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Solid Oxide Fuel Cells
From Electrolyte-Based to Electrolyte-Free Devices
Edited by
Bin Zhu
Rizwan Raza
Liangdong Fan
Chunwen Sun
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xiii
Preface
The fuel cell is a promising clean energy technology, which is not yet fully com-
mercialized. There are different types of fuel cells based on the chemical reac-
tions and charge transportation mechanisms employed, but the solid oxide fuel
cell (SOFC) technology exhibits major potential for large-scale applications. This
technology is, however, still subject to material and technology challenges accom-
panied with high costs. Though the literature on the SOFC technology is ample
covering various aspects such as materials, devices, electrochemistry, and appli-
cations, the contributions on the latest discoveries such as the non-electrolyte
fuel cell principles are rare.
This book is a unique collection of contributions on the development of solid
oxide fuel cells from electrolyte based to non-electrolyte-based technology. Since
the scientific discovery of the fuel cell principle some 180 years ago, a fuel cell has
been constructed with three basic components, namely, the anode, electrolyte,
and cathode, of which the electrolyte plays a key role for the operation of a fuel
cell. The electrolyte serves several important roles such as ion transportation, and
it supports the fuel cell redox reactions (hydrogen oxidation on the anode and
oxygen reduction on the cathode). But it also provides a separator to block against
electrons preventing them to pass through the device and forcing them to move
through an external circuit, thus preventing the fuel cell from short-circuiting.
Thus, the question: how could a fuel cell device at all work without the conven-
tional electrolyte layer is highly justified?
This book aims at giving a more comprehensive understanding on the advances
in fuel cells and to bridge the knowledge from traditional SOFC to the new
concepts. We will track the development from the conventional SOFC to the
non-electrolyte (layer) or single-component fuel cell, covering research on
the anode, electrolyte, and cathode component materials, and development
of devices and stacks for applications. A key area of underlying science of
the book deals with semiconductor and semiconductor–ionic principles for
non-electrolyte-based fuel cells.
This book is divided into three parts. Part I is on the conventional SOFC,
providing an update on the latest development of anode, electrolyte, and cathode
materials as well as the SOFC technologies. Part II discusses the non-electrolyte
or semiconductor-based membrane fuel cells. This new concept fuel cell
devices have been developed in recent years with extensive efforts and broad
innovations from materials, technologies, devices, and scientific principles by
xiv Preface
crosslink research from semiconductor physics and band theory. This new type
SOFCs had been developed from the single-layer fuel cells (SLFCs) or electrolyte
(layer)-free fuel cells (EFFCs) in the first inventions toward semiconductor
and semiconductor–ionic fuel cells. We start with the conceptual proof of this
technology employing both existing SOFC state-of-the-art materials and then
introducing new functional semiconductor–ionic materials to demonstrate
various single-component and semiconductor–ionic fuel cell technologies
without using the electrolyte separator. The emphasis of Part II is on various
new semiconductors and semiconductor–ionic materials including the scientific
principles, materials, device concepts, and fuel cell technology. Semiconducting
materials with ionic properties and mobility and the physics of semiconductor
energy band structures, which play a significant role in a single-component
fuel cell. Part III of the book focuses on engineering efforts from materi-
als, technology, device to stack developments, and various applications and
new opportunities of SOFC using both the electrolyte and non-electrolyte
technologies, including integrated fuel cell systems with electrolysis, solar
energy, etc. Two important issues have been seriously addressed to accelerate
SOFC commercialization: (i) technically the interfaces of the planar cell and
stack and (ii) commercially designed SOFC stack products to meet demands
of customers and applicable uses. The next commercial potential of these
technologies will depend on their advantages and disadvantages, but the new
semiconductor-based materials and technologies exhibit quite a few advantages
over the conventional electrolyte-based fuel cells.
Though this book uses a specific fuel cell technology, the solid oxide fuel cells,
as basis for describing advances in fuel cells, the intention is also to provide a
stronger vision in fuel cell materials and technologies in general. Serious and con-
crete research efforts are necessary to strengthen this field and to provide new
paths for innovations and breakthrough thinking on fuel cells.
The book will serve as important reference work to students, researchers, and
technology developers in the fuel cell field. We hope this book would give readers
fresh ideas, new knowledge, and inspiration.
10 August 2019 Bin Zhu, Rizwan Raza, Liangdong Fan,

and Chunwen Sun (Editors)
Peter D. Lund (Scientific adviser)
Stockholm and Helsinki
v
Contents
Preface xiii
Part I Solid Oxide Fuel Cell with Ionic Conducting

