

From the coated foil, electrodes are cut to make the lithium cells. Two
2
of cells can be constructed. A lOx10 cm electrode can be used to
the surface reactions and electrolyte decomposition using a GC-MS
. Figure 6.5 shows the structure of the cell used for measuring gaseous
s formed during electrolyte decomposition. The graphite electrode is
ted from the metallic lithium electrode by a porous polyethylene
opylene separator soaked with electrolyte. The cell is housed in a
hylene coated aluminum pouch.

Cathode material ( IO x iO cm 2 ) t ToMS

.5. Schematic of Li/graphite cell for in-situ GC-MS analysis of electrolyte


osition during lithium intercalation in graphite electrodes.

2
A 5 cm disc electrode can be used for evaluation of capacity and cycle
sts. Figure 6.6 shows the assembly of this cell. The electrolyte
position occurs on the surface of graphite during initial lithium
lation. In order to investigate the nature of the evolving gas, a special
sembly is constructed to allow the generated gas to escape from the
d be sampled by in-situ GC-MS analysis. Before sealing the cell
in Figure 6.5, a flexible 2 mm diameter tube is inserted in the cell. The
s connected to an on-line GC-MS system. Figure 6.7 shows the
ned GC-MS equipment used for in-situ analysis of the gaseous
ts.
Chapter6

Anodc(CE)

Elc:cuolyte Lithium (RE)

Cathode (WE)

CurTcnt collector

.6. Schematic of lithium cell for evaluation of graphite anodes. WE= working
e, CE =counter electrode andRE= reference electrode.

PLOTTER

.7. Schematic of on-line GC-MS for analysis of gases generated during lithium
tion in graphite anodes due to electrolyte decomposition.
e-Electrolyte Interface in Lithium-Ion Batteries 203

The Lilgraphite cells, after charging and discharging cycles, are


mbled and the electrode is rinsed to remove excess salt. The IR
of the surface film is then obtained using a diffuse reflectance
ory that allows to install the sample inside the dry box and later
rred to the IR spectrometer for analysis.
In order to understand the thermal properties of the surface film, a
is collected from the surface of the graphite electrode (inside the dry
nd placed in a hermetically sealed DSC pan.

GRAPHITE CYCLING AND FILM FORMATION


The lithium intercalation/deintercalation process between the
ne planes of graphitic samples is facile. The high lithium storage in
e with a high lithium mobility, has provided a unique anode for
eable lithium batteries. The voltage of the lithiated graphite is very
o the voltage of metallic lithium (100-300 mV vs. Li). In addition, the
profile of the graphite anode during the lithium
lation/deintercalation process is fairly flat with a very small hysteresis
The graphite can accommodate one lithium per six carbons to form the
ed "stage one" (LiC6) compound. High-pressure intercalation synthesis
lded a lithium rich phase, LiC3. However, the LiC3 phase is not stable
ient pressure. It is interesting to note that the amount of lithium in 1
LiC3 is higher than that of the pure metallic lithium.
The lithium intercalated graphite is highly reactive and reacts with the
lyte solution. The by-product of the electrolyte decomposition forms
film on the surface of the electrode. The electrolyte decomposition
lithium intercalation occurs at about 0.8 V vs. Li. In parallel with the
lyte decomposition, lithium intercalation in graphite also proceeds.
m formed on the graphite surface, called solid electrolyte interface
yer), is electronically insulating and ionically conducting. The SEI
rotects the lithiated graphite from further reaction with electrolyte.
ore, the electrolyte decomposition stops in subsequent charge
ge cycles. The nature of the film formed on the surface of the
aceous anodes depends on the composition of electrolyte. Ethylene
ate based electrolytes tend to form a good compact SEI layer, and in
ommercial lithium batteries the electrolyte contain EC in addition to
carbonate solvents. The use of electrolyte with only propylene
ate solvent has not been successful, due to the co-intercalation of
and exfoliation of the graphitic anode. In practice, usually EC in
ation with other linear carbonate solvents such as dimethyl carbonate,
carbonate, or methyl ethyl carbonates are used. Figure 6.8 shows the
profile of a graphitic anode during the lithium intercalation process.
Chapter6

-0.5

·1.11
· .. :.:.:.:.... . . .
3.0 ... :k .-··
... -1.5
r\ ·.....,

.".c 1.5 r=
·0 10m0 ,._, 0.6 0.7 0.8 0,9 1.0
1.1 1.2

=
u"
=I Cell voltage (volts)

0.5 1=0.50mA 1=0.025mA


0.0 t
0 0.2 0.4 0.6 0.8 1.0 1.2 1.4

6.8. Voltage profile of graphite anode as a function of lithium concentration at 0.025


SmA, and O.lmA constant current charging.

The voltage plateau at about 0.8 volt is due to the electrolyte


position. It is important to note that when charging the electrode at a
current density, a more protective film is formed, and less electrolyte
position occurs. The voltage plateaus between the 0.3-0.01 V are an
tion of the staging phenomena usually observed for the formation of
LiC12, and other diluted phases of LiCn (n = 24, 36, etc). The insert in
6.8 shows the derivative of the voltage profile for the electrolyte
position part of the graph. The first charge-discharge of various
tic electrodes is shown in Figure 6.9. After lithiation in the first cycle,
ectrode/electrolyte interface is stable and does not react with the
lyte. The voltage of the graphite drops to very low value (300 mV vs.
intercalation of a small amount of lithium (Li0.05C6).
All samples have shown some degree of electrolyte decomposition
the first lithium intercalation. The decomposition plateau for BG-35 is
than for the other samples. In samples with a high degree of
llinity, the staging phenomenon is observed with better resolution, as
or the case of highly crystalline KS-44.
The amount of electrolyte decomposition also depends on the
sition of electrolyte. Figure 6.10 shows the voltage profile of an
de made from CPC during lithium intercalation in different electrolyte
sitions. The electrolyte containing EC-DEC-LiPF6 shows less
lyte decomposition. This suggests that the electrolyte containing cyclic
ne carbonate and linear carbonate may provide a safer operation for the
battery. The interface of graphite electrode is stabilized after
cal prelithiation or during the first charge-discharge cycle.
e-Electrolyte Interface in Lithium-Ion Batteries 205

.9. The voltage profile of graphitic electrodes (BG-35, CN-339, CPC, BG-34, CN-
d KS44).

le charge-discharge cycles of a prelithiated graphite anode are shown


ure 6.11. The charge-discharge cycles are very reversible and there is
of an electrolyte decomposition (plateau at 0.8V). At low charging

3.5 S2/CPC
3.0
2.5
V) EC-DEC-LiPF6
2.0
PC-LiPF6
1.5
EC-PC-LiPF6
1.0
0.5
0.0
0 100 200 300 400 500 600
Q (mAh/g)

.10. Voltage profile of CPC graphite anode in different electrolytes.


Chapter6

apacities close to theoretical one (372 mAhlg) are achievable . The rate
ch the electrode can be charged depends also on the amount of active
als loaded on the substrate. For the design of a high rate (power)

0
0 10 20 30 40 50
Time (hours)

.11. Multiple charge-discharge cycles of a graphite electrode after stabilization of the


e/electrolyte interface and formation of the SEI layer.

, the coating is thinner that for the electrode designed for high
applications. The usual loading for high power battery is about 10-20
2
and for the high-energy cells the loading may exceed 100 mg/cm2.
Disordered carbons have also been used as anodes. However, their
ty is almost half that of the graphitic anodes, and their voltage profile
lithium intercalation does not show the staging processes often
ed for the graphitic anodes. Some special carbon anodes with extended
layer graphene sheets, store lithium to a higher level than the
tical capacity. In this case, the lithium is being adsorbed on both sides
graphene sheets and in micropores. However, the cycle life of this type
bon is poor and there is significant capacity loss during multiple
-discharge cycles. In addition, there is a considerable amount of
e hysterises between charge and discharge. The sloping charge
rge profile also suggests that there are various sites for lithium with
nt affinities.
e-Electrolyte Interface in Lithium-Ion Batteries 207

Gas Generation on Graphites


The structure and degree of graphitization of the carbon electrode
critical role in the performance and safety of Li-ion batteries. The
effort is directed to understanding the relationship between the
ochemical properties of carbonaceous materials and their

2. Gas Chromatography and Mass Spectrometry analysis of the various gases


d on the surface of different graphite anodes during the first lithium intercalation

Graphite Electrolytes

BG-35

CPC

CN-39

KS-44

SFG-15

BG-34

chemical performance. The crystallinity and surface area of the


aceous materials, and the nature of the electrolyte used are important
for the electrochemical stability of Li-ion cells and for the nature and
of gases generated during the lithium insertion/extraction process
ble 6.2). Graphite anodes with high degree of crystallinity generate
during the first lithium intercalation cycle.
Chapter6

Careful analysis of various carbonaceous anodes indicates that a gel


ilm is also forming on the electrode surface as a result of electrolyte
position. The nature of this film has a significant impact on the rate
lity and the overall cell impedance.

. Infrared Spectroscopy of SEI Layer on Graphite


Anodes
The film formed on the surface of graphite anode during electrolyte
position can be probed using IR spectroscopy. After initial charge
rge, the cell is opened in the dry box, and a disc is cut from the
de. The sample is then placed in a diffuse scattering IR accessory and
inside the dry box and transferred to the IR spectrometer. The IR
a of non-cycled graphite electrodes were used as a reference. The
a of the film formed on the surface of BG-34 graphite anode after one
arge-discharge cycle in DMC-LiPF6 is shown in Figure 6.12. The
ex IR spectrum, with several absorption peaks, indicates formation of
anic moiety different from the electrolyte used. The peaks around 870-
d 1456 cm- 1 are assigned to the formation of LhC03• There is also an
tion of the formation of lithium-organic compounds such as
1
COLi with an absorption peak around 1600-1630 cm- assigned to the
tretch.
As we observed in the analysis of gaseous species generated when
is present in the electrolyte, the formation of CH2=CH2 also suggests
lowing decomposition reactions:

2Li+ + 2e- + CH30COOCH3 -LhC03 + CH3 -CH3


2Li+ + 2e- + CH30COOCH3 - CH30COLi + CH30Li
CH30COLi + CH30Li + residual H20 -LhC03 + CH30Li +
C02.

Table 6.3 reports the vibrational frequencies in DMC + 1M LiPF6. This


e following tables are self-explanatory.
e-Electrolyte Interface in Lithium-/on Batteries 209

BG-34

; &: DMC-LiPF•

1800 1600 1400 1200 1000 800 600 400

Wavenumber (cm"1)

.12. IR spectrum of the film formed on the surface of graphite anode during
intercalation in (DMC + 1M LiPF6) electrolyte.

3. Vibrational freguencies of the surface la er on BG-34 sra£hite in DMC-LiPF6•


Assignment
served (cm·1) v assigned Bands Compounds
1627br C02 stretch
1456br 1420-1470 Carbonate ion
1441 LhC03
1255SJ2 1280 Dimethz:1 Carbonate
1190m CO stretch
1160m 1150-1170 CH stretch LiOCH3
1050br 1050-1070 CH stretch LiOCH3
1020-1090 CO stretch Carbonate ion
928SJ2 969-914 Dimethz:1 Carbonate
890m
875sh 820-890 Carbonate ion
866 LhCOJ
833m 820-890 Carbonate ion
846 co3 bend LhC03
SlOsh
719sp 680-750 Carbonate ion
738 C02 asym. Li,C03
bend
539m 550-650 LiO stretch LiOCH3
eak, m: medium, s: strong, sh: shoulder, br: broad, v: very, sp: sharp)
Chapter6

TheIR spectrum of the film formed on BG-34 in EC-DMC(1:1mol) +


is more complex, indicating significant involvement of EC
position on the surface of lithiated graphite (Figure 6.13). The peaks
ponding to the formation of organa-lithium compounds as well as
1
3 are present. The peaks at 844 and 1
1483 cm- are assigned to the
m carbonate. The peak at 1083 cm- can be assigned to CH30Li, and
C02Li, various C-H bending of CH3 and CH2 groups.

1.0 .------.:---------------------:J
BG-34
EC-DMC-LiPF6
0.8

0.6

0.4

0.2

o
2000 1800 1600 1400 1200 1000 800 600 400

Wavenumber (cm-1)

6.13. IR spectrum of the film formed on lithiated graphite during the first lithium
ation process in EC-DMC (1: I mol) + 1MLiPF6 electrolyte.

In Table 6.4 the vibrational frequencies in EC-DMC-LiPF6 are


ed.
The IR spectrum of film formed on graphite during first lithium
lation in EC-DEC (1:1mol) + 1MLiPF6 is shown in Figure 6.14. The
ex spectrum with several absorption peaks shows decomposition by
cts of the EC and DEC solvents. The richness of the spectrum indicated
esides LizC03( solid), CH2=CH2(gas)• and CHrCH3(gas) there are various
organa-lithium compounds present. The peaks at around 700-800 cm-1
atched with the bending mode of Oc03 in ROC02Li. Because of the
ous nature of the film formed on the surface of the graphite, there is a
ility of ring opening decomposition of EC and formation of organa
dimers or trimers of EC (similar to the ring opening polymerization).
te-Electrolyte Interface in Lithium-Ion Batteries 211

.4. Vibrational frequencies on the surface layer on BG-35 graphite in EC-DMC-LiPF6.

Assignment
observed (cm'1) v assigned bands Compounds
1958vw
1866w 1870-1750 Organic Carbonate
1870 Ethylene Carbonate
1780sp 1870-1750 Organic Carbonate
1760 Dimethyl Carbonate
1737sh 1870-1750 Organic Carbonate
1638sh 1629 LiPF/
1566sh 1580 0-C-0 stretch RCOOLi
1483sp CH2 bend
1414sp 1441 LhCOJ
1420 LhCOJ
1369sh 1380-1360 CHbend LiOCH3
1198br 1170-1150 CH stretch LiOCH3
1083sp 1089 CO stretch Li,C03
1085 CO stretch RC03Li
1074 Ethylene Carbonate
1083 LiPF.'
977m 974 Ethylene Carbonate
909s
844br 846 C03 bending Li,C03
858 Dimethyl Carbonate
850 LiP
832 LiPF.'
780sp 745-789 LiO
774 Ethylene Carbonate

730sp 738 C02 asym. Li,C03


740 bend Li,C03
C02 asym.
bend
559sp 550 LiP
557 LiPF6'
552 LiO stretching Li202
: weak, m: medium, s: strong, sh: shoulder, br: broad, v: very, sp: sharp)

The peak assignments for SEI layer formed on the surface of graphite
the first lithium intercalation are listed in Table 6.5. The peaks
pond to the formation of residual lithium carbonate with peaks around
1
cm- , formation of various organa-lithium compounds as well as peaks
C=O stretching vibrations at 1650-1800 cm-1 •
The IR spectrum of the film formed on the surface of graphite anode
lithium intercalation in PC-LiPF6 solution is shown in Figure 6.15,
e frequencies and products in Table 6.6. This spectrum is rich in by
cts of the PC decomposition. The IR signals of LizC0 3, around 850 and
1
cm- have also been observed. As already mentioned, the film formed in
se is much thicker than the film formed by EC decomposition, this
ting further electrolyte decomposition upon cycling.
Chapter 6

EC-DEC-LiPF6
3.0

25

05

Wavenumber cm-1

.14. IR spectrum of the film formed on BG-34 in EC-DEC + IMLiPF6 during first
n.

(PC-LiPFti)
-O.Il

-O.Il5

-O.'l

-0.'15

-0.8 1801) lllOCl 141)0 121)1) IC)C)C) (ij)C)

Wavawmher ao. _,

.15. IR spectrum of the film formed on graphite anode in PC-1M LiPF 6.


te-Electrolyte Interface in Lithium-Ion Batteries 213

.5. Vibrational frequencies on the surface layer on graphite in EC-DEC-LiPF6.

Assignment
Observed vassigned bands compounds
1966s
1870 Eth 1ene Carbonate
1809s
1771sE 1750-1870 Orsanic Carbonate
1746m 1750 Diethi:1 Carbonate
1699w
1685w
1652m 1650 C02 stretch RC03Li
1555sp 1580 RCOOLi
1580 LiOH
1505sh 1500 (CHzOLi)z
1479w Eth lene Carbonate
1457w 1450-1480 CHbend LiOCH3
1445 CH, CH3 asy. Ethyl-C03Li
bend
1390w Ethylene Carbonate
1360-1380 CHbend LiOCH3
1374w 1351 COz s m. stretch Eth l-C03Li
1296sh
1267sE 1262 Dieth,rl Carbonate
1195sh CO stretch
1161sp 1162 Ethylene Carbonate
1152 CO stretch Eth,rl-C03Li
1072sp 1074 Ethylene Carbonate
1085 CO stretch Ethyl-C03Li
1100 CO stretch (CHzOLi)z
1017sp 1021 Diethyl Carbonate
1010 CO stretch Eth l-C03Li
973m 974 Eth lene Carbonate
903sh 890 (CHzOLi)z
844sp 858 Diethyl Carbonate
826 co3 bend Ethyi-C03Li
850 LiOH
774sE 774 Eth lene Carbonate
730sh 738
717m 720 C02 as m. bend Eth I-C03Li
666w 660-550 LiO stretch LiOCH3
556sE 500-600 LiO stretch Eth I-C03Li
529w 400-500 LiOH

(w: weak, m: medium, s: strong, sh: shoulder, br: broad, v: very, sp: sharp)

The IR spectrum of the film formed on the surface of lithiated graphite


DMC-LiPF6 is shown in Figure 6.16 (peak assignments in Table 6.7).
lm formed with electrolyte containing PC was always thicker and
in PC decomposition by-products. It is also observed that the film
Chapter6

d from solutions containing EC is also rich in EC decomposition by


ts.
The IR spectra of surface films formed on lithiated graphite anodes in
ns containing both the cyclic and the linear carbonates have been
d. The composition of the film is dominated by the decomposition by
ts of the cyclic carbonates. This observation may suggest that the
carbonates that selectively solvate the u+ in the electrolyte, carry their
on shell to the graphite surface, and preferentially saturate the
de-electrolyte interface with the cyclic carbonate. This observation
xplain the beneficial effect of EC in commercial electrolytes for
batteries.

6. Vibrational frequencies on the surface layer on graphite in PC-LiPF6.

Assignment
observed (cm'1) v assigned bands Compounds
1862sh
1817s
1785sh 1760 Dimethyl Carbonate
1732w
1715br
1630w 1629 LiPF6
1588sh 1580 RCOOLi
1500br
1430br 1441 LhC03
1360br COz sym.
stretch
1338br
1289br 1280 Dimethyl Carbonate
1250w 1263 LiPF6'
1233w
1134m 1122 LiPF6
1088m 1089 CO stretch LhCOJ
1083 LiPF6'
1065w 1060 LhO
960w 969-914 Dimethyl Carbonate
865sp 866 C03 bend LizC03
832 LiPF6'
870 LhO
866 LiO
791sp 793 Dimethyl Carbonate
789-745 LiO
734br 738 COz asym. bend LhCOJ
69lsh 730-689 LiO
562sp 557 LiPF6
650-550 LiO stretch LiOCH3
(w: weak, m: medium, s: strong , sh: shoulder, br: broad, v: very, sp: sharp)
e-Electrolyte Interface in Lithium-/on Batteries 215

CPC
PC-DMC-LiPF

I
0
":!':
:;::
:!:
l::i:!:
...

000 1800 1600 1400 1200 1000 800 600 400


Wawnumber (c:m-1)

6.16. IR spectrum of the film formed on the surface of graphite anode during lithium
ation in PC-DMC (l:lmol) +1M LiPF6.

7. IR frequencies of the surface layer on cycled CPC in PC-DMC- LiPF6.


Assignment
1
observed (cm" ) v assigned bands Compounds
1861sh 1750-1870 Organic Carbonate
1780br 1760 Dimethyl Carbonate
1590w 1630-1590 Carbonate ion
1555sp 1580 RCOOLi
1480sp 1480-1450 CHbend LiOCH3
1455sp 1450-1480 CHbend LiOCH3
1441 LhCOJ
1389sp 1380-1360 CHbend LiOCHJ
1254w 1250-1280 Organic Carbonate
1223w
1176br 1170-1150 CH stretch LiOCH3
1120s
1076w 1070-1050 CH stretch LiOCH3
1089 CO stretch LhC03
1045br
973sp 970-1020 Organic Carbonate
891sp 866 co3 bend LhCOJ
847sp 826 co3 bend Ethy-C03Li
846 co3 bend LhC03
774sp 774-793 C02 asym. Organic Carbonate
bend
709sp 720 C02asym. Ethy-C03Li
bend
625w 550-650 LiO stretch LiOCH3
537w 529 CO bend
weak, m: medium, s: strong, sh: shoulder, br: broad, v: very, sp: sharp)
Chapter 6

Thermal Analysis of SEI Layer on Graphite Anodes


The thermal characteristics of the surface film formed on the graphite
6
during lithium intercalation are very important for practical reasons?
hium battery may be subject to different thermal conditions during its
ional life. Therefore its thermal safety characteristics must be known.
ful tool for evaluating the thermal properties of films formed on a
te anode is the differential scanning calorimetry (DSC). The graphite
de was charged and discharged in carbonate-based electrolytes, and
rface film formed on the anode was collected for DSC study. Figure
shows the thermal behavior of the surface film in contact with LixC6 ,
2, 0.4, 0.6, 0.8, 1.0).

3.0 LiC6
X
X=O.S
2.5
BG-34 X=0.6
2.0
X=0.4
1.5
X=0.2
1.0

0.5

0.0
Before cycling
-0.5

-1.0 100 150 200 250 300 350 400


50
Temperature ( °C)

.17. Differential scanning calorimetry of the surface film formed on graphite anode at
states of charge (x=0.2-0.8 in LixC6).

The sample has an endothermic peak near the boiling point of DMC,
n the exothermic process starts around 150 OC. A major exotherm was
ed at 220-240 OC. The intensity of the exotherm peak correlates well
e amount of lithium remaining in the graphite. It is very important to
the safety aspects of the Li-ion cells when they are exposed to
atures above 150 oc. Further electrolyte decomposition with massive
neration may occur above 150°C, and cell temperature may rise to
e-Electrolyte Interface in Lithium-Ion Batteries 217

the flash point of the electrolyte components. Therefore care should be


ed dealing with lithium-ion batteries with graphitic anodes,
larly in the charged state (x value close to one in LixC6).
A similar thermal behavior was observed for almost all graphitic
. The temperature-induced degradation of the SEI layers occurs first
120-140 ·c followed by an exothermic reaction and the
position of trapped LiPF6 around 210-230 ·C. We have found a direct
tion between the BET surface area of the graphite anode, amplitude of
C exothermic peak and the irreversible capacity losses measured for
ells. Figure 6.18 shows the correlation between the volume of gas
ted on the surface of lithiated graphite anodes and the surface area of
phite material used.

t'iO

50

i .w
; 3:0

20

10
•-
0 2
" Surface area (m 'fg)
6 ll 10 12 14

.18. The correlation between the volumes of gas evolved during lithium intercalation
te anode and the surface area of the graphite. Upper line: PC-DMC; middle: EC
wer: EC-DEC (all with LiPF6).

CONCLUSIONS
he following general conclusions can be made from this study.
Organic carbonates are not electrochemically stable over a lithiated
raphite electrode. However, the decomposition by-products formed on
he surface can protect the electrode, and the electrolyte decomposition
s eliminated in subsequent charge-discharge cycles.
The nature of the film formed on the surface of lithiated graphite
epends on the composition of electrolyte, and in the case of
Chapter 6

electrolyte made of organic carbonates, the by-products are organa


lithium compounds as well as some lithium carbonate.
The composition of the film is dominated by the by-products of cyclic
carbonate decomposition, and less by the linear carbonate
decomposition.
The film formed from the decomposition of cyclic ethylene carbonate
is denser and more protective as compared with films formed from
other carbonates.
The gaseous species formed during the first charge discharge are
mostly flammable and care should be taken when preparing large
lithium cells.
The thermal analysis has shown that the film formed on the surface of
lithiated graphite is not stable above 150 OC. If lithium cells are
exposed to heat, or if internal heat exceeds 150 °C, the protective film
could be destroyed and further electrolyte decomposition of the freshly
exposed surface of lithiated graphite may occur. Therefore, it can be
concluded that the current lithium-ion cells are not very safe above
150°C, and their application in such conditions must be avoided. In
addition, a safer and more robust anode is needed, particularly for large
size applications of high-energy and high-power lithium batteries.

