XRD Solutions for Li-ion Battery

Research
Maykel Manawan
Yanuar BK
Today’s Speakers

Maykel Manawan Yanuar

 Application Scientist  Sales Manager

© 2021 Bruker Innovation with Integrity | 18 October 2021 | 2

- confidential -
Battery tech is hot

Drivers – increasing demand Li-ion “Mega” Battery Market Value (2010 – 2030)
at lower cost Factories Li and Pb based batteries
 Electric vehicles
 Shift to renewable energy Estim. CAGR ~13%
 Portable electronic devices
 Battery cost dropped 80% in last
decade (to ~200$/kWh) Li
 Federal funding (e.g. EU, US)
Pb

https://www.eurobat.org/news-publications/market-data/491-avicenne-study-eu-battery-demand-and-supply-2019-2030-in-a-global-
context-shows-that-in-the-next-decade-lead-and-lithium-batteries-are-critical-to-clean-energy-transition

© 2021 Bruker Innovation with Integrity | 18 October 2021 | 4

- confidential -
Li-ion batteries value chain
BAXS products

Raw &
Cell Application
processed Cell Battery Pack Recycling
components Device
materials

(XRD)
XRD XRD (XRD)
XRM
XRF
XRF
OES

© 2021 Bruker Innovation with Integrity | 18 October 2021 | 5

- confidential -
Li-ion batteries value chain
XRD applications

Raw &
Cell Application
processed Cell Battery Pack Recycling
components Device
materials

Raw materials inspection

Quality Assurance & Control

Materials synthesis XRD is a key characterization

Structural changes during cycling technique for battery R&D

© 2021 Bruker Innovation with Integrity | 18 October 2021 | 6

- confidential -
Why do we need to find better battery materials?

https://www.visualcapitalist.com/explaining-surging-demand-lithium-ion-batteries/

Are current Li-batteries not good enough?

 Specific energy of Li-ion batteries is <250 Wh/kg
 Compare that to petrol (gasoline): 12,000 Wh/kg

 Demand for energy storage increasing rapidly

 Build more batteries

 Finite resources & limited supply of raw materials

 Build better batteries

© 2021 Bruker Innovation with Integrity | 18 October 2021 | 7

- confidential -
Why do we need to make better battery materials?

What is “better”?
 High specific energy  more energy for longer
 Safe  reduce fire hazards & toxicity
 Sustainable  cradle-to-cradle life cycle
 Economical  reduce cost, increase lifetime
 Convenient  fast charging, wide operating range

Mid-term: improvements driven by Li-ion technology

Long-term: new materials/ other energy storage concepts

© 2021 Bruker Innovation with Integrity | 18 October 2021 | 8

- confidential -
 Li-ion batteries:
Structure & Chemistry of Cathode Materials

Layered Structure Spinel Structure Olivine Structure

LiCoO2 (LCO) LiMn2O4 (LMO) LiFePO4 (LFP)
 2D Li transport pathways  3D Li transport pathways  1D Li transport pathways

Julien et. Al; Inorganics 2014, 2, 132-154

© 2021 Bruker Innovation with Integrity | 18 October 2021 | 9
- confidential -
Real world applications

Cathode Chemistry Application

 LiNiCoAlO2 (layered)  Tesla Model S
 LiCoO2 (layered)  Apple iPhone
 LiNiMnCoO2 (layered)  Tesla Powerwall

 LiMn2O4 (spinel)  Nissan Leaf

© 2021 Bruker Innovation with Integrity | 18 October 2021 | 10

- confidential -
BRU KER SOLUTION S F OR BATTER Y RESEARCH

Key components for the D8 ADVANCE and D8 DISCOVER

Component Key benefits

LYNXEYE XE-T • Digital Monochromator Technology (no sample
fluorescence, no K-beta filters)
• Many cathodes contain Fe, Co, Mn, Ni (sample fluorescence)
• Improved background and faster data collection