Electrolyte 1
1 Introduction 3
Bin Zhu and Peter D. Lund
1.1 An Introduction to the Principles of Fuel Cells 3
1.2 Materials and Technologies 5
1.3 New Electrolyte Developments on LTSOFC 10
1.4 Beyond the State of the Art: The Electrolyte-Free Fuel Cell (EFFC) 20
1.4.1 Fundamental Issues 23
1.5 Beyond the SOFC 25
References 28
2 Solid-State Electrolytes for SOFC 35

Liangdong Fan
2.1 Introduction 35
2.2 Single-Phase SOFC Electrolytes 37
2.2.1 Oxygen Ionic Conducting Electrolyte 37
2.2.1.1 Stabilized Zirconia 37
2.2.1.2 Doped Ceria 39
2.2.1.3 SrO- and MgO-Doped Lanthanum Gallates (LSGM) 42
2.2.2 Proton-Conducting Electrolyte and Mixed Ionic Conducting
Electrolyte 42
2.2.3 Alternative New Electrolytes and Research Interests 44
2.3 Ion Conduction/Transportation in Electrolytes 49
2.4 Composite Electrolytes 52
2.4.1 Oxide–Oxide Electrolyte 52
2.4.2 Oxide–Carbonate Composite 53
2.4.2.1 Materials Fabrication 54
2.4.2.2 Performance and Stability Optimization 57
2.4.3 Other Oxide–Salt Composite Electrolytes 60
vi Contents
2.4.4 Ionic Conduction Mechanism Studies of Ceria–Carbonate

Composite 62
2.5 NANOCOFC and Material Design Principle 66
2.6 Concluding Remarks 67
Acknowledgments 69
References 69
3 Cathodes for Solid Oxide Fuel Cell 79

Tianmin He, Qingjun Zhou, and Fangjun Jin
3.1 Introduction 79
3.2 Overview of Cathode Reaction Mechanism 80
3.3 Development of Cathode Materials 82
3.3.1 Perovskite Cathode Materials 82
3.3.1.1 Mn-Based Perovskite Cathodes 83
3.3.1.2 Co-Based Perovskite Cathodes 85
3.3.1.3 Fe-Based Perovskite Cathodes 88
3.3.1.4 Ni-Based Perovskite Cathodes 89
3.3.2 Double Perovskite Cathode Materials 89
3.4 Microstructure Optimization of Cathode Materials 94
3.4.1 Nanostructured Cathodes 94
3.4.2 Composite Cathodes 97
3.5 Summary 102
References 103
4 Anodes for Solid Oxide Fuel Cell 113

Chunwen Sun
4.1 Introduction 113
4.2 Overview of Anode Reaction Mechanism 114
4.2.1 Basic Operating Principles of a SOFC 114
4.2.1.1 The Anode Three-Phase Boundary 115
4.3 Development of Anode Materials 117
4.3.1 Ni–YSZ Cermet Anode Materials 117
4.3.2 Alternative Anode Materials 118
4.3.2.1 Fluorite Anode Materials 118
4.3.2.2 Perovskite Anode Materials 120
4.3.3 Sulfur-Tolerant Anode Materials 124
4.4 Development of Kinetics, Reaction Mechanism, and Model of the
Anode 126
4.5 Summary and Outlook 135
Acknowledgments 137
References 137
5 Design and Development of SOFC Stacks 145

Wanbing Guan
5.2 Change of Cell Output Performance Under 2D Interface Contact 145
5.2.1 Design of 2D Interface Contact Mode 145
Contents vii
5.2.2 Variations of Cell Output Performance Under 2D Contact Mode 147