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M. Thackeray, J.T. Vaughey, A.J. Kahaian, K.D. Kepler, R. Benedek, Electrochem.
mm. 1( 1999) 111.
Akimoto, Y. Gotoh, Y. Oosawa, J. Akimoto, Y. Gotoh, Y. Osawa, J. Solid State
emistry 7 (1997) 129.
. Kartha, D.P. Tunstall, J.T.S. Irvine, J. Solid State Chemistry 152 (2000) 397.
E. Arroyo de Dompablo, A. Varez, F. Garcia-Alvarado, J. Solid State Chemistry 153
00) 132.
van de Krol, Thesis, 2000, Universal Press, Veeneddaal, Netherland.
Sodergren, H. Siegbahn, H. Rensmo, H. Lindstrom, A. Hagfeldt, S.E. Lindquist, J.
ys. Chern. B 101 (1997) 3087.
W. Murphy, R.J. Cava, S.M. Zahurak, A. Santoro, Solid State Ionics 9 (1983) 413.
Ohzuku, A. Ueda, N. Yamamoto, J. Electrochem. Soc. 142 (1995) 1431.
Nishijima, Y. Takeda, N. Imanishi, 0. Yamamoto, J. Electrochem. Soc. 141 (1994)
66.
Shodai, S. Okada, S. Tobishima, J. Yamaki, Solid State Ionics 86 (1996) 785.
Suzuki, T. Shodai, Solid State lonics 116 (1999) 1.
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Ohzuku, A. Ueda, J. Electrochem. Soc. 144 (1997) 2780.
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Novack, K. Miller, K.S.V. Santhanam, 0. Heas, Chern. Rev. 97 (1997) 207.


Bicke, W.F. Chu, W. Weppner, Solid State Ionics 1997, 93.
Arakawa, J. Yamaki, J. Power Sources 54 (1995) 250.
A. Safran, Solid State Physics 40 (1987) 183.
E. Ulloa, G. Kirczenow, Comments Cond. Mat. Phys. 12 (1986) 181.
. Dahn, A.K. Sleigh, H. Shi, J.N. Reimer, Q. Zhong, B.M. Way, Electrochim. Acta
(1993) 1179.
A. Cotton, G. Wilkinson, C.A. Murillo, M. Bochmann,.Advanced Inorganic Chemistry,
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N. Richard, J.R. Dahn, J. Electrochem. Soc. 146 (1999) 2068.
apter 7

THE KEY ROLE OF NANOPARTICLES IN


ACTIVITY OF 3d METAL OXIDES TOWARD
LITHIUM

J-M. Tarascon, S. Grugeon, S. Laruelle, D. Larcher and P. Poizot

boratoire de Reactivite et Chimie des Solides, Universite de Picardie Jules Verne and
CNRS (UMR-6007), 33 rue Saint Leu, 80039, Amiens, France

INTRODUCTION
In response to the needs of today's mobile society and the emergence
cological concerns such as global warming, one of the major
nological challenges in this new century is undoubtedly energy
ration and storage. Ninety percent oftoday's electrical power generation
comes from fossil fuels, and we are constantly struggling to reduce the
on dioxide emissions per unit of electric power so as to help curtail
al warming. It is now mandatory that new and environmentally friendly
gy/storage sources be found. Hence, the fast developing research in that
involving, among others, fuel cells, primary and rechargeable batteries,
supercapacitors. As a result of this worldwide ecological priority,
ical concerns have come into play, and science has suffered from
itisation based on both industrial pressure and media reports, rather than
he clear and rigorous scientific identification of technological stoppers
ent in each storage system. Needless to say, this applies to battery
ms as well.
In the past two decades, intensive efforts have given birth to the
argeable Li-ion battery technology that has dominated the market place,
an be regarded as one of the great successes in modern electrochemistry
te. But these Li-based systems still suffer from the lack of suitable
rode and electrolyte materials, which they require if they are ever to
mmodate the increasing user's demands. Aware of this limitation,
ists have been acting at several levels to incrementally improve the Li
erformance. They have followed a dual approach, dealing with either
ive or negative electrode materials, with efforts centered around: 1) the
fication of existing materials through cationic/anionic substitution,
re modification and surface treatments, 2) the making of composite
Key Role ofNanoparticles in the Reactivity of 3d Metal Oxides Towards Li 221

trodes or electrolytes made of several chemical components, and 3) the


gn of new electrode materials. Such approaches were pursued at the
roscopic scale on electrode materials 1- 3 having a dual electronic-ionic
uctivity, a void structure to insert/de-insert Li ions, or the ability to alloy
Li. They led to the identification of layered LiMn 1_xCrx02 oxides4-5 or
e-dimensional iron phosphates (LiFeP04)6, that stand as a possible
native to LiCo02 or negative electrode materials such as tin-based
es (Sn02, Sn0)/-8 intermetallics (CuSb9, Cu6Sn510, •••), nitrides 11 and
phides, 12• 13 which could be used as alternatives to carbonaceous
rials, once their initial large irreversibility and poor cycle life have been
come.
Recently, our research group pursued a novel approach, deviating
the conventional route aimed at searching for compounds having voids
ture or alloying with Li. We obtained astonishing results with the
ibility for metal oxides (MO), having an interstice-free rock-salt
ture, to reversibly react with Li. 14 Not only did such findings make us
re that high-performing electrode materials may have been wrongly
garded in the past, but also they now comfort us in our approach aimed
ckling electrode materials at the microscopic rather than macroscopic
e. Through our work on metal oxides, which was extended to other
l-based anode materials, we will stress that, when working at the atomic
l, new kinds of effects are apparent, and represent completely new
rtunities in the unusual design of materials.
Thus, this chapter will be organized as follows. First, we will recall
ey observations motivating the reactivity of 3d-metal oxides towards Li,
describe the fundamentals lying beyond such an unusual reactivity.
ndly, we will rationalize these types of reactions, and evaluate their
ntial with respect to applications. Thirdly, we will stress the positive
bute of nanoparticles in enhancing kinetics, therefore enabling different
activity paths.

EXPERIMENTAL
The Co-based metal oxide powders used within this study were
mercial products (CoO), or were synthesized in-house (Co304, Mn304,
203). The other metal oxides (M= Ni, Fe, Mn, Cu) were used as
ved from commercial sources, unless otherwise specified. LiCo02 was
provided by the market.
Powder purity and crystallinity were examined by X-ray diffraction
D), operating in Bragg-Brentano geometry with a CuKa radiation. The
ders morphology and composition were investigated by scanning
ron microscopy (SEM) with a field emission gun (FEG), coupled to an
ument for energy-dispersive X-ray spectroscopy (EDS). High-
Chapter 7

lution transmission electron microscopy (HRTEM) was carried out using


croscope equipped with an EDS analyzer. Magnetic measurements were
ormed on a commercial SQUID magnetometer, at temperatures ranging
5 to 290 K. Electrochemically-driven structural changes were followed
means of an in situ electrochemical cell similar to that previously
ribed 15 , with the studied electrode material deposited behind a beryllium
dow, which acts as the positive current collector.
The materials were tested in either Swagelok™ or standard 2035-size
cells that were assembled in an argon-filled glove box at a dew point of
c. If not otherwise specified, the cell consists of a plastic positive
trode disk containing 64 wt% of MxOy materials, 8 wt% SP carbon black
28 wt.% PVDF-HFP copolymer binder; a 1 cm2 disk of Li foil as the
tive electrode member; and a Whatman GF/D borosilicate glass fibre
t separator, saturated with a 1M LiPF6 electrolyte solution in a 1:1 (by
dimethyl carbonate/ethylene carbonate.
The cells were tested using a VMP automatic cycling/data recording
em that can be operated in both galvanostatic and potentiostatic modes.
reported curve was reproduced three times. Hardly any deviation was
d among the curves.

RESULTS AND DISCUSSION

. Reactivity of 3d Metal Oxides Towards Li

The electrochemical reactivity of 3d metal oxides towards Li has long


studied. A few oxides, such as CuO, which converts to Cu through a
mposition reaction (CuO -7 Cu + 1/202), were spotted as attractive
rode materials, leading to the assembly of primary CuO/Li cells that are
commercialised nowadays.16- 18 However, with the common belief that
mposition reactions cannot be electrochemically reversible, such oxides
been disregarded as reversible Li electrode. The motivation to
estigate them, like most materials advances, is the result of several
rvations/contributions going back to 1996. In 1996, Fuji's researchers7
rted that vanadates-based electrodes displayed, when cycled down to
volt, reversible capacities greater than those expected, assuming a
ction of the constituting metal elements. Later, these results were
19 4
nfirmed by Guyomard's group • Occasionally, for some LiMV0 (M=
i,Co ..) phases, this group reported a surprising capacity enhancement
cycling, which turned out not to be fortuitous, as will be seen later. In
of such intriguing results, our group launched a complete study of the
dates, aimed at identifying the key parameters governing their unusual
ivity vs. Li. Numerous hydrated vanadates of formula RV04 .nH20,
Key Role of Nanoparticles in the Reactivity of 3d Metal Oxides Towards Li 223

r crystalline or amorphous, were surveyed with special attention given


he Fe- and Co-based ones (FeV04 -1.1H20, Co(V03h·n H20) that
layed exceedingly large (800 mAh/gr) reversible capacities.20- Among
23

umerous in situ techniques used to study the electrochemical behaviour


o(V03h·n H20 /Li cells, XANES turned out to be the most fruitful 24•
ed, it indicated that upon charge/discharge cycles, the oxidation state of
was surprisingly converting between 0 and 2, and that of vanadium
een 3 and 5. Knowing that the electrochemical behavior of V205
eeds through an insertion/deinsertion process, we hypothesized that the
pected electrochemical results could be associated to the reactivity of 3d
l oxides towards Li. Thus, our study of the vanadates was narrowed
n to that of the 3d metal oxides as MO (M =Co, Ni, Fe, Mn), which
precluded to react with lithium on the basis of Li insertion-deinsertion
i-alloying reactions.25-30
Several CoO/Li half-cells were electrochemically tested towards Li14
to our surprise, we found that they could sustain a nicely reversible
city when cycled down to zero volt. During discharge (Figure 7.1), two
rent electrochemical processes appear, a plateau at 0.8 V with an
litude of two Li, followed by a continuous uptake of 0.7 additional Li,
n to a voltage of 0.02 V. With the following charge, only about two Li
ormula unit could be removed, leading to a capacity of 700 mAh per
of CoO, a value about twice that of today's graphite negative
rodes. Since such oxide does not contain voids, or a metallic element
alloys with Li, its reactivity had to be different from the classical Li
tion/deinsertion or Li-alloying processes. In an attempt to pin down this
mechanism, Potentiodynamic Intermittent Titration Technique (PITT),
tu X-ray diffraction, and XANES measurements, together with semi in
TEM measurements, were carried out on CoO/Li cells.
PITT electrochemical measurements revealed two very clear and
nct processes. The first one (Figure 7.2) for which the chro
perometry response to the voltage step (E=0.92 V) displays a bell curve
2
e, corresponds exactly to an uptake of 2 Li (e.g., a full reduction of Co+
o).
Beyond .x=2, we observed a continuous decrease in the potential as a
tion of x, as observed in the galvanostatic mode, with a difference in the
ber of reacted Li that reached 1.8 instead of 0.7. This suggests a faradic
ess strongly influenced by the imposed current (e.g., a kinetic influence).
CoO -7 Co conversion process was further confirmed by XANES
urements24 at the Co K-edge, indicating that the spectrum of fully
ted and fully delithiated samples after 10 cycles was superimposing that
etallic cobalt foil and fresh electrode, respectively.
Chapter 7

3.5

C/2

--
3
_
2.5

-
j

V)
> 2
>
1.5
0
1
c
+- 1
0
> 0.5

0 3.5
0 0.5 1 1.5 2 2.5 3
x in "LiXCoO"

e 7.1. Voltage-composition traces for a CoO!Li cell cycled between 0.01 V and 3 a
rate of C/2 (e.g., 1 lithium per formula unit in 2 hours) shown over several s.
Capacity retention for the same cell shown in the inset.

3.5
3
0 Q
5'2.5

r:
-0.05

2 -0.1

0.5
-0.15
0 0.5 1 1.5 2 2.5 3 3.5
0 x in "Li CoO"
X

e 7.2. PITT measurements performed on a CoO!Li cell. The voltage steps are of
V with a current limit Cimin) corresponding to C/300 (e.g., 1 Li in 300 hours).
Key Role of Nanoparticles in the Reactivity of 3d Metal Oxides Towards Li 225

Through the electrochemical reduction process the samples were


wn, as deduced by in situ X-ray measurements,14 to become amorphous,
to remain so upon subsequent cycles. Transmission electron microscopy
then used as a complementary technique to further grasp the electrode
ution morphology upon cycling. We observed (Figure 7.3) that upon
discharge, the sintered CoO particles of dimensions ranging from 1000
000 A, decomposed into 10 to 20 A diameter Co nanograins, dispersed
a matrix.

e 7.3. TEM observations realized on CoO electrodes recovered from CoO!Li cells that were
ed at various discharged and charged states, as indicated by the full circles on the
ge/composition curves. When necessary, the SAED patterns are joined to the micrograph as
ans to indicate the electrode composition. The nanometric character of the composite
her with the growth/disappearance of a polymeric layer are nicely depicted.

At .x=2, the decomposition was completed, and from an indexation of


ollected SAED patterns, we could clearly identify the presence of Co0
ic structure) and Li 20 (antifluorine structure) matrix. Upon further
ation (beyond .x=2), the SAED patterns no longer evolved.
rastingly, we noted the growth of an organic-type layer. The layer
ppeared upon the following charge, and the Co deoxidised , leading to a
nanograin electrode, as deduced from an indexation of the collected
D patterns. Two polymorphic forms, referred to as the high temperature
Chapter 7

oO (PDF n° 48-1719) and the low temperature -CoO forms (PDF n°


300) exist. It was separately reported, as deduced by x-rays, that
allic Co nanoparticles were converting to the low temperature CoO form
31
oted a-CoO) upon oxidation. Therefore, we could not ascertain the
gnment from our HRTEM measurements, since the two CoO
morphic forms have lattice parameters differences falling within the
t of the technique itself.

2. Rationalization and Potential Applications

2.1. Thermodynamic and Kinetic Considerations of the MOM


Conversion

Whatever the a or forms, all the above results convey the message
the reduction of CoO through the first discharge plateau is reversible
rding to the following reaction.

(7.1)

The disappearance of the well-defined first discharge plateau at the


nse of a "sloping voltage plateau" upon subsequent cycling is fully
istent with the nano-sized character of the electro-produced particles,
h generate many new indefinite interfaces with various interfacial
gies. Interestingly, while never observed at room temperature, an
trochemical reaction involving the formation/decomposition of LizO was
dy observed to occur during the electrochemical oxidation/reduction of
32 33
3 or Fe304 in molten salt at 500°C. - As usual, when dealing with the
ibility of any chemical reaction, one must return to basic
modynamics. In short, one must simply calculate the associated changes
tandard Gibbs free energy. If this .:lG turns out to be negative, the
idered reaction is thermodynamically feasible. Then, from Gibbs free
alpy of reactions, one can predict the equilibrium potentials by using the
-known Nernst law .:l,G = -nEF, where F is Faraday's constant. Using
34 35

=
hermodynamic data - given in the literature for massive compounds,
an deduce for CoO a .:l,G -347 kJ/mol that should correspond to a
au located at Eeq = 1.798V vs Li+/Li • Similar calculations can be
0
36 37
nded to most of the 3d metal oxides, - , with the main result being that
tabulated Gibbs free energy values are negative. This result
mbiguously proves that such oxides are, under these conditions,
aneously reducible at Eeq values, as reported in Figure 7.4.
Key Role of Nanoparticles in the Reactivity of 3d Metal Oxides Towards Li 227

o Bard data
3.5
.---.. • Handbook data ·························· ······················i····················· 3
.
s
3 • Kubaschewski data
+.....
.
2.5 ------------------·--r--·-------------------r ---------------------!·----------------------r·----- 2.5
r.n
> 2 ·····················i····················+······················ -- --······ -- ----····................ 2
>'-" i aj •••f • :•oo
Q.)
1.5
.. .
.. . .... ..
0 1
> ··••••••••••••••m ••••• •• •••··••r•:••••••••••••••••r•••••••••••••••• :•••••••••••• ··· 0.5
:·'
.
- --- ---··•··-i·-·····················i······················"·······················f·····················
0.5 '

e 7.4. The equilibrium voltage values of MO < -- > M conversion reaction are
ted for various oxides. The values were obtained by first determining the reaction
nergy (dG) and then by applying the Nernst law.

Thus, by blindly considering a thermodynamic reversible process, one


ld expect the reduction of CoO to occur at 1.798 V. This contrasts with
eduction potential value of 0.8V (Figure 7.1), obtained during the first
harge of a CoO/Li cell. The deviation of about 1 Vis naturally of kinetic
re, and represents the important over potential needed to initiate and
ue the decomposition reaction. Assuming that the 1V over potential
ed to reduce CoO is of the same amplitude as for most of the other 3d
es considered, our difficulty encountered in reducing MnO (Figure 7.5),
ur inability to reduce Ti02 and at fortiori MgO, can be understood.
Since reaction (7.1) is thermodynamically allowed in the forward
ction, it should also occur backwards (that is to say, from right to left), if
applied voltage exceeds the Eeq voltage. Thus, a legitimate question is
was this reaction never observed to proceed at room temperature, when
ures of LizO and Co were mechanically made and reoxydized . The
er is of a kinetic nature, and lies in the difficult task to reconvert,
0
ugh a solid-state reaction, coarse M + Li2 0 particles into a metal oxide
y)- We believe that the reversibility experienced with various MxO/Li
is mainly nested in the high chemical reactivity of the electrochemically
e nanograins, after the electrode has been reduced once. Indeed, with a
easing particle size, an increasing fraction of atoms lies near or on the
ce, making the effect of surface on the chemical/electrochemical
ivity of increasing importance. Thus, the chemical diffusion path in
Chapter 7

ly divided powders becomes close to that of a liquid state, thereby


aining why a reaction occurring at about 500 oc can be produced at
temperature. Nevertheless, electrochemically speaking, reaction (7.1)
ins slow as seen by the substantial difference observed between the
harge and the charge voltage composition curves in cycling (Figure 7.5).
ever, caution has to be exercised, since the capacity associated with the
reduction of the 3d metal through a decomposition reaction does not
account for the measured capacity.

3.5 0.1
Eeq(Mn0/Mn°)=1,03V
+' 3 Eplateau"'0.2V/Li 0.05

2.5
CZl
> 2
0
-0.05
§g
>
1.5
.......
-0.1
..... 1 -0.15 '--'

0.5 -0.2

0 1 1.5 2 2.5 3 3.5 -0.25


0 0.5
x in 'Li01n0'

e 7.5. The voltage composition curves as deduced from PITT measurements for
Li cells cycled between 0.02 V and 3V. The voltage steps were of 10 mY with a t
limit corresponding to C/300.

.2. The Rich Chemistry Associated to the Low Voltage Process

The above observations, while leading to a full understanding of the


process, did not give any clue as to its origin. To further look into this
voltage process, we measured the dependence of I vs. the voltage scan
d (V/s) over the 0 to 1.8 V range (Figure 7.6), and observed a linearity
is reminiscent of a super capacitor-type behaviour. Interestingly, we
ed, by TEM, that the gel-like film formed on CoO was not affected
cycling was limited to the 0-1.8 V range, while vanishing when the
electrode voltage was raised to 3 V. Such a finding suggested that the
n polymer film had an electrochemical activity. However, we do not
any information about its composition. In contrast, its formation is
d in the Co-catalysed electrolyte decomposition, with some of the
Key Role of Nanoparticles in the Reactivity of 3d Metal Oxides Towards Li 229

lting products moving to the negative electrode, as deduced by the one


ne correlation between the phenomena occurring at the CoO and Li
38
rode, as observed by AC impedance measurements. Indeed, we noted
the reversible transition from the CoO Co conversion process to the
rolyte decomposition process was mirrored by a reversible change in the
ectrode resistivity.

0 0.5 1 1.5 2
Scan potential (Volts)
e 7.6. Cyclic-voltammetry data as a function of the scan rate for a CoO!Li cell that
ycled between 0.02 and 1.8 V. One inset shows the linear variation of the current as
ction of the scan rate. The others, a, b, and c are micrographs of CoO electrodes
ered from CoO!Li cells that were fully discharged and fully recharged 10 times
en 0.02 and 1.8 V, and fully recharged to 3 V, respectively.

Aware that the low temperature process was rooted in electrolyte


mposition reactions, we decided to study how it would depend on the
e of the electrolyte used. We went through a survey of various
rolytes encompassing the use of 1 M LiPF6 in either a single solvent,
as EC or DMC, or solvent mixtures, such as EC-DMC and EC-PC. The
of DMC (linear alkyl carbonate) as the sole solvent resulted in fast
city fading, as opposed to EC (cyclic alkyl carbonate), which enables
ined cyclability. The detrimental effect of DMC was considerably
nished when used in a 50/50 weight mixture, with either PC or EC
Chapter 7

ic molecular structures. As cells were cycled, at least during the first


es, we noted on oxidation the partial disappearance of the organic layer
was forming on reduction. Worth mentioning, however, was that the
unt of formed polymeric film was always found to be less in presence of

At this point, a legitimate question was whether such observed effects


d be the simple result of the presence of carbon within our starting CoO
ectrode composite. The observed growth of the polymeric layer in cells
e with thinner carbon-free CoO electrodes ruled out this possibility. The
difference between cells having carbon free (CoO/Li) or carbon
aining CoO positive electrode (CoOJLi) cells resides in the first few
es. The former display a lowest initial capacity that decays more rapidly
the first few cycles than the latter.
With the polymeric layer being the result of an electrolyte
mposition, one could hypothesize its growth to be strongly temperature
ndent. To check this hypothesis, we studied the cycling behaviour of
CoOJLi and CoO/Li cells at various temperatures, namely, 55°C and
(Figure 7.7).

2000
1800
1600
1400
-'

;
1200
d 1000
. 800
600
;

) 400
..
) 200
0
0 50 100 150 200
Cycle number
e 7.7. Variation of the capacity retention of CoO/Li cells, both as a function of
mperature and of the electrode content (e.g., with or without carbon). Effect of
rature sweep between 20°C and 75°C on the capacity values shown as an inset.
Key Role of Nanoparticles in the Reactivity of 3d Metal Oxides Towards Li 231

First, common to all the cells once the first ten cycles were achieved,
ote a continuous increase in the cell capacity that was more pronounced
increasing temperature. At 75°C, a doubling of the initial capacity was
hed after 200 cycles. Such a capacity was found to be reversibly
perature dependent, since a decrease in temperature resulted in a capacity
ease, which is fully recovered as the temperature return to its original
e39 • Worth mentioning is that more than 500 cycles were achieved
out any evidence of short-circuit, reminiscent of dendrite formations.
hermore, on cells opened after 500 cycles, we noted that the polymeric
r has expanded through all the separator, suggesting at first that the
meric layer could not be a good electronic conductor, without which the
would have a short. The feasibility of cycling CoO/Li cells at 75°C at a
ate for more than 400 cycles is somewhat amazing, bearing in mind
these are the best conditions to favour dendrite formation. This can be
ained either by: 1) the fact that the polymer film formed on the CoO
rode prevents dendrite penetration, and by the same token, cell short or
y a modification of the Li surface morphology, due to the deposit of
rolyte degradation products, to the point that it cancelled dendrite
ation. Needless to say these facts could help in engineering better
ectrolyte interfaces so that rechargeable Li batteries could finally
me a commercial reality.
Finally, by conducting cycling measurements with different discharge
ff voltages (Figure 7.7, inset), we reached the conclusion that this
erature-enhanced capacity was the result of electrochemical processes
g place at voltages close to lithium (e.g, over the 0.02-0.15 V).
iously, this result could simply be explained by assuming a temperature
nced electrolyte degradation that would lead to an electrochemically
e polymer. Therefore the amount of this polymer would increase, the
city would increase, and should remain constant whatever the cycling
erature once the film is formed. This is not as simple, since we
rved that the capacity decreases once the temperature is lowered. The
that the temperature-driven extra capacity is located near 0 V vs. Li+/Li 0,
ates that one needs to decrease the cell polarization by rising the cell
erature to tap into this low potential extra capacity. Thus, the capacity
g observed with changing the temperature is the result of polarization
ts, most likely associated to a limited ionic or electronic conductivity of
rown polymeric layer.
To further explain the cycling data at 70°C, we plotted the derivative
es (Figure 7.8) as a function of the cycle number. We noted the
arance of a 1.2V peak corresponding to the Co07Co conversion
ess, which disappeared upon cycling at the expense of a 0.8 V peak.
implies that, upon long cycling, the Co07Co conversion process
lly corresponding to the main part of the overall cell capacity vanished.
Chapter 7

0 0.5 1 1.5 2 2.5 3


U(V/LVLn

0.15V-3V

80 120 160 200 240 280


Cycle number

2.5 3
0 0.5 1 1.5 2
U(Vvs LVLi)

7.8. Derivative dx/dV plots as a function of the cycle number for CoO/Li cells.
ells were cycled at 75°C at a C rate. Two scanning ranges were used, 0.02 to 3 V
.15 to 3 V. Note the appearance of a 0.8 V to the expense of the 1.2 V peak
ponding to the MO < -- > M conversion process, and of a large extra capacity
d around 0.1 V.