EIGER2 R 250K/ • Large 1D detector active area for snapshot mode

500K • Rapid data collection for quick studies and large number of
data points in charge/discharge investigations
DIFFRAC.EVA • Cluster analysis tools for identifying new phases during
battery cycling
• 2D and Waterfall plots for data visualization
DIFFRAC.TOPAS • Batch mode for rapid determination of unit cell parameters,
phase quantification and crystallite size

© 2021 Bruker Innovation with Integrity | 18 October 2021 | 11

- confidential -
BRU KER SOLUTION S F OR BATTER Y RESEARCH
Battery cell for in-situ XRD
For reflection or transmission geometry
 Designed for XRD by battery experts
 Light and compact cell
 Fits in rotation stage
 Different window materials available
 For reflection & transmission
Benefits
 Easy to assemble and use
 Reliable electrochemical performance
 Study cathode, anode or entire cell
© 2021 Bruker
Part No LP (EUR)
A27D70 - Electrochemical cell
(w/o windows)
K430C8 - Be window (29mm)
for reflection
K430C20 - Be windows (29 +
18.4mm) for reflection &
transmission
K430C19 - Glassy Carbon
windows (29 + 18.4mm) for
reflection & transmission
Cell designed by Univ. Amiens (France)
mounted inside the rotation stage
Innovation with Integrity | 18 October 2021 | 12
- confidential -
BRU KER SOLUTION S F OR BATTER Y RESEARCH

Choice of measurement geometry with the new battery cell

Reflection Transmission
 Focus on single electrode  Study complete cell
performance  Hard radiation (Mo, Ag),
 “standard” radiation (Cu) collimated beam
Easily exchangeable
 Top window X-ray transparent  Top and bottom window X-ray windows

transparent Easy materials

loading

Exchangeable screw
for reflection or
transmission

© 2021 Bruker Innovation with Integrity | 18 October 2021 | 13

- confidential -
Potentiostat –
what is it and why do I need it for battery research?

What is a potentiostat? “Dynamic” experiments “Static” experiments

 Device used to control a two (or
more) electrode cell and run
electroanalytical experiments
 The potentiostat controls the
current or voltage applied to an
electrochemical cell

 It’s required to observe changes

to a battery cell in-situ during an
experiment

© 2021 Bruker Innovation with Integrity | 18 October 2021 | 14

- confidential -
BRU KER SOLUTION S F OR BATTER Y RESEARCH

Single channel potentiostat SP-50 (Bio-Logics)

integrated into measurement software

 Plan sequence of CC/ CV/ OCV#

cycles and XRD measurements in the
non-ambient tab of the WIZARD
 Measure at controlled points of the
battery’s charge-discharge cycle
 Transfer of the corresponding
current/ voltage parameters to the
measurement result file (.brml)

# CC/CV/OCV = Constant Current/ Constant Voltage/ Open Circuit Voltage

© 2021 Bruker Innovation with Integrity | 18 October 2021 | 15

- confidential -
New Product Sheets

Product Sheet XRD 57

 Battery Cell for in-operando XRD

Product Sheet XRD 56

 Potentiostat for Battery Research

© 2021 Bruker Innovation with Integrity | 18 October 2021 | 16

- confidential -
Innovation with Integrity
 [×105]
4000
2.50

Incremental Residual
Intensity (counts)

3000 2.00

1.50
2000

1.00
1000

0.50

40 60 80 100 120 140

2theta (degree)

Experimental and First Principle Calculation of

Li-ion Diffusion Path in Battery Materials
// UNHAN // BATAN
// NCPU // RIKEN
// ANSTO // UNHAN
// QUT
Energy Sources
Energy Storage

Moller et.al. (2017) Doi: 10.1016/j.pnsc.2016.12.014

Li-ion Battery Schematic
Why Li-ion Battery?