5.2.3 2D Interface Structure Improvements and Enhancement of Cell
Output Performance 149
5.2.4 Contributions of 3D Contact in 2D Interface Contact 151
5.2.5 Mechanism of Performance Enhancement After the Transition from
2D to 3D Interface 153
5.3 Control Design of Transition from 2D to 3D Interface Contact and
Their Quantitative Contribution Differentiation 156
5.3.1 Control Design of 2D and 3D Interface Contact 156
5.3.2 Quantitative Effects of 2D Contact on the Transient Output
Performance of a Cell 158
5.3.3 Quantitative Effects of 2D Contact on the Steady-State Output
Performance of the Cell 161
5.3.4 Quantitative Effects of 3D Contact on Cell Transient
Performance 163
5.3.5 Quantitative Effects of 3D Contact on the Steady-State Performance of
a Cell 166
5.3.6 Differences Between 2D and 3D Interface Contacts 169
5.4 Conclusions 171
References 172
Part II Electrolyte-Free Fuel Cells: Materials, Technologies,

and Working Principles 173
6 Electrolyte-Free SOFCs: Materials, Technologies, and Working

Principles 175
Bin Zhu, Liangdong Fan, Jung-Sik Kim, and Peter D. Lund
6.1 Concept of the Electrolyte-Free Fuel Cell 175
6.2 SLFC Using the Ionic Conductor-based Electrolyte 177
6.3 Developments on Advanced SLFC 179
6.4 From SLFCs to Semiconductor–Ionic Fuel Cells (SIFCs) 184
6.5 The SLFC Working Principle 196
6.6 Remarks 204
Acknowledgments 207
References 207
7 Ceria Fluorite Electrolytes from Ionic to Mixed Electronic and

Ionic Membranes 213
Baoyuan Wang, Liangdong Fan, Yanyan Liu, and Bin Zhu
7.2 Doped Ceria as the Electrolyte for Intermediate Temperature
SOFCs 214
7.3 Surface Doping for Low Temperature SOFCs 216
7.4 Non-doped Ceria for Advanced Low Temperature SOFCs 222
References 235
viii Contents
8 Charge Transfer in Oxide Solid Fuel Cells 239

Jing Shi and Sining Yun
8.1 Oxygen Diffusion in Perovskite Oxides 239
8.1.1 Oxygen Vacancy Formation 239
8.1.2 Oxygen Diffusion Mechanisms 242
8.1.3 Anisotropy Oxygen Transport in Layered Perovskites 244
8.1.3.1 Oxygen Transport in Ruddlesden–Popper (RP) Perovskites 244
8.1.3.2 Oxygen Transport in A-Site Ordered Double Perovskites 244
8.1.4 Oxygen Ion Diffusion at Grain Boundary 246
8.1.5 Factors Controlling Oxygen Migration Barriers in Perovskites 248
8.2 Proton Diffusion in Perovskite-Type Oxides 249
8.2.1 Proton Diffusion Mechanisms 249
8.2.2 Proton–Dopant Interaction 253
8.2.2.1 Influence of Dopants in A-site 253
8.2.2.2 Influence of Dopants in B-Site 254
8.2.3 Long-range Proton Conduction Pathways in Perovskites 255
8.2.4 Hydrogen-Induced Insulation 256
8.3 Enhanced Ion Conductivity in Oxide Heterostructures 259
8.3.1 Enhanced Ionic Conduction by Strain 259
8.3.2 Enhanced Ionic Conductivity by Band Bending 263
8.3.2.1 Surface State-induced Band Bending 263
8.3.2.2 Band Bending in p–n Heterojunctions 265
8.3.2.3 p–n Heterojunction Structures in SOFC 265
8.4 Summary 266
Acknowledgments 267
References 267
9 Material Development II: Natural Material-based Composites

for Electrolyte Layer-free Fuel Cells 275
Chen Xia and Yanyan Liu
9.1.1 Materials Development for EFFCs 275
9.1.2 Natural Materials as Potential Electrolytes 276
9.2 Industrial-grade Rare Earth for EFFCs 279
9.2.1 Rare-earth Oxide LCP 280
9.2.2 Semiconducting–Ionic Composite Based on LCP 281
9.2.2.1 LCP–LSCF 282
9.2.2.2 LCP–ZnO 284
9.2.3 Stability Operation and Schottky Junction of EFFC 288
9.2.3.1 Performance Stability 288
9.2.3.2 In Situ Schottky Junction Effect 288
9.2.4 Summary 290
9.3 Natural Hematite for EFFCs 291
9.3.1 Natural Hematite 292
9.3.2 Semiconducting–Ionic Composite Based on Hematite 295
Contents ix
9.3.2.1 Hematite–LSCF 295