The hypothesis was directly confirmed by magnetic measurements


re 7.9) that showed no changes in the sample magnetization (equivalent
Key Role of Nanoparticles in the Reactivity of 3d Metal Oxides Towards Li 233

0% of Co in the magnetic state), whether the composite electrode was in


harged or discharged state. In light of such results, it appeared that the
sured capacity, once the CoO conversion process became inactive, must
ue to the polymer-like forming film.
Among the remaining questions are whether, in addition to the key
played by the polymeric layer, these processes could also be rooted in:
he presence of Co surfaces electrochemically attractive to Li deposits at
ntial positive with respect to the Nernst potential (UPD-type processes)
2) in the feasibility of Co, in such highly divided electrodes, to
trochemically alloy with Li. Finding a clue to these questions depends
nding the exact nature and composition of the formed polymeric layer, a
presently being pursued by our group.

140 30 discharges

120
0
U100
4-1
0 80 30 charges

60
::E 40
20

0 ---- ----
4
----
4
---- 4----4 -- 4
0 110 2 10 3 10 4 4 10 5 10 6 10
FIELD (Gauss)
e 7.9. Variation of the room temperature remnant magnetization for fully charged
ischarged CoO electrodes recovered from CoO/Li cells that were cycled 30 and 100
, respectively, at a C rate over a 0.02 to 3 V voltage range.

Under any circumstances, and whatever the exact process, either a


bination of UPD and Li-alloying processes or others, the main result is
reactivity of the 3d metal oxides towards Li stresses the profound effect
divided particles could have within the field of energy storage. Worth
ioning is that the described effect is not specific to Co electrodes, but
occurs with Cu, Fe, Ni and Mn (which, purely coincidentally, are
uently used as catalysts in Fischer-Tropsch type reactions, for instance).
hermore, numerous classes of materials besides the 3d metal monoxides
Chapter 7

14
O, FeO, MnO, CuO), such as 3d metal sesquioxides (Co304), Li-based
27
ary oxides (LiCo02, LiNi02, ...), 3d metal sulphides (CoS) , or nitrides
4041
3N), were found to behave identically, leading to the
ation/decomposition upon cycling of Li2S and LhN, respectively,
ther with the formation of a polymeric gel-like layer. Similarly, there
recent reports describing the potential reactivity of 3d metal-based
tes or phosphates in similar terms, thus suggesting the universality of
a proposed mechanism.

3. Practical Application Considerations


A fundamental understanding was of a great help in optimising these
erials, so that 100% capacity retention was achieved with plasticized
electrodes containing 1-micron particles. Since the measured capacity,
ast within the first hundred cycles, mainly comes from the CoO Co
version process, where two electrons are liberated, rules to increase the
all capacity were established. Hence the need to search for oxides in
ch the metal oxidation state was greater than 2 as well as our interest for
04, although numerous other spinels or layer oxides (LiCo02) could be
as well. We selected Co304 as our negative electrode, and went into the
cise of assembling Li-ion cells with Co304 as carbon alternative. The
o02/Co304 Li-ion cells cycled exceedingly (Figure 7.10) well at both RT
55°C, since no capacity fade was observed.42 Furthermore, these cells,
ng a weight ratio of positive to negative of 8.5, delivered a 2.2 V output
age, resulting in an energy density of about 130 Wh/kg. This value is not
petitive with today's existing value of 180 Wh/kg for LiCo02/C cells,
use the LiCo02/Co304 cells are penalized by both the voltage of the
tive electrode, which is too high as compared to carbon, and the 20%
ersible capacity linked to the use of Co304. These are not show
pers, since, through the large oxide family, there are compounds (MnO)
0
ng a reacting voltage of 0.5V vs. Lt/Li , and others (Li 1+xMn204) that
be used as positive electrodes, while having aLi reservoir to compensate
the initial 20% capacity loss. In this respect, the Li 1+xMn2 0JMn0
em is quite attractive, although still limited in power rate.
It should be realized that the appeal of the metal oxide negative
trodes is that their nano-structure is internally created during the first
trochemical reduction, producing pristine and compact nanoparticles,
h are held together through LizO boundaries domains.43 While it may
aken for granted, let's recall that a similar type of internal grinding
rs on the Ni(OH)z electrode, widely used in today's Ni-based alkaline
ries. Indeed, during the first electrochemical oxidation, there is a drastic
re change in the Ni(OH)z particles that evolve from monolithic to
aic-type. Controlling the size of these electrochemically-made mosaic
Key Role of Nanoparticles in the Reactivity of 3d Metal Oxides Towards Li 235

(b)
4 ,. I
Output Cell '
Voltage , 1
---"--,, I

0
CZl
........
3 ----
,.,I

>
"-"'
2
(!.)
OJ)
C\$ 1
........
0
> 0
0 2 4 6 8 10
x in LixCo 304
0.2
\ Co3b4 /LiCo02
1 I I I I

. 0.15
:_l
<. 0.1
c::
"-"'
;>..
......
u
C\$
0.05 Rate: C/5
u Mr=8.5 T = 25°C
C\$ I I I I I I
0
0 10 20 30 40 50 60 70 80

Cycle number
re 7.10. The first cycle of a LiCo02/Co304 cell cycled between 4.1 and l.IV, as
ured by means of three-electrode configuration, is shown in (a). The cell output
ge is of about 2 V and the weight ratio (M,) of positive to negative equals 8.5. The
city retention for such Li-ion cell is shown in (b).

ains, and in the same way the domain wall boundaries that act as a
er layer, is crucial to the performance of this electrode, since, upon
sequent cycling, the so called "Ni(OHh formation cycle" remains a
able know-how specific to each battery manufacturers. This situation
Chapter 7

rs from externally-made nanostructured powder, or electrodes that can


made either by chemical/physical means, with the greatest difficulty
g to gain maximum control over the size and size dispersion of the
ting particles or cluster of atoms. Therefore there are recent reports of
nced cycling performances obtained with nanostructured LiMn 204 or
P04 electrodes made by ball milling. A remaining difficult task with
nally made nanoparticles lies in the formation of densified electrodes, h
are crucial for practical applications. Therefore, new densification ods,
for instance Magnetic Pulse Compaction (MPC), may be of great
in densifying such highly divided electrode materials.
This novel reversible Li-reactivity mechanism, mediated through the
ation of metal particles, underscores the possibility when working at
atomic level to radically change reaction kinetics and
ical/electrochemical reaction paths. Indeed, one must keep in mind that
rticle size decreases, the amount of surface atoms adheres to that of the
, and becomes greater for particle size smaller than 20 A. Thus, the
considerations of the material electronic band structure or
allographic voids are no longer valid. Our motivation to revisit well
n materials, that were previously disregarded, is investigated next.

4. Acting on Reaction Paths Through Particle Size

When the starting oxides correspond to the lowest initial oxidation


of the metal ion (CoO, NiO, Cu20), we showed that metallic clusters
ormed as soon as the reduction process starts. In contrast, when starting
higher cationic oxidation states (Co304, Fe203), one can expect
mediate reduced phases to be found in the early stage of the reduction
ess. Through all the above studies, we focused on the oxide
mposition reaction occurring at low voltage, using mainly metal oxides
ecursor, with the exception of Co304, which turned out to be one of the
promising negative electrode candidates as a carbon alternative.
ed, this phase adopts the spinel-type structure, having empty tetrahedral
ctahedral sites to host Li. It was then of special interest to really
rstand the interplay between decomposition and insertion reaction,
Co304 was fully reduced to 0 volt. There are early reports4447 regarding
easibility of electrochemically/chemically inserting Li ions in either
4 or Mn304, but the results were poorly reproducible, and the value of
ndetermined, due to the coexistence of secondary phases resulting
the lithiation process. A legitimate question was whether such issues
be related to particle size/morphology. We then initiated a study
d at sensing how the particle size could influence insertion vs.
mposition reactions in oxides having open structures. Our results will be
Key Role of Nanoparticles in the Reactivity of 3d Metal Oxides Towards Li 237
8 49
ented through two pedagogical examples: Co30/ and a-Fez03.
tever the studied oxide, the first step towards such an approach consists
laborating synthesis methods to enable the formation of tailor-made
cles. Hence, each following section will begin with a material synthesis
ocol.

Co304 tailored powders were prepared in two steps. First, crystallized


alkoxides were made from a derived polyol process that involved
2
ing a solution of Co+ acetate tetrahydrate in 1,2-propanediol.
ndly, the precipitated powders were recovered, washed with ethanol,
then fired at various temperatures ranging from 250°C to 800°C. These
ples will be referred to as Co304(2SO) and Co304(SOO) samples, respectively.
C is the temperature needed (as determined by TGA measurement) to
re a total combustion of the structural organic molecules. The x-ray
der patterns of the annealed samples indicated the appearance of broad
s, characteristic of the spinel phase in the 250°C sample that increased
mplitude and sharpened with increasing temperature. From the Scherrer
tion, we noted that the crystallite size evolved with temperature, and
ased from about 150 A to at least 800 A. This particle coarsening
ted in a 60 m2/g to about 3m2/g BET specific surface area decrease
n increasing the sample annealing temperature. The most astonishing
t concerns the maintenance (Figure 7.11) of the precursor spherical
cles through the annealing process. Note also the very narrow size
ibution of the particles constituting the agglomerates. Such tailor-made
4 particles were the ingredient of our in situ X-ray electrochemical
es.
In situ X-ray Co304/Li cells based on Co304(soo) powders were made
discharged at various current rates. We note (Figure 7.12) the
arance of a LixCo304 phase for discharging current rates ranging from
to C/25, and its disappearance, at the expense of a CoO phase, as the
arge current was lowered to C/75. Similarly, in situ X-ray cells having
4 samples, annealed at various temperatures, were discharged at the
(C/12) current rate. The XRD patterns collected during the discharge of
304(2solLi and Co304(soo/Li cells exhibited, respectively, the sole
nce of CoO Bragg peaks and LixCo304 Bragg peaks. A common
minator to these observed effects is the current density sensed by the
cle, with the overall result being that high density favours Li insertion,
e expense of decomposition reactions. Hence Thackeray's difficulties
untered in achieving a pure
Chapter 7

100

90

50 750
150 250 350 450 550 650
Temperature COC)

e 7.11. Weight loss, as determined by thermo gravimetric analysis, for a home


esized Co glycolate precursor that was heated at a 10°C/min. rate. SEM
graphs shown for the initial precursors as well as for materials annealed at 250°C
00°C, respectively.

um-phase, whatever the chemical used or electrochemical approaches.


er reducing conditions and using a strong reducing agent such as n
yllithium, which to a certain extent mimics a cell short circuit (e.g., high
ent density), his chemically prepared samples always contained large
unts of LixCo304.
These findings indicate that the nature of the intermediates, when
04 is electrochemically reduced vs. Lithium, is rate/surface dependent.
intercalated LixCo304 formation suggests that kinetic limitations lower
ability voltage far below the over voltage of the Co304 Co0 reaction.
a poor kinetic is nested in structural aspects that are peculiar to spinel
tures. Indeed, the insertion of Li into Co304 necessitates the migration
o ions from the Sa to the 16c sites (spinel rock-salt). This Li-driven
2
ation of Co+ from Sa to 16 c sites is energetically costly, and competes
the Co304 decomposition reaction associated to the departure of oxygen
ng to CoO, which will then decompose into Co. A similar path was
n to occur for Mn304 that either decomposes into MnO or intercalates
LixMn304.
Thus, an open question is whether such findings regarding the
rtance of particle size on Li-driven reactivity paths could be generalized
her oxides differing from the spinel structure. As a tentative answer, we
Key Role of Nanoparticles in the Reactivity of 3d Metal Oxides Towards Li 239

Co304 : 250°C
2000
Co304 : 800°C
BeO A
BeO + BeO coJ04
Co3 Co304
1750 BeO

1500

1250

1000
ea_n
(.)

750

500

250

x=2.0 u:co304 LixCo30


4 36 36 40 42 44 34 36 36 40 42 44
Scattering Angle (2 8) Scattering Angle (2B)

re 7.12. In situ X-ray data for CoO/Li cells discharged at very low current drains
2)/ close to equilibrium at a C rate. The cells contained either Co0250 or Co0800
rodes .

ided to investigate Fe-based oxides, and more especially a-Fe203


matite), which has the corundum structure, and is known to switch from a
agonal compact to a cubic, close-packed oxygen array at a Li
centration lower than 0.1 per unit formula.

4.2. a-Fez03

Two batches of a-Fe203 (hematite), referred to as M-Fe203 (for


rometric) and n-F 03 (for nanometric), were used in this study: M-Fe203
commercial sample (Aldrich or Prolabo), and n-Fe203 is a homemade
der prepared by forced hydrolysis in acidic medium. More specifically, ic
nitrate hydrate Fe(N03)3.9H20 was progressively dissolved in a HN03
eous solution that was heated in a glass vessel under magnetic stirring,
refluxed at boiling point for 24 hours. Then, the recovered reddish
wn powder was thoroughly washed and dried prior to being investigated.
Aside from some slight deviations in the relative peaks intensities, the
D patterns for M-Fe203 and n-F 03 (Figure 7.13) perfectly match that of

- Ill 300

-
c.
0

200

100
Chapter 7
>
:!:::
0

-
Ill
I::
Q)
1200
I:: 800

400

30 40 50 60 70 80
Scattering Angle (deg.) CoKo:

e 7.13. X-ray powder patterns for commercial and home-synthesized a-Fez0 3


her with, as inset, the SEM image for both samples.

e203• While structurally similar, these two samples strongly differ in the
h of their Bragg reflections. From the Scherrer's equation, we estimated
mean crystallite size at about 200 A for n-Fe203, and at least 1000 A for
e203• By TEM, the lozenge-shaped n-Fe203 particles were found to be
olithic and very small (200 A), in total agreement with the crystallite
deduced from XRD analysis. M-Fe203 particles are much larger (0.5
in mean diameter), as shown by SEM images. The measured BET
2 2
ific surface areas are 60 m /g and 2 m /g for n-Fe203 and M-Fe203•
The first electrochemical discharge curves collected at C/5 rate for the
hematite samples previously described are presented in Figure 7.14.
n discharged down to 0 Volt, 7.2 Li per M-Fe2 03 and 8.3Li per n-Fe203
be reacted, corresponding to capacities of 1200 and 1400 mAhlg. Both
harge curves show a nicely developed and long voltage plateau lying
w 1.0 Volt, until an x value of about 6 (x in "LixFe203"), in agreement
3 0
the theoretical capacity for the Fe + 7 Fe reaction, is reached. The
r excess in capacity measured for n-Fe203 is consistent with its much
r specific surface area, when compared to that of M-Fe203•
Key Role of Nanoparticles in the Reactivity of 3d Metal Oxides Towards Li 241

400Capacity (mAh/g)


200 600 800 1000 ' 1200 1400
30

s. 2.5

r:l.l
2

c 1.5

s
1
Oll
0 0.5

0
0 1 2 7 8

e 7.14. First discharge for a-FezO/ Li cells, using bulk or nano a-Fez0 3 as positive
ode, together with, as insets, the open circuit voltage measurements for similar cells.

However, the most relevant part of the curve, with respect to the
ortance of nano particles, lies at low x values. Indeed, note that the onset
he 1 V plateau is very quickly reached for M-Fe203 (x = 0.1), while it
rs at x=2 for n-Fe203, suggesting a different Li reactivity mechanism
een the two samples. To better isolate such differences, PITT
riments were conducted on n-Fe203 and M-Fe203 up to x=2. Within this
position domain, the reduction of n-Fe203 clearly proceeds in two steps.
, a monophasic process characterized by a continuous decrease in the
i-equilibrium OCV is observed up to x close to 1, and then a biphasic
tion characterized by a constant equilibrium voltage close to 1.85 Volts.
The Li reactivity difference was well diagnosed by in situ X-ray
surements (Figure 7.15), with a continuous shift of the hematite Bragg
s towards low angles for the n-F 03 sample, as compared to a
ressive vanishing of the hematite Bragg peaks for M-Fe203 reflections,
he expense of a new set of reflections. These extra peaks, that were
xed within a cubic symmetry having an axis of 8.422 A, were found to
espond to a Li-Fe-0 rock-salt compound described by Thackeray et al.50
not to a FeO rock-salt phase (as confirmed by EXAFS and Mossbauer),
should have an a axis of 4.31 A (e.g., 2a = 8.62 A).
Chapter 7

12000
00oo ::o--- "-'

10000:;
/1.\"---v
o:- - :::.
In

8000
-n
0ooob
6000 .!!

37 38 39 40 41 42 43 37 38 39 40 41 42
Scattering Angle (deg.) CoKu Scattering Angle (deg.) CoKu

e 7.15. in situ X-ray data for a-F 03/ Li cells, using either bulk or nano a-F 03
ositive electrode. For reasons of clarity, only part of the pattern (33°
< 43°) depicting the evolution of the 104 and 110 Bragg peaks as a function of the
nt of reacted Li is shown. Note a disappearance of these peaks for the bulk sample,
mpared to a shift for the nano-materiaL

Thus, from these measurements, it appears that up to one Li per


ula unit can be inserted into the a-Fe203 corundum structure of n-Fe203,
lting in a 1% volume expanded a-LiF 0 3 end-member phase, having
attice parameters a=5.041(1) A and c=13.815(2) A, while no lithium can
gnificantly inserted into M-Fe 2 03. The feasibility of inducing reversible
rtion reactions in n-Fe203, and not in M-Fe203, is mainly nested in the
that small particles can more easily and uniformly expand to
mmodate strains resulting from insertion reactions than larger ones.
Finally, when either Li/n-Fe203 or Li/M-Fe203 cells were cycled at
rate between 1 and 3.5 V, we observed (Figure 7.16), as expected, that
ones containing nanometric Fe203 display a nicely reversible and
ined capacity upon cycling, while the other cells did not exhibit any
of reversibility.
Key Role of Nanoparticles in the Reactivity of 3d Metal Oxides Towards Li 243

. _-·r-0('1
- - "o .
0 0.
1om
8 --r--------r
45
c::::::
....- 4
, 3.5 -
-
e" il o.
0.
eo L
40.:;,
o..o. --
.a d
OJ)

r JJ -
>
0.1 201;!_
3_ u oL- -- - ---'---' €
> 2.5 -
'""-'
8 12
Cycle number
18 28

2-
1.5-
1
0
>o.5 0 0.5 1
x in LixFe203

,...-._ 5

+.-<
5.....:l
4.5 n-Fe203
4
rJJ
> 3.5
>
'""-'
3
OJ) 2.5
ro
,.-.+..-.>.; 2
0
> 1.5 0 0.5 1
x in LixFe203

re 7-16. Voltage-composition profile for o:-F O/ Li cells, having bulk (upper) or nano
er) o:-F 03 as the positive electrode. Their capacity retention upon cycling is shown by
nsets.

Worth mentioning is the large irreversibility displayed by the Li/n


03 cell, whose origin still remains precisely undetermined, while there is
ng suspicion for the presence of chemical groups, specific to the n-Fe2 03
hesis process, that remain adsorbed at the surface of the highly divided
ders. Further studies must be carried out to sort out this issue.
ertheless, throughout this work we stressed the importance of particle
in controlling Li reactivity mechanisms. We also resolved to unravel
ntial electrode materials that were thus far disregarded. As time elapses,
erous examples, which further emphasise the wonders of nano
pounds in igniting unexpected reactions, appear. They encompass
Chapter 7

es, nitrides, fluorides and sulphides, and another family of materials like
rmetallics. For instance, our group recently reported that the reactivity of
b3 towards Li is reversible. Although Co-Sb bonds are broken during the
harging process, leading to a full disintegration of the CoSb3 structural
ework into Co and LhSb nano particles, we show that upon recharge
e destroyed bonds, due to the high reactivity of the divided metal nano
icles, reformed and arranged to convert back to the initial CoSb3
51 2
cture Such an example, also observed with Cu6Snl , further contrasts
previous beliefs that bond-breakings were prohibited for reversible Li
tivity.

CONCLUSIONS

We have shown, through a few descriptive examples, how the field of


materials can unravel novel reactivity mechanisms so far not expected
ccur at the macroscopic scale. These mechanisms are of tremendous
ortance, since, for instance, the reported reversible reactivity of 3d metal
es towards Li was shown to be universal, and to apply to a wide family
ompounds. Furthermore, although we limited ourselves to electrode
rials, size confinement can also positively affect other battery
ponents, such as electrolyte, current collectors and others. On that issue,
ecalled a few recent reports that dealt with the positive attributes of
ng TiOz or Alz03 nano-particles to polymer electrolyte. This would
nce their conductivity several times. Consider also the make-up of nano
tured electrodes to bypass electronic limitation. The awareness of the
ortance of nano materials is rapidly growing within the battery
munity. A new path of opportunities has been opened. In the quest for
electrode materials, we no longer need materials with good electronic
uctivity or open structures. Thus, a large variety of previously
garded compounds are worth revisiting. As a new field is opened, its
rstanding suffers from the lack of theoretical support to build on.
ding this theoretical platform on nano driven Li electrochemistry stands
great challenge that requires interactive studies between chemists,
rochemists and theorists. An exciting adventure awaits us....

KNOWLEDGMENTS
The authors would like to give special thanks to L. Dupont, M. Dolle,
ayen, F. Badway, and I. Piitz for their contribution to some of the
ented data.
ey Role of Nanoparticles in the Reactivity of 3d Metal Oxides Towards Li 245

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S. Grugeon, S. Laruelle, J.M. Tarascon, J. Electrochem. Soc. submitted (2002).
N. Pereira, L.C. Klein, G.G. Amatucci, ECS and ISE Joint International Meeting, San
Francisco, CA, Sept. 2001, paper 203.
N.Pereira, L. Dupont, J.-M. Tarascon, L. Klein, G.G Amatucci, J. Electrochem. Soc. (in
press).
F. Badway, I. Piitz, S. Grugeon, S. Laruelle, M. Dolle, A.S. Gozdz, J-M. Tarascon,
Electrochem. Solid-State Lett. 5 (2002) A115.
A. Delahaye-Vidal, B. Beaudoin, M. Figlarz, Reactivity Solids 2 (1986) 223.
W.I.F. David, J.B. Goodenough, M.M. Thackeray, M.G.S.R. Thomas, Rev. Chim. Miner.
20 (1983) 636.
M.M. Thackeray, W.I.F. David, J.B. Goodenough, Mat. Res. Bull. 17 (1982) 785.
M.M. Thackeray, W.I.F. David, P.O. Bruce, J.B. Goodenough, Mat. Res. Bull. 18
(1983) 461.
M.M. Thackeray, S.D. Backer, K.T. Adendorff, Solid State Ionics 17 (1985) 175.
D. Larcher, G. Sudant, J-B. Leriche, Y. Chabre, J-M. Tarascon, J. Electrochem. Soc. 149
2002) A234.
D. Larcher, C. Masquelier, D. Bonnin, Y. Chabre, V. Masson, J-B. Leriche, J-M.
Tarascon, J. Electrochem. Soc. submitted (2002).
M.M. Thackeray, J. Coetzer, Mat. Res. Bull. 16 (1981) 591.
.-M.Tarascon, M. Morcrette, L. Dupont, Y. Chabre, C. Payen, D. Larcher, V. Pralong, J.
Electrochem. Soc. in press (2003).
D. Larcher, L.Y. Beaulieu, 0. Mao, A.E. George, J.R. Dahn, J. Electrochem. Soc. 147
2000) 1703.
apter 8

NITRIDE AND SILICIDE NEGATIVE


ELECTRODES

G. G. Amatucci and N. Pereira

Telcordia Technologies, 331 Newman Springs Road, Red Bank, NJ 07701, U.S.A.