EV goal : 150 Wh/kg

& 300 W/kg
PHEV goal

HEV goal

EV : Electric Vehicle
HEV : Hybrid Electric Vehicle
PHEV : Plug-in Hybrid Electric Vehicle
IC : Internal Combustion

Tarascon & Armand (2001) DOI: 10.1038/35104644

Srinivasan & Newman (2004) DOI: 10.1149/1.1785013
Li-ion Battery - Timeline

Kim et.al. (2018) DOI: 10.1039/c8ta10513h

Li-ion Battery – Common Discharge Potential

Nitta et.al. (2015) DOI: 10.1016/j.mattod.2014.10.040

Li-ion Battery – Performance Enhancement

Nitta et.al. (2015) DOI: 10.1016/j.mattod.2014.10.040

Li-ion Battery Energy Density

Nitta et.al. (2015) DOI: 10.1016/j.mattod.2014.10.040, https://batteryuniversity.com

Cathode materials summary (most common)
Lithium Manganese Oxide Lithium Nickel Manganese Lithium Nickel Cobalt
Name Lithium Cobalt Oxide (LCO) Lithium Iron Phosphate (LFP)
(LMO) Cobalt Oxide (NMC) Aluminum Oxide (NCA)
Formula LiCoO2 LiMn2O4 LiNiMnCoO2 LiFePO4 LiNiCoAlO2
Voltage (V) 3.0 – 4.2 3.0 – 4.2 3.0 – 4.2 2.5 – 3.65 3.0 – 4.2
Energy Density (Wh/kg) 150 – 240 100 – 150 150 – 220 90 – 120 200 – 260
0.7;
Charge rate (C) 0.7 – 1.0 0.7 – 3.0 0.7 – 1.0 1.0
faster charge for some
1.0; 1.0;
1.0;
Discharge rate (C) 1.0 10 for some; 25 for some; 1.0
2.0 for some
30 if pulse (5s) 40 if pulse (2s)
Cycle Life 500 – 1000 300 – 700 1000 – 2000 1000 – 2000 500
Thermal Runaway (°C) 150 250 210 270 150
Portable and stationary
Power tools, medical devices, Portable electronics, electric Medical devices, industrial
Applications Small portable electronics appliances requiring high load
electric vehicles vehicles, industrial use uses, electric vehicles
current and endurance
Low energy density,
Short life span,
high self-discharge, Low thermal stability,
low thermal stability, Lower voltage,
Disadvantages Low energy density lower shelf life, Sensitive to moisture,
low specific power, patent issues
sensitive to moisture, higher cost
high cost
require special preparation

https://batteryuniversity.com
Project Abstraction
LIB Material This project aims to find ion diffusion in battery material through the
experimental and first principal approach.
In the experimental method, via X-ray and Neutron diffraction, the possible ionic
diffusion inside the crystal is determined by
• anisotropic displacement parameters (APDs) – required Rietveld
Experimental Ab-initio
refinement
• Nuclear density distribution – Maximum entropy method pattern
fitting
• Valence sum map – Bond Valence Sum calculation
X-Ray diffraction Neutron diffraction Nudged Elastic Band
In contrast with the experimental method, the first principle calculation is
essential to find the information of migration barriers for vacancy diffusion via a
direct-hop mechanism.
Anisotropy Anisotropy Quantum ESPRESSO (PWscf) package and the ultrasoft and the ultra-soft
Displacement - Displacement – GGA pseudopotential formalism of Vanderbilt will be use (1,2,3). The crystal
Rietveld Rietveld pseudopotentials will be constructed using the USPP code14 (4) and tested for
agreement with calculations using other methods and codes (5). The exchange-
correlation functional form will choose the local density approximation (LDA)
Electron density – Neutron density – and the generalized gradient approximation (GGA).
LDA
Fourier MEM 1. https://www.quantum-espresso.org/
2. https://www.quantum-espresso.org/Doc/INPUT_PW.html
3. https://www.quantum-espresso.org/Doc/pw_user_guide/node7.html
4. https://www.physics.rutgers.edu/~dhv/uspp/
Neutron Density - 5. http://users.wfu.edu/natalie/
BVS
 NEB – DFT example on Li3PO4

Du Y.A. & Holzwarth N.A.W. (2007) DOI: 10.1103/PhysRevB.76.174302

 Goal Example on LiFePO4

Nishimura (2008) DOI: 10.1038/nmat2251.