9.3.2.2 Hematite/LCP–LSCF 297
9.3.3 Summary 300
9.4 Natural CuFe Oxide Minerals for EFFCs 302
9.4.1 Natural CuFe2 O4 Mineral for EFFC 302
9.4.2 Natural Delafossite CuFeO2 for EFFC 305
9.4.3 Summary 308
9.5 Bio-derived Calcite for EFFC 308
9.5.1 Bio-derived Calcite for EFFC 309
9.5.2 Summary 312
References 314
10 Charge Transfer, Transportation, and Simulation 319

Muhammad Afzal, Mustafa Anwar, Muhammad I. Asghar, Peter D. Lund,
Naveed Jhamat, Rizwan Raza, and Bin Zhu
10.1 Physical Aspects 319
10.2 Electrochemical Aspects 320
10.3 Ionic Conduction Enhancement in Heterostructure Composites 321
10.4 Charge Transportation Mechanism and Coupling Effects 326
10.5 Surface and Interfacial State-Induced Superionic Conduction and
Transportation 330
10.6 Ionic Transport Number Measurements 331
10.7 Determination of Electron and Ionic Conductivities in EFFCs 332
10.8 EIS Analysis 334
10.9 Semiconductor Band Effects on the Ionic Conduction Device
Performance 335
10.10 Simulations 339
Acknowledgments 343
References 343
11 Electrolyte-Free Fuel Cell: Principles and Crosslink

Research 347
Yan Wu, Liangdong Fan, Naveed Mushtaq, Bin Zhu, Muhammad Afzal,
Muhammad Sajid, Rizwan Raza, Jung-Sik Kim, Wen-Feng Lin, and Peter D.
Lund
11.2 Fundamental Considerations of Fuel Cell Semiconductor
Electrochemistry 353
11.2.1 Physics and Electrochemistry at Interfaces 353
11.2.2 Electrochemistry vs. Semiconductor Physics 355
11.3 Working Principle of Semiconductor-Based Fuel Cells and Crossing
Link Sciences 356
11.4 Extending Applications by Coupling Devices 367
11.5 Final Remarks 368
Acknowledgments 372
References 373
x Contents
Part III Fuel Cells: From Technology to Applications 377
12 Scaling Up Materials and Technology for SLFC 379

Kang Yuan, Zhigang Zhu, Muhammad Afzal, and Bin Zhu
12.1 Single-Layer Fuel Cell (SLFC) Engineering Materials 379
12.2 Scaling Up Single-Layer Fuel Cell Devices: Tape Casting and Hot
Pressing 383
12.3 Scaling Up Single-Layer Fuel Cell Devices: Thermal Spray Coating
Technology 386
12.3.1 Traditional Plasma Spray Coating Technology 387
12.3.2 New Developed Low-Pressure Plasma Spray (LPPS) Coating
Technology 388
12.4 Short Stack 395
12.4.1 SLFC Cells 395
12.4.2 Bipolar Plate Design 396
12.4.3 Sealing and Sealant-Free Short Stack 396
12.5 Tests and Evaluations 397
12.6 Durability Testing 399
12.7 A Case Study for the Cell Degradation Mechanism 400
12.8 Continuous Efforts and Future Developments 404
References 411
13 Planar SOFC Stack Design and Development 415

Shaorong Wang, Yixiang Shi, Naveed Mushtaq, and Bin Zhu
13.1 Internal Manifold and External Manifold 415
13.2 Interface Between an Interconnect Plate and a Single Cell 416
13.3 Antioxidation Coating of the Interconnect Plate 418
13.4 Design the Flow Field of Interconnect Plate 419
13.4.1 Mathematical Simulation 420
13.4.2 Effect of Co-flow, Crossflow, and Counterflow 422
13.4.3 Air Flow Distribution Between Layers in a Stack 424
13.5 The Importance of Sealing 424
13.5.1 Thermal Cycling of the Sealing 428
13.5.2 Durability of Sealing 428
13.6 The Life of the Stack: The Chemical Problems on the Interface 429
13.7 Toward Market Products 431
References 443
14 Energy System Integration and Future Perspectives 447