INTRODUCTION
The search for negative electrode materials which exhibit improved
rochemical properties relative to the widely used graphite intercalation
rials has lead to a renaissance of research on inorganic negative
rodes.
The intercalation of Li+ into graphite follows the basic topotactic
tion process:

(8.1)

Beyond basic binary lithium alloys, a large focus has been on the
lopment of conversion oxides. The conversion oxides MexOy, as
ussed in a previous chapter, consist of metals (Me) which can alloy with
um. Upon the first lithiation, an electrochemically induced conversion
ess occurs creating a nanostructure consisting of nanodomains of Me in
trix of nonstructured Li2 0 (8.2):

2yLi+ + 2ye- + MexOy -+ yLhO + xMe (8.2)


zLt + ze- + yLhO + xMe !::+ yLhO + xLizMe (8.3)

The combination of the nanosized metal and buffer matrix of Li2 0


to reversible alloying reactions (8.3) that have much improved
sibility than traditional LixMe alloys. More recent studies have focused
he use of MexOy initial materials in which Me is a metal which does not
ort alloying reactions with Li. These materials were found to convert
g the cathodic scan analogous to reaction (8.2); however this
Chapter 8

ersion reaction was found to be reversible (8.4):

(8.4)

The quest for new inorganic anodes has recently proceeded into areas
ch have been largely ignored, namely, nontraditional MexXy materials,
re the anion X is N or P. The number of papers on these type of
erials is relatively small, but nonetheless the electrochemistry is found to
urprisingly rich and somewhat exotic. In this chapter, we take a close
at the work that has been done to this point on binary and ternary metal
des along with a look at the often overlooked metal silicides.

. THE NITRIDES

.1. The Ternary Nitrides

1.1. The Antifluorites (Lh,..1MNx)

Metal nitrides have been investigated for their properties related to fast
um ion conduction for the past two decades. The most famous of these
des is the highly conducting Li 3N 1- 7 which exhibits ionic conductivity on
2
order of 1'10- S/cm. A number of papers have been published on this
rial; however, because of its poor resistance to anodic decomposition at
potentials, it has found little use as a solid state ionic conductor in a
tical cell. In spite of this drawback, the initial work spurred interest in
nvestigation of alternative nitrides that could also support appreciable
conductivity as a result of the low polarizability of the nitrogen anion.
y of these structures are related to Li2x_ 1MNx which is based upon the
luorite structure. Containing pathways for facile ion movement, these
rials exhibited appreciable Li+ conductivity. Materials such as Li 3BN2, 8
iN3,9 •10 and Li 3AlN2 all share this structure type and have well
lished ionic activity. Due to their electronically insulative properties,
materials were investigated solely for use as solid state ionic
uctors.
The facile movement of the lithium ions within the antifluorite
ture gave rise to the question whether such structures could be utilized
radaic insertion intercalation electrodes for lithium batteries. This issue
addressed by the use of transition metals as a substitute for M in Lizx-
x. The resulting Lizx_ 1MNx structure gained appreciable electronic
uctivity to parallel the existing ionic conductivity. The materials, due to
ubstitution, were mixed conductors, opening the possibility for their use
e and Silicide Negative Electrodes 249

egative electrode materials. In light of this, the electrochemical activity


i2x_ 1MNx materials were investigated particularly for materials containing
Mn or Fe.

e 8.1. Crystal structure of Li 7 MnN4 from the [110] viewpoint. Dark spheres represent

nN4 can be fabricated through solid state reaction between Li 3N and Mn


Mn4N in a N2 atmosphere. The material crystallizes in the cubic
luorite structure built of isolated MnN 4 tetrahedra where Mn and Li are
ted on tetrahedral sites (Figure 8.1). Li and Mn are present in ordered
ngements with clearly observable three dimensional pathways for
sion. Despite the high formal charge associated with the Mn cation
5
+), the structure is prelithiated; therefore, the cycling of the material
mences with lithium extraction. This feature makes it particularly useful
Li-ion batteries utilizing non-lithiated positive electrodes. The
hiation of Li7MnN4 was found to proceed to Li5.45MnN4, centered on
aus at approximately 1.15 V (Figure 8.2). The initial 0.625 lithium
cted corresponded to a two-phase delithiation in a unit cell with same
metry but different lattice parameter. The remaining lithium was
ved in a single-phase reaction. The structural transformations are
rsible and the material cycles well with a stable 300 mAh/g specific
city.
In Li7MnN4 the Mn cation exhibits an unusually high nominal charge
5
n +. Even more surprising, assuming an ionic model, the Mn cation
6 7
eeds to a mixed oxidation state of Mn +/Mn + upon charge. These
ual electronic attributes combined with the material's relatively low
11
tion potential of 1.2 V spurred Suzuki and coworkers to a deeper
stigation of the electronic attributes of the material leading to its active
rochemistry.
Chapter8

2.0

i§ :::--_; --·---- --- .\. ,


0.5

200 400 600 800 1000

Capacity (mAh/g)

e 8.2. Voltage profile of Li 7MnN4 (from Ref. 12).

The investigation was accomplished through the use of core level


ron energy loss spectroscopy. It was found that in the ground state, there
a number of holes on the N 2p band. This is consistent with the strong
idization of the Mn 3d and N 2p orbitals associated with the covalency
he compound. Analysis of the lithium deintercalated Lh-xMnN 4 where
revealed a strong growth in the N-K spectra related to the amount of 2p
cupied states. Simply stated, lithium deintercalation proceeds with an
ation reaction introducing holes into the nitrogen 2p orbitals. This is in
contrast to the classical situation where holes are introduced into the
ition metal (manganese) 3d orbitals. Therefore, one can make the
ralization that the electronic redox is centered on the N rather than Mn
explains the low redox voltages associated with the Li7MnN4 electrode
rials.
As opposed to Li7MnN4, Li3FeN2 crystallizes in orthorhombic
metry. However, fundamental similarities exist as the structure is a
rted form of the antifluorite structure. The structure can be simply
acterized as Fe4N tetrahedra sharing edges to form one-dimensional
ns along the c direction.
The structural evolution during delithiation was characterized in depth
12
ishijima and coworkers. Delithiation occurred at approximately 1.2 V
he range of Li3FeN2 to LizFeN2• Four phases appeared during the
hiation reaction, all were of orthorhombic symmetry. Relithiation
rred with systematic redevelopment of the phases evolved during
hiation. The reversible lithiation processes occurred with little
/under potential and the crystallinity of the material is maintained for
It should be noted that delithiating Lh-xFeN2 beyond Li 2FeN2 resulted in
ecomposition of the crystal structure.
e and Silicide Negative Electrodes 251

Question still remains to the electronic basis of the redox reaction of


eN2. Nishijima et al. concluded that the redox was classical and centered
3 4
he reversible Fe + -+ Fe + reaction. This conclusion was centered on
lts of Mossbauer spectroscopy. Half a decade later, Suzuki et al. realized y
similarities related to the structural electrochemical features of eN2
and believed the electronic reaction to be similar to that of Li7MnN4
entered electronic redox) although no supporting spectra was offered.

.2. The Hexagonal Lh(Lh.xMx)N Structures

The second major class of ternary lithium transition metal nitrides


s in a structure which is isostructural with the well known Li3N lithium
onductor. These materials take the stoichiometric form of Li 2(Li 1.xMx)N
13
its better known notation, Li3_xMxN. where M= Co, Cu, and Ni. The
structure (Figure 8.3) can be simply envisioned as u+ between layers
1
hN -. The transition metal cations substitute for the Li between the
s; however, it should be noted that this site is slightly unusual as it
ists of a linear N-M-N bond along the c axis and is not octahedral or
hedral in nature. From an electrochemical standpoint, the most
ising and most studied of the transition metal substitutions is Co. 14

..,..,...........,."'"-.:LizN Layer

(Li\M+(l·x)) Layer
01(1

e 8.3. Schematic of Li2(M 1_xMx)N structure.

Lh-xCoxN materials can be prepared by the reaction of Li 3N and Co


l under a N2-based atmosphere. The solid solution range for Lh-xCoxN is
It was quickly identified that the optimum specific capacity could
alized from a composition of Liz. 6Co0.4N.
Small amounts of Li can be inserted into Li3_xCoxN during the initial
arge reaction between 0.5 and 0.1 V (Li/Li+). The amount of lithium
ChapterS

rted is related to Li vacancy population but the specific capacity does not
ed 100 mAh/g. Practically speaking, Liz.6Co0.4N can be treated as being
he lithiated state; therefore, lithium must be deintercalated from the
cture in an initial anodic oxidation. During the first charge, Li 2.6Co0.4N
les the removal of approximately 800 mAh/g of charge at an extended
au at 1.1 V corresponding to a delithiated composition of approximately
Co0.4N. Subsequent discharge and charge results in the reversible
rtion of 800 mAh/g from 1.5 to 0.1 V (Figure 8.4). After the initial
hiation cycle, subsequent delithiations remove capacity in a

2.0,..----------------,

200 400 600 800


Capacity (mAhlg)

e 8.4. Voltage profile of Li2.6Cao.4N vs. Li metal counter electrode. Cycle numbers are
ated (from Ref. 15).

dolinear profile at voltages between 0.5 and 1.1 V. Excellent cycling


lity is observed for this material.
Ex-situ X-ray diffraction revealed that the delithiation reaction
eeds topotactically for Llx=l in Lh 6-xCo0.4N. In this region the reversible
ific capacity is 480 mAh/g and the crystal structure does tend to become
15
rphous with cycle number. More recent data suggests the initial
hiation reaction proceeds concurrent with a systematic and gradual loss
ystallinity. Regardless, extending the initial lithium removal to Llx=l.46
ts in the systematic destruction of the crystal structure and formation of
-ray amorphous compound. It is easy to understand from the inspection
e crystal structure (Figure 8.3) how excess u+ deintercalation can lead
s destabilization and loss of crystallinity. Subsequent cycles revealed an
essively stable specific capacity of approximately 800 mAh/g. To gain
insight on the faradaic activity leading to the electrochemical activity
i2.6Co0.4N, a more localized investigation of the electronic structure of
aterial had to be taken by alternative techniques.
e and Silicide Negative Electrodes 253

As with the Li 7MnN4 antifluorite material discussed in the previous


ion, a number of mysteries exist with respect to the electronic structure
e optimized Liz.6Co0.4N. Utilizing a basic ionic stoichiometry model, the
2.6 0.4 1 3
ge
Li distribution of Li Co N should be +26Co +0 .4N-. Although
1

ovalent cobalt is very rare, characterization by EELS 16 revealed


rising data consistent with the existence of the monovalent cobalt cation.
zing this stoichiometric model, delithiation to Li1. 0Co0.4N would require
to adopt the even more unusual Co5 + oxidation state. EELS
surements were performed on the fully delithiated sample. Figure 8.5
s the N-K spectra of that sample. The band at 403.5 eV is ascribed to
hybridization of the nitrogen 3p band with the lithium 2s band. The

395 400 405 410 415


Energy Loss (eV)

e 8.5. N-K EELS spectra of lithiated and delithiated Li 2.6Cao.4N (from Ref. 15).

hiated Liz.6_xCo0.4N sample reveals an expected decrease of the 403.5


eak consistent with the removal of Li and subsequent decrease of Li-N
s.
The peak at 400 eV is associated to the unoccupied nitrogen 2p band.
thium is removed the intensity increases drastically, consistent with the
lopment of holes on the nitrogen 2p band during electrochemical
hiation. EELS analysis of the cobalt indicated the oxidation state to be
oximately Co3+ after oxidation. This would require the removal of the
ining electrons from the nitrogen bands to effectively charge
pensate. This interplay is clear from the schematic of the electronic
ture of Li2.6Co0.4N. Therefore, like in the case of Li7MnN4, the nitrogen
n plays a crucial role in the redox chemistry of
Li2.6Co0.4N.
Other Lh-xMxN based materials exist. Early on, Lh-xMxN materials
e M = Ni or Cu were also investigated. These materials also crystallized
e space group of P6/mmm. The Li2.6Cu0.4N sample exhibits good
cycling
ChapterS

ility, on par with that of Liz,6Co0.4N. The copper compound revealed 650
h/g in the 0-1.3 V range. The Ni system, in contrast, was found to show
versible specific capacity of only 180 mAh/g in the range of 0.0 to 1.4 V.
Most recently, a layered lithium nitride has been investigated in the
17
uit of a less toxic and more cost effective negative electrode material.
eN2 is a layered nitride with hexagonal LhN layers analogous to the Lh_ N
materials described above. A similar material Li2(Li0.7Fe0.3)N
7Fea.3N) was investigated for its electrochemical performance. The
rial exhibited 550 mAh/g at an average potential (between 0.05 and 1.2
f 0.6 V. Analogous to Li 2.6Co04N, the structure decomposes to a quasi
rphous state upon delithiation.

2.2. The Binary Nitrides

Some of the earliest work on binary nitrides as alternatives for


hite or Li has come by way of thin film work. One of the first
18
pounds to be investigated was that of Sn3N4• Sn3N4 films can be
ared by reactive sputtering_ of Sn in a Ar-N 2 gas mixture. The films
tallized in the hexagonal P 3 ml space group expected for this material.
larly, films of InN were deposited. The lithium reaction mechanism for
of these consisted of a straightforward conversion reaction to a LixSn or
alloy embedded in a matrix of LhN. Subsequent specific capacity is
loped through the alloying reaction with Sn or In, as LhN remains as a
er matrix. As expected, the alloying reaction was found to give relatively
cycling due to the electromechanical grinding induced by large volume
ges within the alloy.

Ge3N4 crystallizes in a hexagonal structure with large tunnels


retically capable of lithium intercalation parallel to the c axis. Lithium
found to be able to reversibly react with Ge3N4 at a voltage of 0.25 V
a reversible capacity ranging from 500 to 1200 mAhlg depending on the
19
allite size (Figure 8.6). Finer crystallites were found to offer much
oved specific capacity. The low voltage at which Ge3N4 is
rochemically active makes it especially suitable for use as a negative
rode in Li-ion. The cycling stability of Ge3N4 was found to be quite
with less than 15% loss after 70 cycles (Figure 8.7). In-situ and ex-situ
e and Silicide Negative Electrodes 255

D revealed that Ge3N4 experienced a large loss of crystallinity during the


discharge. This, combined with an irreversible loss of 30-50% active
rial and a 50% irreversible capacity loss, suggested a portion of the
rial converted during the first cycle concomitant with an alloy
ation:

+ 3x)y Li+ + (12 + 3x)y e· + Ge3N4--+ 3y LixGe + 4y LhN + (1-y)


Ge3N4
(8.5)

().1.5V- 23mAig
-. SO% Irreversible Loss
1.5

c
y
0 0.5
;;.

0.5 1.5 2 2.5 3.5


#LiperGe

e 8.6. Voltage profile of crystalline Ge 3N 4 cycled vs. Li metal between 0 and 1.5 Vat a
ant current of 23 rnA/g.

- 1000 0-0.7V • 23mA/g


1 800

E
1 E 600
c.
...
u
..
0 1t>.O 400
;
-.l/l.=.. 200

Q LW LW LL LLU
0 10 20 30 40 50 60 70 80
Cycle#

e 8.7. Cycle life of crystalline Ge 3 N 4 cycled vs. Li metal between 0 and 0.7 V at a
ant current of 23 rnA/g.
Chapter 8

The reaction products were of exceptionally low crystallinity and


e characterization difficult.
The remaining cycles are believed to incorporate themselves within a
rsible alloying reaction (8.6) (supported by selective area electron
action) on crystallites composed of alloy "shells" grown on core
ctures of unreacted Ge3N4 (Figure 8.8).

ixGe + 4y LhN + (1-y) Ge3N4 !::+ 3y Ge + 4y Li3N + (1-y) Ge3N4 +


u+ +3xy e" (8.6)

The X-ray amorphous nature of the alloy combined with a substrate of


N4 is believed to bring about the uncharacteristically good cycling
ormance for en electrode based on lithium alloying.

Residual Ge3N 4
Amorphous
•Li. Ge +Li3N

e 8.8. Schematic representation of a Ge 3N 4 particle exhibiting an unreacted G N 4 core


unded by an electrochemically active converted shell.

The electrochemical behavior of zinc nitride thin films versus metallic


20
as first reported by Bates et al. It was postulated that the reaction was
lar to the irreversible conversion reaction taking advantage of the
ing properties of Zn. Zn metal alloys easily with Li and as such the Li
21 22
hase diagram exhibits five alloys, LiZn4, LizZn5, LiZn2, LizZn3 and
.

(6+3x) Lt + (6+3x) e- + Zn3N2 -+ 3 LixZn + 2 LhN (8.7)


3 LixZn + 2 LhN !::+ 3 Zn + 2 Li3N + 3x Lt + 3x e- (8.8)

Recent analysis of powder Zn3N2 revealed finer attributes of the


23
rochemistry which was not initially obvious. Zn3N2 reversibly reacts
lithium electrochemically, exhibiting a large reduction capacity of 1325
/g corresponding to the insertion of 3.7 Li per Zn. Of this initial
city, 555 mAh/g was found to be reversible. In-situ and ex-situ X-ray
action revealed the reaction mechanism with lithium was a conversion
e and Silicide Negative Electrodes 257

tion of Zn 3N2 into LiZn and a matrix of LhN, the high-pressure analog
i3N:

(8.9)

Upon oxidation, LiZn transformed into metallic Zn, while Li3N


ributed to the transformation into LiZnN:

LiZn + 2/3 LhN-+ 7/3 e· + 7/3 Lt + 1/3 Zn + 2/3 LiZnN (8.10)

This reversible metal - Li 3N conversion mechanism is analogous to


mechanism (8.4) that was previously isolated to oxides and sulfides.
equent cycles proceed reversibly using the LiZnN and Zn as the
ursor materials. Indeed, the true reaction could be best described as two
llel reactions, one consisting of the reversible alloying reaction of the
Zn material, and the second consisting of a reversible conversion of the
N phase to the LiZn alloy plus Li 3N:

1/3 [LiZn !::+ e- + Li+ + Zn] (8.11)

2/3 [LiZn + f3Li 3N !::+ 3 e- + 3 u+ + LiZnN] (8.12)

The formation of LiZnN as the new end member of the


rochemical reaction with lithium was identified as the cause of the
ersible loss observed during the first cycle. Therefore, LiZnN can be
ed as a negative electrode material from the beginning as it would
bit 930 mAh/g with no initial irreversible capacity loss.
The cycle life of Zn3N2 was found to be poor. The poor cycle life was
ly attributed to the electromechanical grinding of the Li-Zn alloying
ion which contained appreciable volume change with alloy
position.

Cu3N crystallizes in the anti-Re0 3 cubic structure type. The structure


ists of NCu6 octahedra connected at the corners resulting in a 3D array
3D tunnels. Cu3N was found to involve a complex series of
rochemically induced transformations, of which the origins are not yet
24
known. The initial cathodic reduction of Cu 3N with u+ involved a
-step reaction mechanism (Figure 8.9). X-ray diffraction revealed that
attice parameter was found to expand during the first step. This was
ChapterS

2.5

2
>
';' 1.5
0.0
1 SEI

0.5

0 2 3
#LiperC N

e 8.9. First cycle voltage profile of a Cu 3N electrode cycle vs. Li metal between 0 and 3
constant current of 22.4 mA/g (equivalent to a C/6 rate).

istent with lithium intercalation into the open structure of Cu3N


urrent with copper displacement. Copper metal was detected by SAED
is region and the reaction was found to be irreversible. The second step
e electrochemical process was identified, using a combination of XRD,
D and TEM, as the conversion of the remaining copper nitride into a Cu
3N nanocomposite which promoted the formation of an organic layer at
urface of the nanocomposite. The latter two processes were found to be
rsible. The reversible nature of the Cu + Li3N nanocomposite is similar
at observed for the reversible nitride conversion mechanism of Zn3N2•

(8.13)

Cu3N electrodes showed excellent cycling efficiency at high rate


ivalent to 1.67 C) (Figure 8.10). Extended cycling seemed to promote
evelopment of electrochemical processes above 2V during delithiation
eas the cycling stability of the copper nitride conversion process was d
to be poor. These seem to be associated with the formation during
hiation of Cu20 and CuO believed to be rooted in electrolyte
adation. The reversible copper oxide conversion processes may
ribute to the increase in capacity with cycle number.

3. Summary - Nitrides

The metal nitrides exhibit an exceptionally wide range of reaction


hanisms with lithium, ranging from metal nitride conversion and
equent lithium alloying, reversible conversion, redox reactions
e and SiliridP NPuntivP PIPrtrnrlP<' 259

700

c:
.. . : 600

.§,
c
· ;:;
500

400
"-
u"'
2 "?
300
.."c::' 200
\.
-
100
i5
0 200
0 50 100 150
Cycle#

e 8.10. Cycle life of Cu 3N cycled vs. Li metal between 0 and 3 V at a rate equivalent to
c.

ciated to the anion, to simple topotactic insertion. The reaction


hanisms of these materials are closely tied to the electronic configuration
thermodynamic stability of the phases upon reduction. Some of the
l nitrides' uniqueness is a result of the low electronegativity and
lent character of the nitrogen atom. This places the Fermi level close to
of the nitrogen 2p bands as opposed to the transition metal 3d bands
ally encountered in oxides. These materials have also presented to the
archers an added complexity to material characterization to uncover
e mechanisms as many of them occur within quasi-amorphous structures.
It is still too soon to comment on the expected viability of metal
des as negative electrodes in Li-ion batteries of the future. However,
Co0.4N has shown its viability by being successfully implemented into
25
n cells. High specific capacities, exceptional cycling stability and
voltage profiles have been demonstrated within the metal nitrides
ussed in this chapter. However, the combination of all of these attributes
g with low air sensitivity and cost have yet to be demonstrated in one
rial. Regardless of the eventual outcome, the nitrides offer a new path
rds next generation negative electrodes with a rich electrochemistry
ed by few other materials.

SILICIDES

1. Introduction

Binary lithium alloys have long been considered as alternative


tive electrode materials as they exhibit greater specific capacities,

cially volumetric capacities, than carbonaceous materials. The Li-Si


m shows the highest theoretical capacity of over 4000 mAh/g with the
ChapterS

ation of Li44Si. Unfortunately, the cycle life of binary alloys is poor as


e volume changes are associated to repeated alloying/dealloying
lting in the pulverization of the electrode. One area of research to
ove the performance of Li-Si alloys focuses on silicon-based
composites. Silicon has been dispersed in different types of materials
bonaceous materials, ductile metals, TiN, etc...).
An alternative approach to the silicon-based nanocomposite considers
investigation of silicides for use both at elevated and ambient
erature. The examination of several binary silicides26' 27 showed only a
reacted with lithium significantly at ambient temperature. This section
mostly focus on magnesium silicide, Mg2 Si, which exhibits interesting
rochemical properties, such as high capacity and low potential, even at
ient temperature.