Dr. Maykel Manawan
Prof. Jia Hong-Pan
Prof. Evvy Kartini
Dr. Maxim Avdeev
 https://doi.org/10.1107/S1600576721008700

400 K
Intensity (a.u.)

300 K

100 K

3K

20 40 60 80 100 120 140

2theta (deg)

0.040
Thermal Parameter (A2)

Li1 Li2
U11 U11
U22 U22
0.030 U33 U33

0.020

0.010

0
0 100 200 300 400 0 100 200 300 400
Temperature (K)
https://doi/10.1021/acs.cgd.1c00727
https://doi.org/10.1016/j.isci.2021.102991
https://doi.org/10.1016/j.physb.2017.11.079
 Dr. Maykel Manawan
Dr. Sih Wuri Andayani
Dr. Masayu Elita Hafizah
Dr. Sovian Aritonang
Fathan Bahfie S.T., M.Si
Ir. Riyadi Juhana, M.T., M.Han
RIRN 2017-2045 : Advance Material

Simlitabmas Ristekdikti, 2020

Indonesia Strategic Minerals

ESDM, 2020
Material Processing Technology

Bahan Teknologi Nilai Masa

Alam Proses Tambah Depan

• Tambang • Pemurnian • Lapangan Pekerjaan • Kota mandiri

• Mineral • Smelter • Penguasaan Teknologi • Pusat ekonomi baru
• Batu Bara • Proses kimia • Pusat Pelatihan • Sumber energi baru
• Migas • Industri • Pajak • Jaringan global
• Non-tambang • Bahan jadi • Dikenal dunia
• Pertanian/Perkebunan
• Perikanan dan hasil laut
Material Processing Impact

Bahan hasil non-

tambang

Bahan hasil tambang

BPPT, 2019
Nikel laterite untuk Stainless Steel

Nickel laterit deposit Nickel pig iron Stainless Steel HRC Household Engineering

Mining Smelter Product Product Product

Smelter Stainless Steel Slab Stainless Steel CRC Turbine

Total Nickel deposit > 21 billion metric ton => Indonesia No.1 in the world (U.S. Geological Survey, 2019).
Nickel ore USD 30/ton → USD 160/ton ferronickel → USD 2300/ton stainless steel plate (www.benchmarkminerals.com/)
PT.IMIP, 2019
Nikel laterite for LIB Materials

Nickel ore USD 30/ton → USD 2300/ton nickel sulfate (www.benchmarkminerals.com/)

PT.IMIP, 2019
NMC-series Crystal Structure

NMC - 111 NMC - 532 NMC - 622 NMC - 811

CIF database coutersty ICDD Data PDF-4+ 2020

Experimental Method
Characterization
•Electrogravimetry, ICP, XRF, Nickel
XRD, SEM-EDS Matte/Laterite

Characterization Nickel Sulfate

•XRF, XRD Mangan Sulfate
Cobalt Sulfate

Characterization
•XRF, AAS, XRD NMC-series

Characterization
•SEM-EDS, GI-XRD Coating

ICP : Inductively coupled plasma

Characterization
•Cyclic Voltametry, EIS, In-situ
operando XRD, Battery Tester
XRF : X-Ray Fluorescence
SEM : Scanning Electron Microscope
Half/full cell
pack EDS : Energy Dispersive X-ray Spectroscopy
XRD : X-Ray Diffraction (XRD)
EIS : Electrochemical Impedance Spectroscopy
Professional Community & Collaborators
https://www.researchgate.net/profile/Maykel_Manawan

SCOPUS ID : 57202359553
Web of Science ID : O-8852-2018
Education Subcommittee
ORCHID ID : 0000-0003-3782-1307
Google Scholar : R6tOeqMAAAAJ&hl
SINTA ID : 6193883
TERIMA KASIH