Ghazanfar Abbas, Muhammad Ali Babar, Fida Hussain, and Rizwan Raza
14.1 Solar Cell and Fuel Cell 447
14.2 Fuel Cell–Solar Cell Integration 450
14.3 Solar Electrolysis–Fuel Cell Integration 452
14.4 Fuel Cell–Biomass Integration 453
14.5 The Fuel Cell System Modeling Using Biogas 454
Contents xi
14.5.1 Activation Loss 457

14.5.2 Ohmic Loss 457
14.5.3 Concentration Voltage Loss 458
14.6 The Fuel Cell System Efficiency (Heating and Electrical) 458
14.6.1 The Effect of Different Temperatures on System Efficiency 458
14.6.2 The Fuel Utilization Factor and Efficiencies of the System 458
14.6.3 The System Efficiencies and Operating Pressure 460
14.7 Integrated New Clean Energy System 460
14.8 Summary 462
References 462
Index 465
1
Part I
Solid Oxide Fuel Cell with Ionic Conducting Electrolyte

3
Introduction
Bin Zhu 1,* and Peter D. Lund 2,*
1
Southeast University, School of Energy and Environment, No.2 Si Pai Lou, Nanjing 210096, China
2
Aalto University, School of Science, P.O. Box 15100, Puumiehenkuja 2, Espoo FI-00076, Finland
1.1 An Introduction to the Principles of Fuel Cells

Fuel cells have been under development for more than 180 years since its
discovery in the early nineteenth century. Several types of fuel cells have resulted
from extensive research and development work, but only two types have reached
a stage of commercialization. One is the polymer electrolyte membrane fuel
cell (PEMFC) and the other is the solid oxide fuel cell (SOFC). It is a generally
accepted opinion that the former is better applicable for transportation and the
latter for stationary power applications. This book focuses on SOFCs ranging
from traditional electrolyte-based to electrolyte-free or non-electrolyte-based
devices. The focus of contents will be on materials and technologies.
Going back to the history of fuel cells, the first major step in development was
the discovery of the water electrolysis to split water into hydrogen and oxygen
using electricity at the beginning of the nineteenth century. Electrolysis is actu-
ally a reverse process to the fuel cell. The fuel cell principle was discovered by
Humphry Davy in the early nineteenth century, which was followed by the pio-
neering work by Christian Friedrich Schönbein and Sir William Grove in 1838,
who realized the fuel cell concept by inventing the “gas voltaic battery.” In Grove’s
series of experiments on a gas battery in 1838/1839, an electric current could be
produced from an electrochemical reaction between hydrogen and oxygen over
a catalyst electrode couple [1]. Figure 1.1 shows the first laboratory prototype
device using iron and copper sheets as hydrogen and oxygen redox electrodes
(anode and cathode), and a solution of sulfate of copper and dilute acid as the
electrolyte. This is very similar to a phosphoric acid fuel cell.
The term fuel cell appeared in literature first in 1889, when researchers devel-
oped coal gas, also referred to fuel gas, and coal directly as a fuel to generate
electricity. Thus Grove’s gas battery was naturally named as “fuel battery” and
then “fuel cell.” The fuel cell (FC) is more suitable to present Grove’s invention,
*Corresponding authors: Dr. Bin Zhu, binzhu@kth.se; Dr. Peter D. Lund, peter.lund@aalto.fi
Solid Oxide Fuel Cells: From Electrolyte-Based to Electrolyte-Free Devices,

First Edition. Edited by Bin Zhu, Rizwan Raza, Liangdong Fan, and Chunwen Sun.
© 2020 Wiley-VCH Verlag GmbH & Co. KGaA. Published 2020 by Wiley-VCH Verlag GmbH & Co. KGaA.
4 1 Introduction
Water Figure 1.1 Sketch of William