2. Ternary Li-Si-M Systems at Elevated Temperature


.1. Thermodynamics

Anani and Huggins28 proposed a methodology, based on the principles


rnary thermodynamics, to predict how the addition of a third component
binary system could alter both the capacity and the potential of the
y counterpart. They aimed at ternary alloys, using Li-Si-M alloys for
tration, with improved electrochemical performance for use as negative
rodes in thermal batteries, using FeS2 as cathode material and operating
e 400-450°C temperature range.
The reactions of an initial Si-M alloy with lithium were predicted
g the isothermal equilibrium phase diagram of the Li-Si-M ternary
m at the adequate temperature (400°C in this case). The construction of
phase diagrams was based on the free energy of formation, or Gibbs
energy, of all the binary and ternary phases known to exist in the Li-Si
ystem. An estimation of the theoretical potential, at which the
ibrium reactions (or three-phase equilibria) should occur, was obtained
the Nernst relation. Table 8.1 shows the theoretical potential and the
etical capacity of several M-Si alloys (where M = Ca, Cr, Mg, Mn, Mo,
Ni, Ta, Ti and V) used as starting materials. The maximum theoretical
ific energy (MTSE) values provided in the table were obtained as
ws:

MTSE = (26.805 · n · Eav) I W (8.14)


e and Silicide Negative Electrodes 261

8.1. Estimated thermodynamic properties of several Li-Si-M ternary systems (from


28).

em • Starting Phases in equilibrium Electrode Electrode MTSE


composition potential capacity (Whlkg)
(mV vs. Li)
Li/Si Li/g
(x103)
-Si Li7 Si3 Li7 Si3-Li13Si4 158 0.92 18.1 428
Mg Mg2Si Mg2Si-Mg-Li13Si4 60 3.25 32.7 574
Mn MnSi MnSi-Mn 5Si3-LhSi3 163 0.93 10.4 316
MnsSi3 MnsSi3-Mn3Si-Li13Si4 45 1.44 11.1 350
Mn3Si Mn3Si-Mn-Li33Sis 43 4.40 19.7 474
Mo MoSi2 M oSi2-M osSi3-Li13S i4 120 2.28 24.8
502
MosSi3 MosSi3-Mo3Si-Li22Si5 3 1.96 9.7 328
Ni Ni1Si13 Ni 7SiwN iSi-Li12Si7 316 0.79 12.1 317
Nb NbSi2 NbSi,-NbsSh-LhSi3 184 1.63 19.0 432
Ta TaSi2 TaSi2-Ta5Si3-Li7 Si3 211 1.63 12.6 344
-V VSi2 VSi,-V 5Si3-Li1Si3 191 1.63 25.2 486
Ca CaSi CaSi-Ca2Si-Li22Sis 13 2.2 26.4 544
Cr CrSi2 CrSi2-CrSi-LhSi3 223 1.17 18.8 420
CrSi CrSi-Cr5Si3-Li7 Si3 205 0.93 10.8 315
Cr5Si3 CrsSi3-Cr3Si-Lit 3Si4 138 1.44 11.6 341
Ti TiSi TiSi-Ti5Si3-LhSi3 182 1.55 11.3 328
Li-Si

re n is the number of moles of lithium involved in the reaction, Eav is the


rence between the positive (FeS2) and negative electrode (M-Si alloy)
ntials and W is the weight of active material. Because the ternary Li-Si
Li-Si-Mo and Li-Si-Mg systems exhibited improved maximum
retical specific energy (544, 502 and 574 Wh/kg, respectively) with
ect to the binary Li-Si system (428 Whlkg), they appeared as potential
native negative electrode materials for thermal batteries.

2.2. The Li-Si-Mg System

The theoretical results provided in the previous section were verified


29
rimentally using the ternary Li-Si-Mg system. ' 30 Mg2 Si is the only
metallic compound existing in the Mg-Si system. Thermodynamics
icted a three-phase equilibrium at 400°C that can be depicted by the
wing reaction:

4 Mg2Si + 13 Li 8 Mg + Li 13Si4 (8.15)

According to equation (8.15), the theoretical potential and capacity of


Si upon reaction with lithium correspond to 0.06 V vs. Li/Lt and 876
ChapterS

h/g, respectively. Coulometric titration techniques with current densities


he 5-20 mNcm2 range were performed at 440°C using three-electrode
. Mg2Si was used as working electrode and a 44% Li-Si alloy served as
ter and reference electrode while the electrolyte consisted of a LiCl-KCl
ctic. The resulting Mg2Si voltage profiles showed a specific capacity of
mAh/g at an average potential of 0.07 V vs. Li!Lt; these data agree
with the theoretical values predicted by thermodynamics (Table 8.1). In
of these results, the use of Mg2Si as negative electrode would provide a
of higher specific energy than a cell utilizing a Li-Si binary alloy (based
he Li7Sh-Li 13Si4 equilibrium).

3. Silicides at Ambient Temperature

Two conflicting mechanisms have been found for the reaction of


Si with lithium at ambient temperature. One scenario involves the
calation of lithium into Mg2Si to form Li 1Mg2Si while the formation of
ique ternary LizMgSi phase intervenes in the second scheme.

.1.1. Formation of Li1Mg 2Si

Huang et al.31• 32 reported the insertion of up to 2 lithium per Mg2Si


is equivalent to a specific capacity of 700 mAh/g. The working
rode, constituted of 98 wt% Mg2Si active material and 2 wt% ethylene
ylene-diene binder, was tested versus lithium metal down to 0 V at
58 mNcm2 . X-ray diffraction showed the material maintained its
alline structure upon reaction with up to one lithium but became
rphous thereafter. As opposed to the results predicted by
modynamics at 400°C, there was no evidence of Mg and Li 13Mg4
phases mbient temperature. In the ternary Li-Si-Mg isothermal
equilibrium
e diagram at ambient temperature, a line that does not exist at 400°C
ects Mg2Si to Li. Mg2Si crystallizes in an antifluorite structure where Si
pies the octahedral sites to form a face-centered cubic arrangement
e Mg occupies the tetrahedral sites. This structure offers vacant
hedral sites favorable for lithium intercalation that supports the theory of
gle-phase intercalation process with the formation of a Li 1Mg2Si phase.
Kim et al.33 investigated the electrochemistry of Mg2Si versus lithium
more detail as it exhibited an initial capacity of 1370 mAh/g
sponding to the insertion of up to 3.9lithium (Figure 8.11). This value
exceeded the capacity reported by Huang et al.31' 32 at ambient
e and Silicide Negative Electrodes 263

erature (2 lithium) and also the capacity predicted by Anani and


29 30
gins • at elevated temperature (3.25 lithium) (Table 1.1). Although the

+ third second first


\ t/
I
...J
1.5

c:.
ii 1.0
:;::;

l
r:::
.!
0
0.5
11.
0.0 0 200 400 600 800 1 000 1200 1400

Capacity (mAh/g)

e 8.11. First three cycles voltage profile of an Mg 2Si electrode cycled vs. Li metal
en 0 and 2 Vat a constant current of 10 mA/g (from Ref. 33).

rode exhibited high initial cycling efficiency (78.4% in the first


e), the electrode failed within 10 cycles.
The evolution of the structure was examined using ex-situ X-ray
action. The Mg2Si structure, which remained crystalline during cycling,
nded during lithiation and contracted during delithiation. The
nsion/contraction of the lattice with cycling was consistent with an
calation process. The emergence of Mg metal at 0.17 V and a Li-Mg
on further lithiation suggested the decomposition of the LixMg2Si
e. Although no evidence of any Li-Si phase was obtained by XRD,
er electron spectroscopy performed in the lithiated stated revealed the
xistence of a LixMg2Si phase with Li-Si and Li-Mg alloys. Similarities in
differential capacity plots of the Mg2 Si electrodes with the ones ined
for Si-based materials, such as Si metal and SiO, and Mg also
ested the formation of Li-Si and Li-Mg alloys, respectively. In brief,
um was proposed to intercalate into the vacant octahedral sites of the
Si antifluorite structure until the concentration of lithium in the LixMg2Si
hed a critical value. At this point, the material decomposes into Li-Si s
and Mg, which alloys with lithium on further lithiation.
The rapid degradation of Mg2Si electrodes was proposed to result from
large volume changes associated to the Li-Si and Li-Mg alloying
ions. Scanning electron microscopy revealed cracking and crumbling
10 cycles while XRD analyses showed an increase of the amount of
ual Mg metal and Li-Mg with respect to the Mg2Si phase with cycle
ber.
ChapterS

3.1.2. Formation of a Ternary Li2MgSi Phase


34
Moriga et al. proposed a two-step reaction mechanism for the
tion of Mg2Si with lithium at ambient temperature that differed from the

+ ..L
§ 1•• step
I
2•d step

L:r
.;
>

=----
Ill
Cl

0
> 0.1
0.0
0.0 0.5 1.0 1.5 2.0 2.5 3.0 3.5 4.0
x In Li.Mg2Si

e 8.12. First discharge voltage profile of an Mg 2Si electrode cycled vs. Li metal at a
2
ant current of 0.5 mA/cm (from Ref. 34).

described above. The first discharge voltage profile in Figure 8.12 shows
voltage remained quite flat during the insertion of the first two lithium
e it gradually decreased during further lithiation. The first step was
ved to involve the extraction of Mg from Mg 2Si concomitant to the
ation of a ternary LhMgSi phase (equation 8.16). The second step was
ciated to the alloying reaction of lithium with the extracted Mg metal
ation 8.17).

Mg2 Si + 2 Li+ + 2e· . LhMgSi + Mg (8.16)


Mg + y Lt + y e· . LiyMg (8.17)

XRD patterns obtained at various points of discharge revealed Mg l


and a new cubic phase emerged while Mg2Si vanished. The new cubic e
was associated to LhMgSi based on the XRD pattern simulations of
-aSi with half-occupation of the 8c Mg sites. On further lithiation, Mg
l disappeared and a body-centered cubic Li phase identified as a Li-Mg
appeared. Good correlation existed between the XRD pattern obtained
rimentally upon insertion of 3.5 Li and the JSRD pattern obtained by
lation using the LhMgSi structure with a Fm 3m space group depicted
gure 8.13. The later has a 2aFX2aFX2aF structure, where aF is the lattice
meter of the initial Mg2Si cubic structure. In the proposed structure, two
e and Silicide Negative Electrodes 265

of LizMgSi were alternatively arranged. The second unit was obtained


otating the first one clockwise for 90° about the a axis. Finally, DV-Xa
ulations revealed electrons were introduced in the Mg 3s orbitals for
ge compensation during lithium insertion, resulting in the reduction of
+ ions. This was consistent with the extraction of Mg (supported by
) from Mg2 Si.
35
More recently, Roberts et al. confirmed the formation of Mg metal
LizMgSi by XRD during lithiation of Mg2Si. Because the reconstitution
ions in the Li-Si system are kinetically hindered at ambient temperature
36
only selective equilibrium is achieved, the Li-Si alloys may be difficult
etect using XRD. Therefore, although the structural characterization of
lectrode at different points of charge and discharge showed no evidence
i-Si alloy formation, the authors proposed electrochemical evidence for i
alloying with extensive cycling. The anodic differential capacity plot n
Mg2Si electrode lithiated down to 5 mV exhibited a peak in the same ge
range as obtained for pure silicon. Finally, the material was shown to form
back to Mg2Si during delithiation.

Si

Li

(A) (B)

a
Tetrahedron
occupied by Mg
/ ,L. /

;>
r
--
--....
./ ' '{3)

12.83A <"
/
--
1 / (A) ' \:J /,
/

e 8.13. Schematic illustration ofLi 2MgSi structure (from Ref. 34).

.2. CrSh
36
Lithium was found to intercalate into the CrSiz structure. Because the
ChapterS

rochemical insertion of lithium into CrSi2 is very slow at ambient


erature, ternary Li-Si-Cr samples were fabricated by reaction of pure
um with CrSi2 at 360°C using various initial Li:CrSiz stoichiometry
s. The resulting materials were characterized by XRD in order to
tify the chemical reactions of CrSiz with lithium. Table 8.2 exhibits the
med chemical reactions along with the initial Li:CrSiz ratio at which the
rent phases were observed. It also provides the theoretical capacity
ciated to these reactions and the experimental delithiation capacity.
ium intercalation occurs for initial stoichiometry ratios up to 60:40. A
er increase in the initial lithium content results first in the formation of
h and LhSh, then Cr5Si3 transforms into Cr3Si and finally Li 13Si4 and
Si5 were observed. No ternary phase was found.
The Li-Si-Cr samples prepared by solid-state reaction were tested
us lithium metal under a constant current equivalent to a C/60 rate. The
ples exhibited lithiation capacities ranging from 661 to 811 mAh/g and
rsible delithiation capacities of up to 800 mAh/g that are rooted in binary
i alloying reactions. Although the theoretical specific
cities of ternary Li-Si-Cr system are smaller than the binary Li-Si
em, the capacities obtained experimentally for the ternary system

8.2. Reconstitution reactions as found from X-ray diffraction analyses after chemical
ion of CrSi2 (from Ref. 36).

sumed chemical reaction Found for initial Calculated Experimental


stoichiometry capacity delithiation
ratio of Li:CrSi2 (mAh/g) capacity (mAh/g)
hium intercalation into CrSi2 up to 60:40
CrSh + 49 Li - 3 Cr5Si, + 7 Li,Si3 75:25
669
rSi2 + 35 Li - 3 Cr3Si + 5 Li7Si3 80:20 771
496
CrSi2 + 65 Li - 4 Cr3Si + 5 Li 13Si4 85:15 996
682
rSh + 21 Li- Cr 3Si + Lh1Si5 88:12 1197 836

eded the ones obtained with the binary system. This benefit in capacity
be related to the Cr-Si phases. The latter remain mostly
rochemically inactive after the first discharge and may act as stabilizing
uctive matrix.

.3. NiSi

Preliminary results showed nanosize NiSi synthesized by high-energy


ng reacts with lithium reversibly.37 The material consisted of
omerates of small particles with an average crystallite size of 4-6 nm as
de and Silicide Negative Electrodes 267

rmined from the width of Bragg peaks using the Scherrer equation. The
harge voltage profile (Figure 8.14), which is smooth and approximately
ows a half parabolic curve down to 0 V, shows high initial capacity, 1180
h/g. Even though 80% of the initial discharge capacity was reversible,
capacity fade during cycling is significant as NiSi electrodes retained
65% of the initial discharge capacity after 25 cycles. Based on previous
rts of Sn-Sb materials, NiSi was proposed to decompose into Li-Si
ys and Ni during the first lithiation (equation 8.18). In subsequent charge
discharge, the Li-Si alloys reversibly transform into Si metal, which
titutes the active center of the electrode, while Ni metal remains
trochemically inactive (equation 8.19).

NiSi+ Xu++ X e' -+ LixSi + Ni (8.18)


LixSi + Ni Si + Ni +Xu++ X e' (8.19)

4. Summary - Silicides

Several binary silicides have been examined as potential negative


trode materials first for thermal batteries and then for batteries operating

2.5

2.0
..J 1.5

C:.
Gl 1.0

g 0.5

0.0

0 200 400 600 800 1000 1200


Discharge Capacity (mAh/g)

e 8.14. Discharge voltage profile of a nanosize NiSi electrode cycled vs. Li metal at a
ant current of 0.08 mNcm2 (from Ref. 37).

mbient temperature. Using Mg2Si as an illustration, thermodynamics was


en to be an excellent tool for screening silicides with improved specific
city and energy with respect to the binary Li-Si system for use in
ChapterS

mal batteries operating in the 400-450°C temperature range. Mg 2Si was


found to react with lithium reversibly at ambient temperature. Even
gh this system exhibits initial high capacity, its short cycle life limits its
zation in commercial applications. The rapid failure of the electrode was
buted to the large volume changes associated to the Li-Mg and Li-Si
ated alloying/dealloying reactions occurring during cycling. These alloys
lt from the decomposition of a LixMg 2Si solid solution or a ternary
gSi phase during lithiation. There still exist a conflict as for the actual
tion mechanism of Mg2Si with lithium at ambient temperature. CrSh and
were also investigated. In general, silicides show high capacity at low
ntials that make them very attractive as negative electrodes for Li-ion
ries; however their poor cycle life needs to be improved.

FERENCES

. Knutz, S. Skaarup, Solid State lonics 9&10 (1983) 371.


M. Richards, J. Solid State Chern. 33 (1980) 127.
Bittihn, Solid State Ionics 8 (1983) 83.
. Meyer, H. Rickert, U. Schwaitzer, Solid State lonics 9&10 (1983) 689.
. F. Bell, A. Breitschwerdt, U. Alpen, Mater. Res. Bull. 16 (1981) 267.
R. Rea, D.L. Foster, Mater. Res. Bull. 14 (1979) 841.
A. Boukamp, R. A. Huggins, Mater. Res. Bull. 13 (1978) 23.
. Yamane, S. Kikkawa, M. Horiguchi, M. Koizumi, J. Solid State Chern. 65 (1986) 6.
Juza, H. H. Weber, E. Meyer-Simon, Z. Anorg. AUg. Chern. 48 (1953) 273.
H. Yamane, S. Kikkawa, M. Koizumi, Solid State lonics 25 (1987) 183.
. Suzuki, T. Sodai, Solid State lonics 116 (1999) 1.
M. Nishijima, Y. Takeda, N. lmanishi, 0 Yamamoto, N. Takano, J. Solid State Chern.
113 (1994) 205.
. Asai, K. Nishida, S. Kawai, Mat. Res. Bull. 19 (1984) 1377.
M. Nishijima, T. Kagohashi, M. Imanishi, Y. Takeda, 0. Yamamoto, S. Kondo, Solid
tate lonics 83 (1996) 107.
. Shodai, Y. Sakurai, T. Suzuki, Solid State lonics 122 (1999) 85.
S. Suzuki, T. Shodai, J. Yamaki, J. Phys. Chern. Solids 59 (1998) 331.
. Rowsell, V. Pralong, L. Nazar, J. Am. Chern. Soc. 123 (2001) 8598.
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N. Pereira, M. Ba1asubramanian, L. Dupont, J. McBreen, L.C. Klein, G.G. Amatucci,
ubmitted, J. Electrochem. Soc. (2002).
.B. Bates, N.J. Dudney, B. Neudecker, A. Ueda, C.D. Evans, Solid State /onics 135
2000) 33.
A. D. Pelton, J. Phase Equilibria 12 (1991) 42.
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. Pereira, L. Dupont, J.M. Tarascon, L.C. Klein, G.G. Amatucci, submitted, J.
lectrochem. Soc. (2002).
e and Silicide Negative Electrodes 269

. Takeda, M. Nishijima, M. Yamahata, K. Takeda, N. lmanishi, 0. Yamamoto, Solid


tate lonics 130 (2000) 61.
.A. Huggins, Solid State lonics, in press (2002).
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S Patent 5,294,503.
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2000) 386.
G.A. Roberts, E.J. Cairns, J.A. Reimer, J. Power Sources in press (2002).
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37.
W. G.X. Wand, L. Sun, D.H. Bradhurst, S. Zhong, S.X. Dou, H.K. Liu, J. Alloys and
amp. 306 (2000) 249.
ter 9

ALLOYS AND INTERMETALLIC ANODES

R. A. Huggins

culty of Engineering, University of Kiel, Kaiserstrasse 2, D-24143 Kiel, Germany

INTRODUCTION
Early work on the commercial development of rechargeable lithium
es to operate at or near ambient temperatures involved the use of
ntal lithium as the negative electrode reactant. Binary phases, generally
ing a solid solution of lithium in one of the forms of carbon, are
tly employed on the negative side of lithium cells.
There is considerable interest in finding alternative materials that might
re attractive than the lithium-carbons. Improvements might involve the
to operate safely at higher current densities, less first cycle irreversible
ty loss, better cycling behavior, reduced specific volume, and lower

A number of possible alternative negative electrode materials are


sed in other chapters of this book. The intent of this chapter is not to
t a catalog of possible materials and their properties. Instead, emphasis
placed upon the principles involved in understanding the behavior of
multi-component alloys, starting with their equilibrium or near
rium behavior at both elevated and ambient temperatures. Information
g to equilibrium conditions provides the theoretical limits of the
als and capacities of electrodes in electrochemical systems. The
ties that are actually observed under operating conditions will, of
, deviate from these values due to kinetic factors.
Especially interesting have been recent results on materials that
strate significant deviations from equilibrium behavior, including the
ion of amorphous structures, at low temperatures. The use of materials
ch amorphous silicon is formed in situ during cycling appears to be
larly attractive.
d lntermetallic Anodes 271

ALLOYS AS AN ALTERNATIVE TO PURE


LITHIUM

ttention has been given to the use of lithium alloys as an alternative to


tal lithium for some time. Groups working on batteries with molten
ctrolytes that operate at temperatures of 400-450°C, well above the
point of lithium, were especially interested in this possibility. Two
irections evolved. One involved the use of lithium-aluminum alloys,
eas another was concerned with lithium-silicon alloys.3 -s
hereas this approach can avoid the problems related to lithium
, as well as the others mentioned in the literature, there are always at
o disadvantages related to the use of alloys. Because they reduce the
of the lithium, they necessarily reduce the cell voltage. In addition,
sence of additional species that are not directly involved in the
hemical reaction always brings additional weight and, often, volume.
he maximum theoretical values of the specific energy are always
compared to what might be attained with pure lithium. The energy
is also often reduced. But lithium has a large specific volume, so that
ot always the case.
n practical cases, however, the excess weight and volume due to the
alloys may not be very far from those required with pure lithium
es. It is generally necessary to have a large amount of excess lithium
argeable cells in order to make up for the capacity loss related to the
e or filament growth problem upon cycling.
ithium alloys have been used for a number of years in the high
ture "thermal batteries" that are produced commercially for military
s. These devices are designed to be stored for long times at ambient
tures before use, where their self-discharge kinetic behavior is very
hey must be heated to elevated temperatures when their energy output
ed. An example is the Li alloy/FeS2 battery system that employs a
molten salt electrolyte. In order to operate, the temperature must be
o over the melting point of the electrolyte. This type of cell typically
her Li-Si or Li-Al alloys in the negative electrode.
he first use of lithium alloys as negative electrodes in commercial
s to operate at ambient temperatures was the employment of Wood's
loys in lithium-conducting button type cells by Matsushita in Japan.
ment work on the use of these alloys started in 1983,6 and they
commercially available somewhat later.

Lithium - Carbon Alloys


was also shown in 1983 that lithium can be reversibly inserted into
Chapter 9

7
te at room temperatures when using a polymeric electrolyte. Prior
ments with liquid electrolytes were unsuccessful due to co-intercalation
cies from the organic electrolytes that were used at that time. This
m has been subsequently solved by the use of other electrolytes.
There has been a large amount of work on the development of graphites
lated carbon-containing materials for use as negative electrode materials
ium batteries in recent years. This is due in large part to the successful
pment by Sony of commercial rechargeable batteries containing
ve electrodes based upon materials of this family.
Lithium-carbon materials are, in principle, no different from other
-containing alloys. However, since this topic is treated in more detail
ere, only a few points will be briefly discussed here.
One is that the behavior of these materials is very dependent upon the
of both the nanostructure and the microstructure. Therefore, the
sition and the thermal and mechanical treatment all play important
in determining the resulting thermodynamic and kinetic properties.
als with a more graphitic structure have more negative potentials,
as those with less well organized structures typically operate over much
potential ranges, resulting in a cell voltage that is both lower and more
f-charge dependent.
Another important consideration in the use of carbonaceous materials
gative electrodes in lithium cells is the common observation of a
erable loss of capacity during the first charge-discharge cycle due to
sible lithium absorption into the structure. This has the distinct
antage that it requires that an additional amount of lithium be initially t
in the cell. If this irreversible lithium is supplied from the positive
de, an extra amount of the positive electrode reactant material must be
to the cell during its fabrication. As the positive electrode reactant
als often have relatively low specific capacities, e.g., around 140
, this irreversible capacity in the negative electrode leads to a
ment for an appreciable amount of extra reactant material weight and
e in the total cell.
There are some other matters that should be considered when
ring normal metallic lithium alloys with the lithium-carbons. The
c volume of some of the metallic alloys can be considerably lower than
the carbonaceous materials.

PRINCIPLES DETERMINING THE POTENTIALS


AND CAPACITIES OF ALLOY ELECTRODES
UNDER EQUILIBRIUM CONDITIONS
The theoretical basis for understanding and predicting the potentials
d Intermetallic Anodes 273

pacities of both binary (two element) and ternary (three element)


alloys under equilibrium and near-equilibrium conditions has now
tablished. Under these conditions, these important practical parameters
ctly related to the thermodynamic properties and compositional ranges
ertinent phases in the respective alloy systems.
ne can often understand their behavior under dynamic conditions in
f simple deviations from such equilibrium conditions. In other cases,
r, metastable phases, either crystalline or amorphous, may be present
properties are considerably different from those of the
dynamically stable phases and compositions.

Relations Between Phase Diagrams, the Composition


Dependence of the Potential, and the Capacity of
Electrodes

hase diagrams are figures that graphically represent the equilibrium


a chemical system. They can be very useful thinking tools to help
and the fundamental electrochemical properties of electrodes. There
ous types of phase diagrams, but in the most common case they are
ensional plots that indicate the temperature and compositional
ns for the stability of various phases under equilibrium conditions.
binary phase diagram is a plot of temperature versus the overall
ition for alloys composed of two different elements. It shows the
ture-composition conditions for the stability of the various phases that
m in a given system, and is commonly used in materials science. It will
that there are regions in which only a single phase is stable, and
in which two phases are stable. Although not of particular importance
ochemical experiments, there are also special conditions under which
ssible for three phases to be present in a binary system. According to
bs Phase Rule, this can only happen at a specific temperature. At both
and below that unique temperature only one-phase and two-phase
are possible. This means that at that particular temperature the three
n equilibrium must contact a horizontal (constant temperature) line in
ram. Two will touch it at the ends, and the third will only do so at a
omposition between them.
n the construction of binary phase diagrams the same rules apply
the phases present in the relevant ranges of temperature and
ition are liquids or solids. At any fixed temperature single phase
are always separated by two-phase regions, and in two-phase regions e
in the overall composition is accomplished by variation of the
amounts of the two phases at its limits, each of which maintains a
--
Chapter 9

a+ Liquid
Liquid

a l

--------'-----------------
/ U+ p \
---------------------- '-•
I
I

--
p+y \
I
II
I

p \
Pure A Pure B

9.1. Schematic binary phase diagram with an intermediate phase 13, and solid solubility
inal phases a andy.

composition.
A schematic diagram for a hypothetical binary alloy system A-B is
in Figure 9.1. In this case there are four 1-phase regions. The
hases are designated as phases a, and y. In addition, there is a liquid
at higher temperatures. It can be seen in the figure that the single phases
separated by 2-phase regions as the composition moves horizontally
rmally) across the diagram.
According to the Gibbs phase rule all intensive properties, including the
cal potential, vary continually with the composition within single phase
s in a binary system. Correspondingly, the intensive properties are
sition-independent when two phases are present in a binary system.
the equilibrium electrical potential of such an electrode, E, in an
chemical cell is determined by the lithium activity, it also varies with
sition within single phase regions, and is composition-independent
there are two phases present under the equilibrium conditions that are
ed here.
The variation of the electrical potential difference V (voltage between
ctrode and some reference potential) with the overall composition in
pothetical system at temperature T 1 is shown in Figure 9.2. It is seen
alternately goes through composition regions in which it is constant
tial plateaus) and those in which it varies. If B atoms are added to pure t
A the overall composition is initially in the solid solution phase a and
ctrical potential varies with composition. When the solubility limit is
d lntermetallic Anodes 275

, the addition of more B causes the nucleation and growth of the


wo phases are then present, and the potential maintains a fixed value.
he overall composition reaches composition at the ex+ /line all of the
will have been consumed and there will only be phase present.
urther compositional change within thephase, which is assumed to

a
<I t><l t>
a+ +1

Pure A PureB

2. Variation of electrical potential with composition across the binary phase diagram
Figure 9.1.

very narrow range of composition in this illustration, the electrical


l again becomes composition-dependent. When the upper
itional limit of the phase is reached, the overall composition again
2-phase (and y) range and the potential is again composition
dent. Upon reaching composition at the +y/y line the potential again
ith composition.

An Example, the Lithium-Antimony System


s a concrete example to demonstrate these principles consider the Li
em, which has been studied both experimentally and theoretically in
8 10
tail. - The phase diagram is shown in Figure 9.3.
elow 615°C there are two intermediate phases between Sb and Li,
nd LhSb. Both have rather narrow ranges of composition and are
ted simply as vertical lines in the phase diagram. Thus, if an electrode
s pure Sb and lithium is added, it successively goes through two
Chapter 9

nt reactions. The first involves the formation of the phase LhSb, and
written as:
2 Li + Sb = LhSb (9.1)

Upon the addition of more lithium a second reaction will occur that
in the formation of the second intermediate phase from the first. This

1600

1400 1320
Liquid
1200
.a
(/)
.P
....1
1000
"'"
795
BOO

630.7
600 89 99
.a .a
(I)
(/)
.!)
....1 .$:1
400 I!
....1

200 Sb-

10 20
00 30 40 50 60 70 80 90 100

Li Atomic Percent Sb Sb

.3. Lithium-antimony phase diagram.

written as:
(9.2)

This process can be studied experimentally by the use of a simple


chemical cell whose initial configuration is similar to that shown
atically in Figure 9.4.
By driving current through this cell from an external source that causes
ltage between the two electrodes to be reduced, lithium will leave the
e electrode, pass through the electrolyte, and arrive at the positive
de. If the chemical diffusion rate within the LixSb electrode is
ntly high relative to the rate at which lithium ions arrive at the
de surface, this lithium will be incorporated into the bulk of the
d lntermetallic Anodes 277

de crystal structure, changing its composition. That is, the value of x in


itive electrode material LixSb will increase.
f the lithium is either added very slowly, or stepwise, allowing
rium to be attained within the positive electrode material after each

Li +- conducting Li b
Li electrolyte

4. Schematic drawing of the electrochemical cell used to study the Li-Sb system.

e influence of the lithium concentration in the positive electrode upon


ential under equilibrium or near-equilibrium conditions can be
ated. This procedure was called electrochemical titration by Wagner,
st used it to study the properties of the phase "Ag2S" as a function of
11
/S ratio. The result of such an experiment on the Li-Sb system,
10
ed at 360°C, is shown schematically in Figure 9.5.
We can understand these results by consideration of the Gibbs phase
hich was mentioned earlier. It can be written simply as:

F = C-P+2 (9.3)

F is the total number of degrees of freedom, C the number of


ents, and P the number of phases. In this case there are two
ents, Li and Sb. In an experiment conducted at constant temperature
ssure two degrees of freedom are specified. Thus, if two phases are
the number of residual degrees of freedom will be zero, and all
e variables will be fixed, independent of the overall composition. In
se, this means that the electrical potential will be constant over
itional interval where two phases are present in the phase diagram. On
r hand, the potential will vary with the concentration in composition
in which only one phase is present in the phase diagram. After an
nvisibly narrow, range of solid solution, the first plateau in Figure 9.5
onds to compositions in the phase diagram in which both (almost pure)
the phase LhSb are present. Thus it is related to the reaction in
Chapter 9

on (9.1).
There is also a very narrow composition range in which only one phase,
is present and the potential varies. Upon the addition of further Li the

YS.
mv)
1oocP
L.
I I I
1000
I I ·
-Asec/o Sb

I I
2000
I 2!K)()
Li1SII
600 E
vs. AI."LiA(
800 Li 1SD 400 (mv)

600
200

400r- -
r- 0

200r- T • 360-c

1- -200
I I
0
0 2 3
y in Li.ySb
9.5. Results of coulometric titration experiment on Li-Sb system.

l composition moves into the region of the phase diagram in which two
are again present, in this case LhSb and LhSb, and the potential
s along a second plateau related to Equation (9.2).

Relation Between the Potentials and Thermodynamic


Data
The potentials of the two plateaus in Figure 9.5 can be calculated from
dynamic data on the standard Gibbs free energies of formation of the
ases, LhSb and LhSb. According to Ref. 10, these values are - 176.0
and - 260.1 kJ/mol, respectively, at that temperature.
The standard Gibbs free energy change, Gr0 , related to reaction (9.1)
ply the standard Gibbs free energy of formation of the phase LhSb,
hSb). From this we can calculate the potential of the first plateau from:

(9.4)

Eo is the potential of pure Li. This is found to be 912 mV.


d lntermetallic Anodes 279

he potential of the second plateau is related to virtual reaction (9.2),

(9.5)

his case:
(9.6)

ult is that the potential of this plateau is 871 mV vs. pure Li.
his is the same result that would be found if it were assumed that the
diate phase, LhSb, did not form, and that there is only one voltage
If the electrochemical titration curve were calculated from this value y,
it would have only a single plateau, at a voltage that is the weighted of
the voltages of the two reactions. This is false, due to the lack of tion
of the existence of the intermediate phase. Thus one has to be to be
aware of all of the stable phases when making predictions from
ynamic data.
his discussion has assumed that thermodynamic data are available,
one wants to predict the electrochemical properties. The opposite can
done, of course; experimental measurements can provide information
he relevant phase diagram and the thermodynamic properties of the
phases.
imilar experiments have been made on a number of other binary
systems under conditions such that equilibrium can be reached. This
ment is fulfilled within reasonable times much more easily at elevated
tures. In some cases, however, equilibrium data can also be obtained
ent temperatures, albeit with a bit more patience. Elevated temperature
a number of phases in the Li-Al, Li-Bi, Li-Cd, Li-Ga, Li-In, Li-Pb,
i-Si, and Li-Sn binary lithium alloy systems, made using a LiCl-KCl
salt electrolyte, are listed in Table 9.1.

Temperature Dependence of the Equilibrium Potential


addition to the experiments in the LiCl-KCl molten salt electrolyte,
ments have also been made on some of these systems using lower
0
ture molten salts, LiNOrKN0/ , and also with organic electrolytes at
temperature. This provided information on the temperature
nce of the potentials and capacities.
he results of experiments carried out on materials in the Li-Sb and Li
ems over a wide range of temperature demonstrate the principles
d. Each of these systems has two intermediate phases at low
tures. The data are shown in Figure 9.6.
he temperature dependence of the potentials of the plateaus due to the
e of two-phase equilibria in the Li-Sb system was straightforward,
Chapter 9

g upon two straight lines, corresponding to the reactions of equations


and (9.2) above.

9.1. Plateau potentials and composition ranges of a number of binary Li alloys at


d temperatures.

age vs. Li/Li+, V e


0.047
0.058
0.080
0.089
0.09
0.122
0.145
0.156
0.170
0.237
0.271
0.283
0.283
0.300
0.332
0.373
0.375
0.387
0.430
0.455
0.495
0.507
0.558
0.565
0.570
0.750
0.750
0.760
0.875
0.910

In the Li-Bi case, however, where the comparable reactions are:

Li + Bi = LiBi (9.7)
d lntermetallic Anodes 281

2 Li + LiBi = LhBi (9.8)

perature dependence of the plateau potentials is different. There is a

3
<
.•<
r
...

600

.6. Temperature dependence of the potentials of the two-phase plateaus in the Li-Sb i
systems.

in slope at the eutectic melting point (243°C), and the data for the two
s converge at about 420°C, which corresponds to the fact that the LiBi
s no longer stable above that temperature. These features can be seen
phase diagram for that system, shown in Figure 9.7. At higher
tures there is only a single reaction:

3 Li + Bi = LhBi (9.9)

n addition, the potentials of the second reaction fall along two straight
ments, depending upon the temperature range. There is a significant
in slope at about 210°C, resulting in a negligible temperature
ence of the potential at low temperatures, due to the melting of
.
s before, all the potentials are related to the standard Gibbs free
changes G,o relating to the relevant reactions.
Chapter 9

12001 ----------------------------------------------,

1000
Liquid
800

415
400 400
..,
:::;
iii
200

o;nrrrrrrrrmmmmmmnnnrrrrrrmmmmmmnnrrrrrrrrmmmmmm rrrrmmmm
0 10 20 30 40 50 60 70 80 90 100
Bi Atomic Percent Li Li

.7. Lithium-bismuth binary phase diagram.

The temperature dependence of the values of Gr0 can be seen from the
g equation:
(9.10)

Mlr 0 is the change in the standard enthalpy and Sr0 is the change
in ndard entropy resulting from the corresponding reaction. Thus it can
be at:
(9.11)

From these data, one can obtain values of the standard molar entropy
es involved in these several reactions. They are shown in Table 9.2.
llows the prediction of the potentials at any temperature within this

.2. Reaction entropies in the lithium-antimony and lithium-bismuth systems.

Reaction Molar Entropy of Reaction Temperature Range


(J/K mol) ("C)
2 Li + Sb = Li2Sb -31.9 25-500
Li + Li2Sb = Li3Sb -46.5 25-600
Li + Bi = LiBi 0 25-200
2 Li + LiBi = Li3Bi - 36.4 25-400
d lntermetallic Anodes 283

Experiments at Ambient Temperature


xperiments have also been performed to determine the equilibrium
of the electrochemical potentials and capacities in a number of binary
21 22
systems at ambient temperatures. ' Because of slower kinetics at
emperatures, these experiments took longer to perform. Data are
ed in Table 9.3.

LIQUID BINARY ALLOYS


Although the discussion here has involved solid lithium alloys,
considerations apply to those based on sodium or other species. In
, it is not necessary that the active material be solid. The same
es hold for liquids.

. Plateau potentials and composition ranges of lithium alloys at low temperatures


uilibrium conditions.

oltage vs. Li/Li+,v System Range ofy Temperature°C Ref.


005
055
157
219
256
292
352
374
380
42
449
485
530
601
660
680
810
828
948
956
Chapter 9

An example that was of great interest some years ago involved the so
sodium-sulfur battery that operates at about 300°C. In this case, both of
ctrodes are liquids, and the electrolyte is a solid sodium ion conductor,
only called sodium beta alumina. This configuration can be described as
S/L system. It is the inverse of conventional systems with solid
des and a liquid electrolyte, SILlS systems. The negative electrode is
sodium, and the positive electrode is the product of the reaction of
m with liquid sulfur. Thus the basic reaction can be simply written as:

(9.12)

The potential of the sodium electrode is constant, independent of the


t of sodium present. The composition of the positive electrode changes

900

BOO

u 700

''
'
\
\

90 ICO
SULPHUR ,
Percont

.8. Part of the sodium-sulfur phase diagram.


d Intermetallic Anodes 285

sodium concentration varies, however. Thus its potential is


ition-dependent.
he relevant portion of the Na-S phase diagram is shown in Figure 9.8.
en that at about 300°C a relatively small amount of sodium can be
ed in liquid sulfur. When this concentration is exceeded, a second
hase with a composition of about 78 atomic percent Na is nucleated.
s a composition that is roughly Nao.4S. As more sodium is added, the
composition traverses the two-phase region, and the amount of this
phase increases relative to the amount of the sulfur-rich liquid phase.
potential plateau is expected over this composition range. When the
concentration exceeds that corresponding to about Nao.4S the overall
ition moves into a single phase liquid range, and thus the potential
The maximum amount of sodium that can be used in this electrode
onds roughly to Nao.67S. At higher sodium concentrations, a solid
phase begins to form from the liquid solution. This tends to form at
erface between the solid electrolyte and the liquid electrode, and s
the ingress of more sodium, thus blocking the reaction. The
n of the potential with the composition of the electrode is shown in
9.9.

OPEN CIRCUIT VOLTAGE VS STATE OF DISCHARGE

2.0

I I I
Na 2S15 Na2S4 Na 2s3
1.0

DEPTH OF DISCHARGE,%
e 50 H WO%

MOLE RATIO SODIUM I SULFUR

9. Voltage versus sodium as a function of the composition of the positive electrode.


Chapter 9

MIXED-CONDUCTOR MATRIX ELECTRODES


In order to be able to achieve appreciable macroscopic current densities
maintaining low local microscopic charge and particle flux densities,
battery electrodes that are used in conjunction with liquid electrolytes
oduced with porous microstructures containing very fine particles of the
reactant materials. This high reactant surface area porous structure is
ated with the electrolyte.
This porous fine-particle approach has several characteristic
antages. Among these are difficulties in producing uniform and
ucible microstructures, and limited mechanical strength when the
re is highly porous. In addition, they often suffer Ostwald ripening,
ng, or other time-dependent changes in both microstructure and
ties during cyclic operation.
Furthermore, it is often necessary to have an additional material present
er to improve the electronic transport within an electrode. Various
dispersed carbons are often used for this purpose.
23 25
A quite different approach was introduced some years ago - in which
demonstrated that a dense solid electrode can be fabricated which has a
site microstructure in which particles of the reactant phase or phases
ely dispersed within a solid electronically-conducting matrix in which
ctroactive species is also mobile, i.e. within a mixed conductor. There
a large internal reactant/mixed-conducting matrix interfacial area. The
active species is transported through the solid matrix to this interfacial
, where it undergoes the chemical part of the electrode reaction. Since
atrix material is also an electronic conductor, it can also act as the
de's current collector. The electrochemical part of the reaction takes
n the outer surface of the composite electrode.
When such an electrode is discharged by deletion of the electroactive
s, the residual particles of the reactant phase remain as relics in the
tructure. This provides fixed permanent locations for the reaction to
lace during following cycles, when the electroactive species again
the structure. Thus this type of configuration has the additional
age that it can provide a mechanism for the achievement of true
tructural reversibility.
In order for this concept to be applicable, the matrix and the reactant
must be thermodynamically stable in contact with each other. One can te
this possibility if one has information about the relevant phase ms
as well as the titration curves of the component binary systems. The y
window of the matrix phase must span the reaction potential of the
nt material. It has been shown that one can evaluate the possibility that
onditions are met from knowledge of the binary titration curves.
d lntermetallic Anodes 287

ince there is generally a common component, these two binaries can


treated as a ternary system. Although ternary systems are not
ly discussed here, it can be simply stated that the two materials must
comers of the same constant-potential tie triangle in the relevant
mal ternary phase diagram in order to not interact. The potential of the
ngle determines the electrode reaction potential, of course. An
nal requirement is that the reactant material must have two phases
in the tie triangle, but the matrix phase only one.
he kinetic requirements for a successful application of this concept are
understandable. The primary issue is the rate at which the
ctive species can reach the matrix/reactant interfaces. The critical
ter is the chemical diffusion coefficient of the electroactive species in
rix phase. This can be determined by various techniques, as discussed
re.
he first example that was demonstrated was the use of the phase with
inal composition Li13Sn5 as the matrix, in conjunction with reactant
in the lithium-silicon system at temperatures near 400°C. This is an
lly favorable case, due to the very high chemical diffusion coefficient
m in the Li13Sn5 phase.
he relation between the potential-composition data for these two
under equilibrium conditions is shown in Figure 9.10. It is seen that
se Lh,6Sn (Li13Sn5) is stable over a potential range that includes the
wo-phase reconstitution reaction plateau in the lithium-silicon

0.7

0.5

c .1 ,
0.1
T

yin
10. Composition dependence of the potential in the Li-Sn and Li-Si systems.
Chapter 9

0.39
40mA.tml
D.38

-20 mA/etr/- 037

0.01
- 0.36

D.35

l !) O.JJ
-
>
- l ,.sl plateau IOCVI

::-0.01 0.33-

ci -0.02
rnAicrn2 -
!i!
l-0.03

-0.04

-!!.05 charging •
0.28
-0.06 - I I I I t t
0 10
charge stored as% o1 CCij)CIC:ily -

9.11. Charge and discharge curves of the Li-Si alloy in the matrix of the
hemically inert mixed-conducting Li-Sn alloy at different current densities.

ore, lithium can react with Si to form the phase Lit.71Si (Li12Si7) inside
solid composite electrode containing the Lh_ 6Sn phase, which acts as a
-transporting, but electrochemically inert matrix.
Figure 9.11 shows the relatively small polarization that is observed
the charge and discharge of this electrode, even at relatively high
t densities. It is seen that there is a potential overshoot due to the free
involved in the nucleation of a new second phase if the reaction goes
pletion in each direction. On the other hand, if the composition is not
quite so far, this nucleation-related potential overshoot does not
, as seen in Figure 9.12.
This concept has also been demonstrated at ambient temperature in the
of the Li-Sn-Cd system.26•27 The composition-dependence of the
ials in the two binary systems at ambient temperature is shown in
9.13, and the calculated phase stability diagram for this ternary system
wn in Figure 9.14. It was shown that the phase Li4.4Sn, which has fast
cal diffusion for lithium, is stable at the potentials of two of the Li-Cd
titution reaction plateaus, and therefore can be used as a matrix phase.
d lntermetallic Anodes 289

Q.l9

0.38

0.37
I• 40 mA/cm'
0.36

0.35 r
r--+-------S-i-U-171Si plateau IOCVI------------ 0.34
0.33

0.32
:g
. o.J'll
Q.30
l
0.29

:;-o-----:;10----:t20::---::J!:'o---:4 o---:s o:----t.eo::- , ;-o--•eo --. """'al'·28


charge stored as % ot capacity

12. Charge and discharge curves of the Li-Si, Li-Sn composite if the capacity is
o that the reaction does not go to completion in either direction. There is no large
n overshoot in this case.

1000 r-------------------------------------

..........
aoo-

sao- \
.. .. .
• U·Sn

• • • • •• • •
400
•• ... •
•••

. ........

200
• •
••
....
LI·Cd

0
AMA ... A
•••
0 2 3 4 5

.13. Potential versus composition for Li-Sn and Li-Cd systems at ambient
re.

havior of this composite electrode, in which Li reacts with the Cd


nside of the Li-Sn phase, is shown in Figure 9.15.
n order to achieve good reversibility, the composite electrode
Chapter9

Sn

9.14. Calculated phase stability diagram for the Li-Cd-Sn system at ambient
ture. Numbers are voltages vs. Li.

tructure must have the ability to accommodate any volume changes


ight result from the reaction that takes place internally. This can be
care of by clever microstructural design and alloy fabrication
ques.

DECREPITATION
A phenomenon called "decrepitation" can occur in materials that
o significant volume changes upon the insertion of guest species. It is
ometimes called "crumbling". These dimensional changes cause
nical strain in the microstructure, often resulting in the fracture of
es in an electrode into smaller pieces.
This can be a striking, and sometimes disastrous, phenomenon, for it is
ecifically related to fine particles, or even to electrochemical systems.
example, it has been shown that some bulk solid metals can be caused
ture, and can even be converted into powders by repeated exposure to
en gas if they form metal hydrides under the particular thermodynamic
ons present. This is, of course, different from the hydrogen
tlement problem in metals with body-centered cubic crystal structures,
d lntermetallic Anodes 291
100
5"
> ..
g01 60
IIi

·····························
01
80
>
.§.
Q)
•.•···•··•·· .-..=:Ch;a.rg.e.. EQUifibtium
• •
0 •
01
4

..... ...............D.is.
J: +
(...). 0 ••
2

·0.2 0.0 0.2 0.4 0.6 0.8


Fraction or Electrode Capacity

15. Charge-discharge curve of the Li-Cd system with a fast mixed-conducting phase
ium-tin system at a current density of 0.1 mA/cm2 (ambient temperature).

involves the segregation of hydrogen to dislocations within the


ructure, influencing their mobility.
ecrepitation is often particularly evident during cycling of
hemical systems. It can readily result in the loss of electronic contact
reactive constituents in the microstructure and the current collector.
nsequence, the reversible capacity decreases.
his phenomenon has long been recognized in some electrochemical
in which metal hydrides are employed as negative electrode reactants.
phenomena also occur in lithium systems employing alloy electrodes,
f which undergo very large changes in specific volume if the
ition is varied over a wide range in order to achieve a large capacity.
ecause of its potentially large capacity, a considerable amount of n
has been given recently to the Li-Sn system, which is a fine example
phenomenon. The phase diagram of the Li-Sn system shows that there
intermediate phases. The thermodynamic and kinetic properties of the
t phases in this system were investigated some time ago at elevated
17 28 21
tures and also at ambient temperatures. ' ' ' The volume
22 26 27
'
that occur in connection with phase changes in this alloy system are
he phase that forms at the highest lithium concentration, Li 4.4Sn, has a
volume that is 283% of that of pure tin. Thus Li-Sn electrodes swell
nk, or "breathe", a lot as lithium is added or deleted.
bservations on metal hydrides that undergo larger volume changes
own that this process does not continue indefinitely. Instead, it is
hat there is a terminal particle size that is characteristic of a particular

l. Particles with smaller sizes do not fracture further.


Chapter 9

Experiments on lithium alloy electrodes have also shown that the


ochemical cycling behavior is significantly improved if the initial
29
e size is already very small, and it is reasonable to conclude that this
ted to the terminal particle size phenomenon.
A theoretical paper on the mechanism and the influence of the
tant parameters related to decrepitation appeared recently ? It uses a
0

e one-dimensional model which allows the calculation of the conditions


which fracture will be caused to occur in a two-phase structure due to
ic volume mismatch. This model predicts that there will be a terminal
e size below which further fracture will not occur. The value of this
teristic dimension is material-specific, depending upon two parameters,
agnitude of a strain parameter related to the volume mismatch and the
re toughness of the lower-specific-volume phase. For the same value of
e mismatch, the tendency to fracture will be reduced and the terminal e
size will be larger the greater the toughness of the material. The of
this model calculation are shown in Figure 9.16.