Grove’s 1839 fuel cell, Grove’s
ox hy 1839 gas voltaic battery
diagram. Source: Grove 1839
[1]. Reproduced with
permission of Taylor &
Francis.
ox hy ox hy ox hy ox hy
Sulfuric acid solution
which also indicates its clear difference from battery energy storage due to the
nature of conversion. Shortly since demonstrated in 1839 by Sir Grove, all FCs
have been constructed with three functional components: anode, electrolyte, and
cathode, together called the membrane electrode assembly (MEA). In all current
FC technologies, the electrolyte has to be dense to prevent gas permeability [2].
The anode and cathode need hydrogen and oxygen catalysts and sufficient ionic
and electronic conductivity to create fuel (e.g. H2 ) oxidation and oxidant (e.g.
O2 ) reduction processes. H+ or O2− ions are subsequently transported through
the electrolyte to convert the fuel’s chemical energy into electricity, as shown in
Figure 1.2.
Phosphoric acid
Cathode Anode
[H] +
Solid polymer
Cathode Anode
[H]+
Alcaline solution
Cathode Anode
Air [OH]– Fuel
Molten carbonates
Cathode Anode
[CO3]2–
Solid oxides
Cathode Anode
[O]2–
Figure 1.2 Classical five types of electrolyte-based devices in fuel cell family.
The three-component MEA technology requires a complex FC structure and

technology as all components have to be stable and compatible. The interfaces
between electrolyte and anode and cathode, respectively, contribute to major
polarization losses [3], while the FC delivers power, and a complex technology
leads to high costs as well, delaying FC commercialization. Among the three com-
ponents, the electrolyte is the key [4]. It is often called as a membrane because
a fuel cell device is an assembly based on the electrolyte membrane, which acts
as the separator between the anode and cathode to block electronic conduction
to avoid electron short-circuiting problem. Therefore, the electrolyte is the pure
ionic conductor, and any electronic conduction can make electrochemical leak-
age leading to losses in the device voltage and power output. On the other hand,
the electrolyte must transportions to support the fuel cell redox reactions, i.e.
hydrogen oxidation reaction (HOR) and oxygen reduction reaction (ORR).
Several types of FCs have been developed based on the type of electrolytes,
such as PEMFC based on H+ transport in a polymer electrolyte, AFC (alkaline
fuel cell), OH− ions in a solution, PAFC (phosphoric acid fuel cell) with H+ in
phosphoric acid, MCFC (molten carbonate fuel cell) with CO=3 in molten car-
bonates, and SOFC with O2− in ceramic oxides [4, 5]. The electrolyte type and its
electrical properties determine which type of FC technologies and final system
can be used and which energy conversion efficiency can be realized at a certain
temperature. Figure 1.2 shows these five types of classical fuel cells classified by
the electrolyte used.
PAFC, MCFC, and AFC have been used in different special applications: e.g.
kW-sized AFC was used in Apollo’s moon landing program in the 1960s and
1970s with success to produce both power and water. PAFC and MCFC were pre-
commercialized in the late 1980s, and there are still ongoing MCFC commercial
demonstration plants, but these technologies never reached the scale of commer-
cialization. Only PEMFC and SOFC are left pushing toward commercialization.
1.2 Materials and Technologies

SOFC research and development are dominated by the yttria-stabilized zirconia
(YSZ) electrolyte. In 1899 Nernst first discovered that YSZ could reach oxide ion
conduction at around 1000 ∘ C (0.1 S cm−1 ). Today, the YSZ is still the choice of the
electrolyte material for high-temperature SOFC. A temperature of 800–1000 ∘ C
is typically needed for the YSZ electrolyte in order to obtain a sufficiently high
ionic conductivity [6, 7], which puts major constraints to the choice of construc-
tion materials and has resulted in high costs, thus slowing the commercialization
for the last decades. There has been much effort to develop alternative electrolyte
materials for SOFCs to lower the operating temperature [4, 8, 9]. Examples are
fluorite-structured ion-doped ceria [10], perovskite-type oxides [11], O2− con-
ducting oxides [12], and proton conducting ceramics [13] as well as other com-
plex materials such as La2 Mo2 O9 [14], BaIn-based oxides [15], and apatite-type
oxides [16]. Goodenough proposed that SOFC should be developed toward lower
enough temperatures to make it technically useful [17]. His approach was to
develop oxide ion conductors by design from structures based on discovered
6 1 Introduction
O2– ion Host cation (4+)
Dopant Cation Vacancy