50

45

40

35 -·-5

. a!
s 30
2 25
--o--10
-•-15

20 ----<>-- 20
.tj
._ 15
!'12

·c
u
10

0
0 2 3
Dilation strain parameter

9.16. Variation of the critical particle size as a function of the dilation strain and the
toughness of the phase in tension.
d Intermetallic Anodes 293

FORMATION OF AMORPHOUS PRODUCTS AT


AMBIENT TEMPERATURE

his chapter has been primarily concerned with understanding the


r of alloys under equilibrium or near-equilibrium conditions, from
he potential and capacity limits can be determined. Actual behavior in
lications always deviates from these limiting values, of course.
here have been a number of observations that the operation of oxide
electrodes at very high lithium activities can result in the formation of
ous, rather than crystalline, products, whose properties are different
ose of the corresponding crystalline materials.
he spectrum of materials in which amorphous phases have been
under electrochemical conditions is now quite broad, and include ls
of potential interest as positive electrode reactants, such as some m-
based materials with the general formula RV04, where R is Al, Cr,
31
r Y.
A group of interesting nitride alloys with structures related to that of
hich is known to be a fast ionic conductor for lithium, but in which
f the lithium is replaced by a transition metal, such as Co, have been
o become amorphous upon the first insertion of lithium.32 -35
xperimental evidence for the electrochemical amorphization of alloys
36
i-Si, Li-Sn or Li-Ag systems was studied by Limthongkul. In the
o cases, this was only a transient phenomenon.
specially interesting, however, have been experiments that gave
e for the formation of amorphous silicon during the initiallithiation of
er of silicon-containing precursors, including SiB3, SiO, CaSh and
39
- The electrochemical behavior of these materials after the initial
n cycle was essentially the same as that found in Si powder that was
amorphous. There was, however, an appreciable amount of
ible capacity in the first cycles of these precursors, about 1 mol of Li
case of SiB3 and the disilicides, which was evidently due to an
ible displacement reaction with Li to form one mol of amorphous
In the case of SiO the irreversible capacity amounted to about two
Li, which was surely related to the irreversible formation of LhO as
the amorphous silicon. Some of these materials with amorphous Si are

. Reversible capacity of several materials that contain amorphous silicon.

Material Reversible Capacity,


mAh/g
SiB3 440
SiO 675
Amorphous Si >1000
Chapter 9

nsiderable potential interest as negative electrode reactants in lithium


s, as their charge/discharge curves are in an attractive potential range,
ave reasonable kinetics, and their reversible capacities are very high, as
in Table 9.4.

SUMMARY
Because of safety and cycle life problems with the use of elemental
m, essentially all rechargeable lithium batteries use lithium alloys as
ve electrode reactants today. The theoretical limits of the potentials and
ies of such electrodes can be determined from a combination of
odynamic data and phase diagrams. This has been demonstrated for
l examples of binary systems.
There are two general types of reactions that can take place: homophase
ns, in which guest atoms are inserted into an existing phase, often
ctically, and reconstitution reactions in which phases nucleate and grow
terophase microstructures. The potential varies with the overall
sition of an electrode in the insertion reaction homophase case, but is
sition-independent when reconstitution reactions take place in
phase microstructures.
The electrochemical titration method can be used to investigate the
nt parameters experimentally. Experimental results are now available
number of systems, both at elevated temperatures and at ambient
ratures.
Under equilibrium, or near-equilibrium, conditions the potentials are
y related to the standard Gibbs free energies of formation of the phases
ed. Thus thermodynamic data can predict experimental results.
ise, experiments can provide thermodynamic data. As an example, the
rature dependence of potential plateaus can be used to determine the
rd entropy changes in the relevant reaction. These experimental data
orrelate with the stability of phases in the phase diagram. Furthermore,
aximum theoretical specific energy of an electrochemical system can
e determined from the equilibrium electrochemical titration curve and
ated thermodynamic data.
These principles are applicable to liquid, as well as solid, binary
als. An example is the Na-S system, which is the basis for a high
rature LIS/L battery system that uses sodium beta alumina as a solid
lyte.
Composite multiphase microstructures can be useful in some cases, if
ermodynamic and kinetic properties of one binary system are
tible with those of another binary system. The critical question is the
ial range in which the desired reaction takes place. It must be within
d Intermetallic Anodes 295

ility range of the other phase with fast kinetics. Experiments have
trated that this mixed-conductor matrix concept can be used at both d
temperatures and ambient temperatures.
ne of the practical problems with a number of alloy systems in which
lues of capacity are achieved by the use of large composition changes
d to the corresponding volume changes. This can lead to decrepitation
ctronic disconnection of reactant particles. The general features of this
r, and the importance of the particle size and the mechanical
es of the respective phases are now understood in principle.
n interesting recent development relating to alloys has been the
nce of experimental results showing that electrochemical lithiation
se the appearance of amorphous phases with quite different properties
ose of the equilibrium phases. Especially interesting, and potentially
nt, is the observation that displacement reactions can take place during
n of some materials containing silicon that result in the formation of
ous silicon as a product. This amorphous silicon can then react
ly with lithium at attractive potentials and with a high capacity.

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ai, J. Electrochem. Soc. 123 (1976) 1196.


harma and R.N. Seefurth, J. Electrochem Soc. 123 (1976) 1763.
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eppner and R.A. Huggins, J. Electrochem. Soc. 125 (1978) 7.
oench and R.A. Huggins, J. Electrochem. Soc. 129 (1982) 341C.
ng, P. King and R.A. Huggins, Solid State Ionics 20 (1986) 185.
ng, I.D. Raistrick and R.A. Huggins, J. Electrochem. Soc. 133 (1986) 457.
Boukamp, G.C. Lesh and R.A. Huggins, J. Electrochem. Soc. 128 (1981) 725.
Boukamp, G.C. Lesh and R.A. Huggins, in Proc. Lithium Batteries,
Chapter9

. Venkatasetty, Ed., Electrochem. Soc. (1981), p. 467.


. Huggins and B.A. Boukamp, US Patent 4,436,796.
Anani, S. Crouch-Baker and R.A. Huggins, in Lithium Batteries, A. N. Dey, Ed.,
trochem. Soc. (1987), p. 382.
Anani, S. Crouch-Baker and R.A. Huggins, J. Electrochem. Soc. 135 (1988) 2103.
. Wen and R. A. Huggins, J. Solid State Chern. 35 (1980) 376.
ang, M. Winter and J. 0. Besenhard, Solid State Ionics 90 (1996) 281.
A. Huggins and W. D. Nix, Ionics 6 (2000) 57.
iffard, F. Leroux, D. Guyomard, J.-L. Mansot and M. Toumoux, J. Power Sources 68
97) 698.
Nishijima, T. Kagohashi, N. Imanishi, Y. Takeda, 0. Yamamoto and S. Kondo, Solid e
Ionics 83 (1996) 107.
hodai, S. Okada, S-i. Tobishima, and J-i. Yamaki, Solid State lonics 86-88 (1996) 785.
Nishijima, T. Kagohashi, Y. Takeda, N. Imanishi and 0. Yamamoto, B'h IMLB (1996),
02.
hodai, S. Okada, S. Tobishima and J. Yamaki, B'h IMLB (1996), p. 404.
imthongkul, Ph.D. Thesis, Mass. Inst. of Tech. (2002).
lausnitzer, Ph.D. Thesis, University ofUlm (2000).
etz, Ph.D. Thesis, University of Kiel (2001).
etz, R.A. Huggins and W. Weppner, Il'hiMLB (2002), Abstract No. 47.
apter 10

CURRENT ISSUES OF METALLIC LITHIUM


ANODE

M. Ishikawa and M. Morita

Department of Applied Chemistry and Chemical Engineering,


Faculty of Engineering, Yamaguchi University, Yamaguchi, Japan

1. INTRINSIC ADVANTAGES AND DRAWBACKS


OF METALLIC LITHIUM ANODE

Metallic lithium has the highest theoretical specific capacity (3860


/g) and the most negative redox potential among all metals. These
ures have attracted the interest of battery investigators, who have
mpted to put lithium metal into practical use in rechargeable battery
ems. Its poor charge-discharge cycleability, however, and its potential
hazards have hindered thus far the development of cells with a metallic
1
um anode.
The essential reaction of metallic lithium anode is very simple:

Discharge
Li < > Lt + e-,
Charge

in spite of this simplicity, the practical application of Li metal to a


argeable anode has been very difficult due to some crucial issues. The t
important one is that Li metal usually tends to deposit as a dendritic or
sy structure during charge, and the disordered metallic deposit gives rise
poor coulombic efficiency. This happens because such a fine Li metal
n acts as an active site inducing reductive decomposition of electrolyte
ponents. Part of the deposit may become electrically isolated and
ding may also occur. Furthermore, the fine metallic Li can easily
trate into the separator and eventually cause internal short, this resulting
at generation and contingent ignition. To turn batteries with a metallic
node into actual utilization more efforts should be made to overcome
e problems.
Chapter 10

2. HISTORICAL ASPECTS IN RECHARGEABLE


METALLIC LITHIUM BATTERIES

Before the successful commercialization of Li-ion batteries, i.e.,


nd 1990, in prototype and commercialized secondary Li metal-based
ries, major strategies to compensate for poor Li cycling efficiency could
ategorized into two ways. They were: (i) compensation for the low
ge-discharge reversibility of the Li anode by loading excess amount of
etal, and: (ii) suppression of irregular (mossy or dendritic) Li deposition
sing aLi-alloy anode as listed in Table 10.1.
Although these schemes could somewhat make up for the poor
eability of Li metal, their effects were still unsatisfactory. The use of
ss amount of Li (scheme i) resulted in an increase of the total weight of
ries. Furthermore, even with excess metallic Li, cycling life was still
t: 200-300 cycles.
On the other hand, Li-alloy anodes (scheme ii) were applied mainly to
-type cells for memory back-up. Cells with Li-alloy anodes could stand
oximately 1000 cycles because memory back-up applications do not
and deep charge-discharge cycles.2' 3 However, a secondary metal
ed with Li increases the total anode weight, and induces a positive shift
he potential; for instance, Li-Al alloy anodes typically have a redox
ntial of 0.3-0.5 V vs. Li/Li+. The energy density of cells containing a
loy anode was usually much lower even than that of cells with an excess
unt of Li metal. In addition, such Li-alloy anodes cannot be applied to
drical cells, which need wound electrodes, because the Li-alloy anodes
oo brittle and hard to be wound.
Besides AI, some metals can form with Li intermetallic compounds
g as Li-alloy anodes, which can be easily handled and control
morphology of the Li deposit.4 Unfortunately, however, such anodes
crucial problems; the change in electrode volume during
ge-discharge is remarkably large, and the electrodes gradually become
erized, limiting the cycle life. "Wood's metal alloy" is a eutectic alloy
isting of Bi, Pb, Cd and Sn, and can form an intermetallic compound
Li.5 However, the pulverization of Wood's metal is still inevitable like
Li-alloy anodes.
To overcome this problem we might assemble a cell using "originally"
erized alloy powders instead of an intact alloy sheet as an anode.
rally, however, it is very difficult to optimize their binding and
rsion conditions, and there is severe trade-off between their long cycle
nd high energy density.
nt Issues of MetaUic Uthium Anodes
299

Rechargeable lithium batteries in commercialization or test production before 1990.


Baltcr)l system

Anode-Calhode

"s metal alloy·


c:alhode

loy-liS,

r grapllite-

ous V:Os

oy-Polyaniline

oy-LIOII/ MnO,

loy-Vi),

,composite oxide

e,

,
,

Lithium metal rechargeable batteries developed after 1990.

Applicalion

iah·temperBtun:
3
battety)

eralUtC operation)'

(polymer gel battety)'

(polymer gel battety6)

(polymer gel battery)'

IEPI (Central Research Institute ofEieclric Power Industry, Japan)j 'NEooiDENSO; 3USABC/Hydro-Quebec/3M; 4 USABC/ANU
T-America; 'Malsushita 8altcry Industrial; 'Lithium Technology; PolyPius
Chapter 10

-up coin-type cells, research activity for such alloy electrodes is now
g diminished. In Europe, nonetheless, Besenhard and co-workers
inue basic studies on alloy electrodes,6 and in the USA mainly USABC
veloping rechargeable batteries for high-temperature applications with
Al anode for vehicles.7

. RECENT TRENDS IN THE DEVELOPMENT OF


BATTERIES WITH ALi ANODE

After the start of commercial production of Li-ion batteries, the goal


eveloping rechargeable batteries with a metallic Li anode became more
nite than that before the '90s: the performance of Li metal batteries must
ehow exceed that of batteries with a carbon anode in practical use.
e 10.2 shows batteries under development with a Li metal anode. In n
there have been projects utilizing a Li metal anode conducted by
DO" (New Energy and Industrial Technology Development
nization) aiming at power sources both for transportation and stationary
ications.8
One of the fields where a Li metal anode is attracting much interest is
of polymer battery systems. These systems are considered promising
only for portable electronics but also for electric vehicles. As just
ribed, the practical use of Li metal anode is still considered to be worth
ffort. On the other hand, with respect to investigations on the basic
istry of Li metal electrode behavior, several important factors affecting
reversibility of Li cycling have become fairly clear based on
rochemical tests (ac impedance spectroscopy and scanning vibrating
rode technique [SVET]), chemical tests (typically ESCA [XPS] and IR),
microscopic tests (TEM, SEM and AFM, analyses of Li anode surface).
he basis of such characterizations, novel electrolyte systems as well as
rolyte additives compatible with a Li anode have been proposed.
ils will be given in the next section.

. OPTIMIZATION OF THE LITHIUM ANODE


INTERFACE
.1. Fundamentals
An essential strategy to obtain a satisfactory performance from a
llic Li anode is to optimize chemically as well as physically the
facial structure between Li anode and electrolyte. Without a design
d on this strategy, it is practically impossible to have a practical Li
Current Issues of Metallic Lithium Anodes 301
de showing high coulombic efficiency and adequate safety.
Since the reducing power of Li metal is extremely high, i.e., its
modynamic redox potential is very low, reductive decomposition of an
trolytic solvent and/or salt occurs at the pristine Li interface as soon as

e 10.3. Chemical composition of passivation films on Li metal.

Electrolyte

Without electrolyte (native film)

General PC systems

PC/LiPF6

PC/LiCl04

General EC systems

General DMC systems

General DEC systems

S021LiAlC14

General THF systems

THF/LiAsF6

General 2MeTHF systems

2MeTHF/LiAsF6

General DME systems

DME/LiAsF6

General BL systems

General DOL systems


Chapter 10

get in contact. Some components of the decomposition products form


so-called solid electrolyte interface (SEI). If the latter can protect
nst further electrolyte decomposition, as does a passivation layer in
rrosion process of some metal, the SEI can prevent perpetual side
tions of an electrolyte with Li, and hence even the thermodynamically
able Li metal can get pseudo-stability in an organic electrolyte.
With regard to a rechargeable Li anode interface, however, it should
ot only protective against side reactions, but should also not impede the
sion of Li ions across the interface during cycling. As the components
n interface layer depend obviously on the nature of electrolytes (see
e 10.3), appropriate electrolytes have to be selected to favor Li cycling.
surface layer is known to crucially affect the morphology of Li metal
the charge/discharge efficiency. It is recognized that a grained or lumpy
ace structure can lead to a high efficiency of Li cycling, while a
ritic or mossy Li structure is undesirable.
For instance, LiPF6, an electrolytic salt with perfluoro anion, leads to
ormation of a LiF layer at a metallic Li interface. 9- 11 This layer has a
protective ability, and if its thickness is appropriate, the morphology of
sited Li becomes grainy, resulting in an improved cycling efficiency.

10.4. Additives used to enhance the cycling efficiency of Li metal.

oup

HF

ganic AII3, Mgl2,


s 2-
X

2Me-furan,

derivatives

Cetyltrimethylammonium
ganic
chloride

Nonionic

Crown ethers

Benzene

C02
as
N20,CO
Current Issues of Metallic Lithium Anodes 303
.2. Effect of Additives

Another approach to the improvement of Li cycling efficiency is


uding some additives in the electrolyte formulation. This method can
rol or modify the thickness, morphology and chemical composition of
Li surface layer. The main additives so far investigated for
argeable Li battery electrolytes are listed in Table 10.4.
These organic, inorganic and gaseous additives can improve the
ing efficiency of a Li anode. They can be categorized roughly into two
ps with different mechanisms: (i) formation of a protective surface
r by reaction of Li with an additive, (ii) formation of a protective
i-layer by adsorption of a non-reactive additive.
Not only major components but also minor impurities in the
trolytes can have a serious influence on the surface composition via
reactions with Li, and hence a change in cycleability can occur. In
tion, trace impurities in the controlled atmosphere used to form a Li
t would also affect the Li surface. Usually, a Li metal sheet is made in
tmosphere containing C02 to provide a LhC03 layer as a "native"
face at a Li sheet surface, while oxygen and moisture must be
oughly excluded from the atmosphere. The LhC03 interface is widely
15
wn to be favorable for Li cycling. 12 -
Addition of a small amount (5% or less) of another metal to bulk Li
reported as an alternative method for improving Li surface properties.
scheme is different from the utilization of "conventional" Li-alloys
aining relatively large amounts of another metal. Few percents of AI, Sn,
etc. can decrease the interfacial resistance between anode and
trolyte. These anodes may modify the morphology and interfacial
edance of deposited Li while keeping their redox potentials as low as
16
of pure Li.

. PHYSICAL FACTORS AFFECTING THE LITHIUM


INTERFACE

Besides chemical factors such as electrolytes and additives, some


ical factors have an influence on the Li interface structure. Temperature
stacking pressure on the anode have long been known as such factors.
as reported that cycling a metallic Li anode under a certain pressure can
17
ove Li morphology and hence can provide a good cycling efficiency.
respect to the temperature effect, a uniform surface morphology and
igher cycling efficiency can be obtained cycling Li in some
temperature electrolytes (e.g., LiPF6-based binary carbonate-type
rolytes: LiPF6-PC/DMC, LiPF6-EC/DMC) in comparison with that in
Chapter 10

corresponding electrolytes at ambient-temperature. 18" 19 Furthermore, a


efficiency can be obtained at ambient-temperature after
temperature "precycling" in such electrolytes. This result suggests
there is a "hysteresis effect" of electrolyte temperature upon Li anode
ormance. 18' 19

6. RECENT ADVANCES IN THE RESEARCH ON


METALLIC LITHIUM ANODE

Besides the above instances, many efforts have been focused on


ble electrolytes for the improvement of metallic Li anode. Fringant et
tudied multi-solvent electrolytes containing a mixture of PC and EC,
-permittivity solvents, with DMC, a low-viscosity co-solvent which
20
ributes to a good cycleability of metallic Li anode. As an electrolytic
LiAsF6 has been widely known to provide high Li cycling efficiency,
ugh it has a serious drawback, high toxicity.
Aurbach et al. have investigated the relationship among electrolyte
position, corresponding Li surface chemistry, ionic conductivity at the
ace layer and morphology of Li deposit. 19• 2123 - They suggested that

LiFlayer(f((lm LiOHand Li,CO,)

e 10.1. Chemical structure of passivation films on Li metal anode, a) under Ar


phere, b) immersion in 1.0 M LiBF4 I PC or y-BL for 3 days, c) immersion in 1.0
PF6 I PC or y-BL for 3 days.
Current Issues of Metallic Lithium Anodes 305
lcarbonate-type electrolytes, such as PC, first give lithium
lcarbonate, which then react with some impurities to form LhC03 and
. It is notable that a reaction leading to a surface layer tends to be
inated by a solvent component in mixed-solvent electrolytes.
Kanamura et al. have investigated the relationship between inorganic
ponents at a Li surface and the composition of electrolytes by XPS
10 24
ysis, • and proposed chemical models with a multi-layer structure
isting of inorganic components as shown in Figure 10.1. Furthermore,
d on such information, they reported the treatment of Li metal surface
25 26
HF to suppress Li dendrite formation. •
Another topic of research on salts suitable for a Li anode is the
zation of new salts with an organic anion as alternatives to conventional
ganic salts. Among them, lithium bis(perfluoroalkylsulfonyl)imides
especially proved interesting. They have been tested in various cell
ems, where aLi imide has been used not only as a single electrolytic salt
also in mixture with another salt, e.g., LiN(S02C2F5h with LiPF6•
y useful imides have two perfluoroalkylsulfonyl groups linked to a
ral nitrogen atom asymmetrically [e.g., LiN(S02C2F5)(S02C3F7)], as
as symmetrically [e.g., LiN(S02C2F5)2], with the exception of lithium
rifluoromethylsulfonyl)imide [LiN(S02CF3)z], which is known to cause
vere corrosion of the aluminum substrate at the cathode.
Naoi et al. reported that electrolytes containing some
um
100
•••·•--·------·g-··· ----·-····--
..._
0
>-.
80 -.....-...
_ ,. . /-Q.-c:;
/ -... - =..-=:c :::;.-- ---..... --
.... - ....
c
d)

0 60
i:E
d)

. 40
E
0
:::I
0 20
u
0
0 5 10 15 20
Cycle number

e 10. 2. Addition effects of 2MeF, 2MeTp, and benzene on coulombic efficiency of Li


with LiCI04 (1 moVdm3); current density: 1.0 mA/cm2 ; charged: 0.1 C/cm2 ; a:
: PC + 2MeF (0.5 vol %), c: PC + 2MeTp (0.5 vol %), d: PC +benzene.
Chapter 10

erfluoroalkylsulfonyl)imides provide a LiF layer which is thinner than


derived from electrolytes containing LiPF6; this thinner layer can
ct
Li surface and promote efficient Li cycling.27 They emphasized that
formation mechanism of the LiF layer in lithium imide-based
rolytes should be completely different from that of LiF layer in
6-based electrolytes. In the latter, LiF is formed thanks to the small
unt of HF contained in the LiPF6 systems, while in the imide systems
comes from the direct reaction of the imide anion with Li metal.
To modify a metallic Li surface, as already stated, some additives to
rolytes have been investigated. Figure 10.2 shows the effect of
ral representative additives, 2-methylfuran (2MeF), 2-methylthiophene
eTp), and benzene, on the coulombic efficiency of Li cycling in
04-PC.
The addition of 2MeF and 2MeTp can restrain a decrease in Li
28
ng efficiency. On the other hand, a positive effect of benzene
ion appears at a higher concentration when compared to the effective
entration of 2MeF and 2MeTp. According to interface analyses such
c impedance measurement, the origin of the positive effect of these
28
ives can be explained with the help of Figure 10.3.

A)
@
@@
Reacti @ --..
High resistance film
Limetal

Good conductive film


Limetal Li metal

e 10.3. Working mechanisms of organic additives, A) without additive, B)


ve additive such as 2MeF or 2MeTp, C) adsorption-type additive such as
ne.
Current Issues of Metallic Lithium Anodes 307
2MeF and 2MeTp react with Li metal to form an ion-conductive
ective layer which provides uniform Li deposition at the Li surface.
the other hand, although benzene does not react with Li metal, it is
mulated, or adsorbed, at the Li interface due to its low polarity, and the
lting quasi-layer acts as a barrier separating electrolyte components
Li metal.
Figure 10.4 shows the effect of adding a small amount of metal ion
2 29
+ and Sn +). A positive effect of these additives on the Li cycling
iency can be clearly observed. Here, it should be significant to know
difference in ionic current distribution on the Li metal anode

100 e

d ...... .,.- --...1'!1--" .. _....


......... --..... -·, "'""- -c--
90 . ,'

80
. ,'
---..--
70

60

50
0 5 10 15 20
Cycle number

e 10.4. Addition effects of Lil, Snl2, AII3 , and AII3 + 2MeF on coulombic
2
ency of Li in PC with LiCI0 4 (1 moVI); current density: 2.0 mA/cm ; charged
2
ricity: 0.2 C/cm2 ; a: PC, b: PC+ Lil (r 300 ppm), c: PC+ Snl
2 (Sn + 100 ppm),
d: AII3 (ArJ+ 100 ppm), e: PC +AII3 (Al3+ 100 ppm)+ 2MeF (0.5 vol %).

without additives; to observe this, the scanning vibrating electrode


29
nique (SVET) was applied. ' 30 The outline of the in situ SVET system
rawn in Figure 10.5; this system can offer potential gradient profiles
ced by the Li ionic currents on the surface of the Li-deposited electrode
ng discharge. The scanning vibrating (SV) electrode (a Pt wire
trode) attached to a sensor probe is vibrated (with a certain frequency
een 100-1000 Hz) along a vertical axis (Z-direction) in the vicinity of a
specimen electrode surface by a piezoelectric oscillator; typical distance
Chapter 10

een the SV electrode and the test electrode is 2-50 ).!m.


One can obtain a potential gradient value which is the difference
een the potential detected by the SV electrode at the highest position
that at the lowest position during the vertical vibration of the
lectrode.

SCSI Board

r--· '--------,
........... lll!llfl!lllll-.. - lIl
Actuator 1I
eootro er II
II

Galvanoatat
Pot.ntlosblt 1-----*1

--Signal Lile
NlSubstr11t. --- RS-2320
···-GPIB

e 10.5. Scheme of SVET instrumentation.


Current Issues of Metallic Lithium Anodes 309
trode. The distance between the highest and the lowest positions was
he sub-micron order: say 0.5 f..lm. In this case, therefore, the potential
ient values correspond to the potential gaps along a distance of 0.5 f.!m
he vertical axis on the test electrode surface. This potential
ient is proportional to the ionic current in the vicinity of the
trolyte-test electrode interface because the resistance of the
trolytes can be
rded as a constant. The X-Y stage, on which the SV electrode is
nted, is moved horizontally by a stepping motor. By gathering the
ntial gradient values at various X-Y positions, a two-dimensional
ntial gradient map on the test electrode can be obtained. After all, on
basis of the above measurement criterion, a potential gradient map must
elate directly with ionic current distribution on a test electrode.
Figure 10.6 indicates the potential gradient maps of Li metal anode
ace with anodic polarization with and without additives. When the
als (Al and Sn) deposit at Li metal surface with cathodic polarization,
change into a thin Li-alloy surface layer, which can ease the
ularity of Li anode interface. Thus the distribution of Li ionic current
mes relatively regular at the surface with anodic polarization as shown
igure 10.6. Ishikawa et al. revealed the compatibility of metal ion
tives with electrolytes; for example, an additive such as All3 can fairly
nce the cycleability of the Li metal anode especially in lithium
e-based electrolytes.31'32
On the other hand, as for gaseous additives, Osaka et al. analyzed the
ct of saturating electrolytes with C02 upon Li metal cycle performance
he basis of ac impedance measurement, and found this addition effective
14 15
he enhancement of Li anode cycleability. ' Furthermore, some
33 34
actants were reported to have such an enhancement effect. •
Again, representative mechanisms of the aforementioned additives
be briefly summarized as follows: (a) formation of organic polymer
ive layer with a good ionic conductivity as a protective interface derived
28
organic compounds such as 2-methylfuran (2MeF) or its analogues,
adsorption of inactive additives at a Li interface to inhibit a reaction
ing a low-conductive passivation films resulting in uneven Li
osition, i.e., nonpolar additives such as benzene and dekalin28 as well as
ic or nonionic) polymer or oligomer additives such as surfactants,33• 34 (c)
lloy layer formation by co-deposition of Li with another metal such as
rom an electrolyte containing a small amount of metal salt additive, e.g.,
, to control the morphology of Li deposit (in other words, to suppress
dritic deposition of Li),2932- (d) formation of an uniform inorganic
ective layer from a dissolved gas such as C0212- 15 or inorganic acid, e.g.,
s.z6
These working mechanisms appear to have independent origins, so
Chapter 10

we are likely to observe "synergistic effects" when we use some


ives with different mechanisms simultaneously. In fact,
imultaneous use of All 3 and 2MeF results in a better Li cycleability
n compared to the effect of each additive (Figure 10.4).29 In addition,
e of

-1
"D
JS
t3 0.5

J
01)

All3: 200 ppm

....
c 2$

e
t o.s
c:l ! l ..
00
Sni2: 100 ppm

.....
c
m

J Q.S

J 35

10.6. Potential gradient maps of Li-deposited Ni substrate (X-Y plate) in


2Me-THF!LiC104 during discharge (25 mV vs. LilLi+); 2 mA/cm 2 and 0.2 C/cm2
-deposition.
Current Issues of Metallic Lithium Anodes 311

above additives have been known to provide "sustained" effect, even


transfer of aLi anode from an electrolyte with an additive to another
trolyte without additives, the Li anode "treated" with the additive, in
e cases, still retains the effect of the additive.35
This means that "pretreatment" of a Li anode with some additives
enhance the cycling efficiency in the subsequent cycles in a "clean"
trolyte without additives?5 This treatment sequence may be promising
use we could avoid some undesirable effects of such additives upon
r battery components: for instance, internal self-discharge originated
the shuttle effect of redox active additives between anode and cathode,
n unforeseen negative effect of the additives on cathode performance.

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L159.
Y. Matsuda, M. Ishikawa, S. Yoshitake, M. Morita, J. Power Sources 54 (1995) 301.
M. Ishikawa, S. Machino, M. Morita, J. Electroanal. Chern. 473 (1999) 279.
M. Ishikawa, S. Machine, M. Morita, Electrochem. 67 (1999) 1200.
T. Hirai, I. Yoshimitsu, J. Yamaki, J. Electrochem. Soc. 141 (1994) 2300.
K. Naoi, M. Mori, M. Inoue, T. Wakabayashi, K. Yamauchi, J. Electrochem. Soc. 147
2000) 813.
M. Morita, M. Ishikawa, Final Report on Electrochemistry of Ordered Interfaces: by
Grant-in-Aid for Scientific Research on Priority Area (No. 282) from The Ministry of
ducation, Science, Sports, Culture, Japan, 2000, 57.
apter 11

TRENDS IN CATHODE MATERIALS FOR


RECHARGEABLE BATTERIES

1 2 3
M. Pasquali , S. Passerini and G. Pistoia
1
Dipartimento ICMMPM, Universita di Roma La Sapienza, Rome, Italy
2
Enea Casaccia, Rome, Italy
3
Consultant, Rome, Italy (E-mail: pistoia@libero.it)

. INTRODUCTION

This chapter will not provide an exhaustive review of the work on


des for rechargeable Li batteries, but will try to focus on the most
ficant recent advances in both fundamentals and applications.
Commercial Li-ion batteries were successfully introduced into the
1
et by Sony in 1991. They used LiCo02 as a cathode and more than a
de later this is still the cathode of choice. Nonetheless, the research on
de materials has been more intense than ever and remarkable success
een met both at the practical and at the theoretical level. Improving the
o02 synthesis has contributed to double the specific energy of
mercial batteries in 10 years: from 80 to 165 Wh/kg. A new cathode,
n 204, has been introduced by NEC24 a in 1996 and Sanyo4 b in 2001,
ugh for a limited market. Some other materials, derived from LiCo02,
LiNi 1_x-yCoxMy0 2 (x+y<0.25, M=Mg or Al, preferably), have become
us candidates as future cathodes.
A wealth of knowledge has been acquired in terms of: synthesis
iques, reaction mechanisms, effect of particle size, interfaces, structural
fications, effect of doping, electrochemical and thermal stability, etc.
knowledge has allowed to revisit the criteria of choice of an efficient
de. The classical criteria based on thermodynamic and kinetic
iderations are:
1. The cathode must intercalate (if layered) or insert (for mono- and
tri-dimensional structures) u+.
2. To show a high OCV, it has to have low electron energy (hence low
Fermi level) and low site energy for Lt.
3. The electrode potential should have limited variations as a function
Chapter II

of Li+ content.
4. The number of sites for Lt has to be high and the hosting molecule
has to feature low weight and high density (high gravimetric and
volumetric capacity).
5. The coupled diffusion of electrons and Lt in the host, as a function
of concentration gradient, must be fast enough to grant a good rate
capability (high power).
6. The Lt intercalation/insertion has to be reversible, i.e., with no or
reversible structural changes, to allow cyclability.
7. The cathode must be stable towards the electrolyte over the entire
operating voltage range.
To these criteria, one has to add the prerequisites of:
8. Low cost.
9. Lack of toxicity.
10. Ease of synthesis.
However, it is becoming evident that the above are necessary but non
cient criteria. One has also to add:
11. A favourable interface formed in contact with the electrolyte (a
cathode may be stable in a given electrolyte, but affected by a
highly resistive interface).
12. The synthesis has to be not only simple, but also reproducible and
must allow the production of a material with the desired particle
size (the latter feature being of the utmost importance).
13. It should be possible to prepare a material encapsulated by another
one to protect it from unwanted reactions with the electrolyte.
14. The material has to be easily processed into a practical electrode.
Indeed, some materials may be difficult to fabricate as sheets (e.g.,
a LiNi02 slurry tends to be thixotropic).
Furthermore, the choice of a cathode is oriented by the applications.
instance, in portable devices, a material can be tolerated which is
ively expensive and moderately performing at high rates; conversely for
power applications, such as in EV, cheapness and rate capability are
datory.
In Table 11.1, materials which have particularly attracted the attention
esearchers in the last 10-15 years are reported together with their
ating voltage ranges. More details on them will be given in the
opriate sections. Before starting the description of selected cathode
rials, we think it useful reviewing the principal methods of synthesis.
section will be followed by two other sections dealing with the effect of
cle size on cathode performance and with the properties of the cathode
ion interfaces. These aspects are of a general character and can apply to
athode materials.
s in Cathode Materials for Rechargeable Batteries 317

ll.J. Cathode materials of interest and their V range.

V Range Typical Materials

5 LiMnz_xMx04 (x .5)
4 LiNiOz, LiCoOz, LiCol-x-yNixMy0z,
LiMnz04, Lil+yMnz-xMx04 (low x andy)
4-3 LiMnOz, LixMnl-yMyOz, Li[LixMyMnl-x-y]Oz
3.5 LiFeP04
3 Mn Spinels, LixMnOz, LixVyOz
2 Sand Polysulfides
1.5 FeSz

. METHODS OF SYNTHESIS
For many years, the only way of synthesizing cathode materials was
hermal treatment at high temperatures of mixtures of reactancts.
sion limitations in the solid state impose both long reaction times and
nding between subsequent firings. Even so, the possibility of having less
pure final products remains high. This can be partially alleviated if a
ant has a low melting point, so that the melt can impregnate the solid
impregnation technique). However, especially if the solid reactant has
particles and limited porosity, the core of the solid may not be reached
e viscous melt, again leading to incomplete reactions.
Since the 90's, alternative methods of synthesis have been proposed.
neral, they tend to form a better mixture of the precursors and to reduce
the time and temperature of the reaction. The most popular of these
sses is sol-gel synthesis. Originally, this term was used for the
lysis of an alkoxide and subsequent heating of the hydrolysis product
ve an oxide. At present, we call solution-sol-gel (or sol-gel, for short)
process in which a solution gives, through a chemical reaction, a sol
h converts into a gel. The latter is typically converted by annealing or
nt-exchange into the desired ceramic (normally an oxide) .
The sol-gel process allows a high degree of control over the physico
ical characteristics of the product obtained with high purity and
geneity. This is made possible by the initial solution step, as the
mixing of the reactants may reach the molecular level. Then, lower
eratures and shorter firing times are necessary to achieve materials with
Chapter 11

electrochemical characteristics. Quite often, this approach allows one


tain small particle size materials and, so, faster reactions through faster
sion of intercalating ions. However, the particle size issue is a rather
ate one, as lowering this parameter may bring about such shortcomings
w packing density, poor thermal stability, higher reactivity with the
rolytes and enhanced solubility. We shall return to this topic in the
wing sections.
In a typical sol-gel process, a mixture of reactants is dissolved in
r, and a solution with a chelating agent is then added and mixed. Slow
oration of the solvent generates a sol and moderate heating of the latter
s a gel, which is then is calcinated at the appropriate temperature. An
ple of sol-gel process is reported in Figure 11.1 for a synthesis of
n 204, using adipic acid as a chelating agent.5

Li(CH3C02) • 2H20
Mn(CH3C02)2 • 6H20 Adipic acid
aqueous solution aqueous solution

I I
I Mixing

Adipic acid/metal acetate


aqueous solution

l Drying at 80-

90°C
Adipic acid/metal sol

I Drying at 90-1oooc

Gel precursors

1 Calcination at 300-800°C in air

Polycrystalline LiMn204
powders

11.1. Typical sol-gel scheme (from Ref. 5).

Control of the pH and concentration of the chelating agent is required


ptimized characteristics. Several chelants have been proposed, e.g.
acrylic acid) (PAA), poly(vinylalcohol) (PVA), and monomeric acids
ccinic, adipic, glycolic, stearic, citric, propionic, oxalic. A technique
tly described is the so-called combustion synthesis. The reactants (e.g.
s in Cathode Materials for Rechargeable Batteries 319

nd Mn nitrate in the case of Mn spinel) are dissolved in a solution


ther with a fuel (e.g., urea or PAA). The powder formed on reaction is
and then calcined at the appropriate temperature while igniting.
bustion is thought to accelerate the reaction and to bring it to
pletion.6 -9
A peculiar technique combining the features of sol-gel and
10
bustion is the so-called Pechini process applied to Mn spinels. To a
ion containing Li and Mn compounds, a solution of citric acid and
lene glycol is added. The polymeric gel obtained is pre-ignited at
ively low temperature before being calcined. As in the case of sol-gel
hesis, particles in the submicron range, with surface areas higher than
e typical of thermal treatments, are obtained.
Solution techniques with reduction or oxidation processes have also
11
exploited. For instance, Mn spinel can be obtained by reduction of the
12 2 13
anganate with such reducing agents as fumaric acid or Mn +.
2
versely, Mn + aqueous solutions can be oxidized with lithium peroxide,
om temperature and in the presence of LiOH, and the precursors can be
at t<500°C to give Li4Mn 5012 with unusually good performance in the
14
range (Figure 11.2). A material which can be prepared by reduction in
15
ion and shows excellent electrochemical behaviour is V02(B).
ed, the nanocrystalline product so obtained can insert into its

Capacity (mAh/g)
0 50 100 150 200

2
O.lmA/cm

3 --------------
/t'\

,
lOth 5th lst

3
[\. .............-···-·-·-·-·-·-. ..
0.5mA/cm
2
/t""
40th 20th IOth 1st

2-

1 --.---.--.---.--,---.--.
0.0 0.5 1.0 1.5 2.0 2.5 3.0 3.5
x in Li 4+Mn sO 12

Figure 11.2. Discharge curves of Li 4 Mn5012, synthesized by a solution technique, in the


3 V range (adapted from Ref. 14).
Chapter 11

odimensional tunnels 0.9 Li per vanadium 16 (290 mAhlg) vs. 0.5 Li per
dium for the thermally prepared analog.
A peculiar synthesis of LiNi02 (and LiNi1_xCox02) is carried out by
izing, in a LiOH solution, Ni(OH)2 to NiOOH with Na2S208, followed
17
he H+;u+ exchange in the same solution. This form of LiNi02 shows a
4 -7 2
electron redox reaction (Ni + Ni +) to which a specific capacity of 300
2
/g corresponds in the potential range 4.2-1.5 V. 30 cycles at 0.9 mA/cm
eported, with a final capacity of 260 mAh/g.
Ion-exchange has been frequently exploited in the last years,
cially to obtain LiMn02 or similar materials. Orthorhombic LiMn02 was
prepared by Dahn et al. by ion exchange in an acetonitrile solution from
18
OH and LiOH. Bruce et al. have substituted Li for Na in NaMn02 and
4Mn02 19by21 ion exchange in alcoholic solutions at moderate
eratures. - The products so obtained show high capacities and long
e lives. They will be more extensively treated in another section of this
ter.
An interesting solution procedure, sometimes utilised to tailor
rials 22with
25 structures otherwise difficult to achieve, is hydrothermal
hesis. - By controlling such parameters as the pH of the medium,
erature, solvent, time and, optionally, size of the templating cation (if a
ial architecture is sought), modified oxide cathodes may be obtained. An
ple is the layered MxMn1_yCoy02 (M=Na or K) which has an electronic
uctivity two orders of magnitude higher than pure KxMn02 .Z Also, a
4

ed Mn oxide can be stabilized 26 by placing pillars (e.g., of vanadium


e) between the Mn02 sheets. The opposite is also possible, that is
26
lizing the layered structure of a vanadium oxide with Mn ions.
27
Other peculiar synthesis techniques include spray drying , emulsion
28 9
ng and freeze drying? In all of them the precursors are initially
lved (suspended) in aqueous solutions enabling the formation of sub
on particles. Whether or not these rather complex techniques can really
seful is difficult to say as limited data on battery cycling have been
rted.
30 31 32
Recently, the synthesis of Li cobaltate and Mn spinels · by
owaves has been reported. The former has been cycled for over 300
s in a lithium-ion cell. Li-rich and fluorinated spinels have been
2
hesised in a domestic microwave oven in less than 40 minutes?
rtunately, no electrochemical data were provided.
A technique which has been emerging 33 in the last34 few
35 years is
hanochemistry. LiM02 (M=Ti, Mn, Fe) and spinels · have been
hesized by ball milling mixtures of Li compounds and Mn oxides. It is
ising that a definite compound may be formed in a limited milling time.
nstance, in 10 minutes LhC03 and Mn02 give rise to spinel formation.
cceleration of the solid state reaction is due to the close contact of the
ents imposed by grinding and plastic deformation of particles.
s in Cathode Materials for Rechargeable Batteries 321

equent thermal treatment to the desired stoichiometry and degree of


allinity may be carried out. Tarascon's group has shown a satisfactory
cycle even for a non-annealed spinel after 8 hrs of grinding. Sub
2 35
on particles of high surface area (12-18 m /g) are obtained. "

. EFFECT OF PARTICLE SIZE AND


MORPHOLOGY ON CATHODE BEHAVIOR

The choice of a synthesis technique to produce a cathode material of


ntial use in Li batteries should take into account the kind of particles
ned by that technique. Indeed, the size (and its distribution),
hology and density of the particles play a fundamental role on their
rmance. It is also possible to modify the particle size by simple
ing after the synthesis and, in some instances, the behaviour of the
fied material may be surprisingly different.
When evaluating if a material with given particle characteristics is
ble as a cathode, one has to assess its behaviour not only in typical room
erature cycling but also in high temperature storage and cycling. Indeed,
ese latter conditions, unwelcome reactions with the electrolytes, e.g.,
mposition and dissolution processes, may more easily be identified. A
k of its thermal stability is also necessary, as this important parameter
deteriorate with smaller particle sizes.
Compounds based on nanoparticles constitute a relatively new class of
des with, at least, one excellent characteristic, i.e., elevated cyclability.
comes from much shorter diffusion paths for Lt diffusion and the
rrence of smaller dimensional changes upon cycling. Some examples
rovided below.
Nanosized V205, synthesized by the combustion flame-chemical vapor
36
ensation process giving particles of -40 nm, has a capacity of 170
lg (14 cycles), while coarse V 205 has only 130 mAhlg. Furthermore, the
ersible capacity loss after the first charge is negligible for the former,
6% for the latter.
LiMn 204 cannot be cycled in the 3 V range, as the Jahn-Teller (J-T)
t changes the cubic phase (da=1) into a tetragonal one (da=l.16). The
ting large volume increase causes particle fracture and loss of contact.
4 3
ntly, this problem was alleviated by using spinels having a Mn +/Mn +
11
higher than 1, such as Li4Mn5012• However, a surprising result has
reported by Goodenough et al. who could cycle a nearly stoichiometric
l (Li1.03Mnl.9104, Mn oxidation state=3.64), after ball milling, in spite
apparent J-T distortion.37• 38 It has been observed that ballmilling (1-2
produces three effects: generation of lattice strains, partial oxidation of
to 3.76) and formation of nanosized grains within the particles. The
induced by the J-T effect is supposed to be better accommodated in
Chapter 11

mall particles, i.e., it is less anisotropic also by virtue of the pre-existing


n.
A similar effect has been reported for a spinel created by the
rochemical cycling of orthorhombic LiMn02 (o-LiMn02) obtained at
temperature.39 This spinel has a nanodomain structure with particles of
0 nm within the pristine particles. At low rates (3.3 rnA/g), a capacity
of
mAh/g can be obtained, which is 95% of the theoretical value.
ording to the authors, the J-T effect is suppressed in this case due to
n disorder (partial occupation of the lithiated spinel tetrahedral sites)
the occurrence of nanodomains.
The above mentioned excellent cyclability of o-LiMn02 could only be
rved after several cycles. Indeed, the initial capacity was below 40
lg and reached a steady value after 30-40 cycles. Lee and Yoshio have
prepared o-LiMn02 by high temperature synthesis (1000°C followed by
40
ching) and observed the same low initial capacities. However, after a
milling to bring the surface area from 0.55 to 9.25 m 2/g, these authors
d obtain a material providing 193 mAh/g in the first cycle. The
sional limitations due to the relatively large particles (5-15 f-Lm) were
come with the smaller ones obtained by milling.
The above positive effects stemming from the use of small particles
balanced by the drawbacks mentioned in the previous section. In
ical batteries, relatively large particles are now preferred. For instance,
i-ion cells by Sony have LiCo02 produced by a synthesis process using
4, Li 2C03 and PVA resin as precursors, so to obtain a material with
cles of 20 f-Lm, instead
41 of the 1-3 f-Lm which are obtainable in the
entional synthesis. In this way, a better packing density and an
nced safety are obtained.
The importance of particles with a predetermined shape and size is
sed in some articles related to LiNixCo1 _x02• Cho et al. were able to
hesize this material starting from coprecipitated NixCo1_x(OH)2 with
42
rical particles. Reaction of the latter with LiOH at 650-750°C
uces LiNixCo1_x03 2 with the same 3 spherical particles of -15 f-Lm and a tap
ity of 2.9 g/cm (vs. 2.6 g/cm for the analogous product obtained by
mal synthesis). This material cycles much better than the one obtained by
ary thermal synthesis and, furthermore, has a higher volumetric energy
ity as the uniform spherical particles improve the packing density.
The same cathode material (with the exact composition
0.74Co0.2602) was investigated, in its electrochemical and43thermal
vior, with 3 different particles sizes, namely 5, 13 and 25 f-Lm. When
d at the 1C rate, the 5-f-Lm material shows a fairly constant capacity of
mAhlg for 70 cycles. Under the same conditions, the cathodes with 13
25 f-Lm show a final capacity of 160 mAh/g, which is still remarkable at
igh rate used. On the other hand, DSC experiments have shown a large
s in Cathode Materials for Rechargeable Batteries 323

hermic peak for the 5-!.lm material, while the heat evolved by the two
r materials is rather limited. The conclusion is that the large surface area
2
m /g) of the 5-f..lm cathode and the subsequent reaction with the
rolyte prevent its use in practical batteries.
A similar solution technique ("controlled crystallization") was used by
et al. to obtain spherical LiNi 0.8Co0.202.44 These authors could obtain
cles with a very high tap density (3.24 g/cm\ while a commercial
le not based on spherical particles has a density of 2.27 g/cm3• The
er material could maintain a stable capacity of 170 mAh/g when cycled
2
5 mA/cm for 50 cycles.
A study of commercial Mn spinels has again stressed the importance
e morphology factor in determining the electrochemical performance.
ng the different samples, those having uniform spherical particles
ting from the agglomeration of spherical crystallites showed better
45
bility.
The issue of capacity fading for the Mn spinel upon storing and
ng, especially at high temperatures, has received a wealth of attention.
we wish to point out the reported implication of the spinel particle size
is phenomenon. Tarascon et al. have investigated in detail this aspect
ound a correlation between surface area and capacity loss on storing or
ng at 55°C.46 They prepared samples with different surface areas and
d that as this parameter increases the irreversible self discharge also
ases, due to the enhancement of both electrolyte oxidation and Mn
lution. A low surface area of 0.5-1 m2/g is considered optimal by these
ors.
The issue of spinel surface area vs. capacity fading has also been
essed by Cho through measurements of the surface area by both a
entional BET method and methylene blue (MB) method.47 With the
the area is measured through N2 adsorption, while the second is based
e adsorption of MB molecules. The difference between the two lies on
act that N2 can access the nanopores of the particles, while the larger
molecules, having the same size of the electrolyte molecules, -15 A,
ot. When evaluating the electrochemical characteristics of 5 samples
particles in the 5 to 50 f..lm range, a precise correlation was found
een irreversible first cycle capacity (and capacity fading) vs. MB
ce area. As the latter increased, higher values for the irreversible
city and capacity fading on cycling were measured. Interestingly, BET
MB surface areas did not correlate and even had opposite trends for the
es in the 13-25 f..lm range.
There are some discrepancies in the literature about the influence