(2+ or 3+)
Figure 1.3 Goodenough proposed oxide ion conductor by design: a structural method by
cation doping to create oxygen vacancy. Source: Reproduced with permission from
Goodenough [17]. Copyright 2000, Springer Nature.
materials. For example, the YSZ fluorite structure is presented in Figure 1.3. By
using a lower valency cation, e.g. 2+ or 3+, to replace higher valent Zr4+ , some
oxygen vacancy must be produced in order to maintain the electrical neutrality
in the crystal. In most cases, trivalent Y3+ is chosen to replace tetravalent ions,
Zr4+ , to create the oxygen vacancy so that O2− can move through vacancies in
the Y-doped zirconia structure.
However, this approach is constrained by the structure and the objective has
not yet been realized (to be discussed later). Using modern thin film technologies
to reduce the thickness of the YSZ electrolyte from millimeter to meter, to even
nanometer level, the electrolyte resistance and the operational temperature
could be reduced. Following this, strong development efforts have been made on
employing various advanced thin film technologies such as sputtering, atomic
layer deposition (ALD), molecular extension growth, laser deposition, spark
plasma sintering, and in situ surface nanoparticle exsolution methods, to fabri-
cate thin film YSZ-based electrolyte. For example, Kosacki prepared a thin (down
to 15 nm) film with highly textured YSZ membrane through PLD (plasma layer
deposition) [18]. Surprisingly, the conductivities could be significantly enhanced
to 0.6 S cm−1 at 800 ∘ C with significant low activation energy (Ea ) of 0.45 eV. This
conductivity is about one order of magnitude higher than that of a conventional
YSZ at this temperature. The bulk YSZ reaches 0.1 S cm−1 at around 1000 ∘ C
LSTN–YSZ top view LSTN –YSZ top view
LSTN
–YSZ
1 μm
STS
(a) (b) (c)
NIO–YSZ, YSZ targets LSC target Pt target

Current collector: Pt
Cathode: LSC
La Sputtering Electrolyte: YSZ
PLD se
r Anode: NiO–YSZ
Substrate: LSTN–YSZ/STS
Mask
(d) (e) (f)
Figure 1.4 Schematics of the fabrication process of micro-SOFC supported on LSTN–YSZ/STS

substrate. (a) Tape casting. (b) Lamination. (c) Fired substrate in H2 . (d) MEA deposition. (e)
Current collector deposition. (f ) Micro-SOFC. Source: Kim et al. 2016 [21]. Reproduced with
permission of Springer Nature.
and activation energy is around 1.0 eV. The first development of micro-SOFCs
(μSOFCs) using the thin film YSZ membranes of 50–150 nm thicknesses was
successfully fabricated using sputtering technology with the Pt electrode. The
device delivered 60 and 130 mW cm−2 at 350 and 400 ∘ C, respectively [19]. The
pinhole-free, composition-controllable, and conformable electrolyte membranes
were fabricated by ALD technology [20]; the device operational temperature
was further reduced to 265 ∘ C while maintaining sufficient performance. These
pioneering studies have in turn stimulated extensive research on nanofilms
for μSOFCs, both from fundamental and applied perspectives. Kim et al. [21]
reported some details on μSOFC fabrication by PLD (see Figure 1.4); achieving
decent performance, the peak power density was 235, 370, and 560 mW cm−2 at
450, 500, and 550 ∘ C. Figure 1.5 displays its microstructure with a cross-sectional
view of the dense YSZ around 1.5 nm in thickness.
With low temperature (LT) <600 ∘ C SOFC developments in addition to
reducing electrolyte resistance by thin film technologies, another critical issue
arises involving insufficient kinetic process and catalyst function leading to espe-
cially slower ORR for the cathode reaction and power output. This is actually
a limiting factor to determine the device performance and efficiency for low
temperature operations. To overcome the sluggish kinetics from the electrodes,
especially to minimize the cathodic polarization loss and enhance the ORR,
to enable the device sufficient efficiency and power output, most research and
development have been focused on new functional cathode materials together
with microstructure controlling in the device fabrications. Various effects on
the microstructure include the composition, particle and pore sizes and their
distributions, particle connections, porosity, tortuosity, specific surface area,
ionic and electronic conductivities, electrode thickness, and interfacial bonding,
which are noted for research and development of a new cathode material,
8 1 Introduction
Pt
LSC
500 nm
YSZ
1 μm
(c) Ni–YSZ
YSZ
(a)
Ni–YSZ
500 nm
(d) LSTN–YSZ
LSTN–YSZ
(b)
1 μm
(e)
Figure 1.5 Image of micro-SOFC. (a) Schematic of a thin film MEA supported on porous STS
substrate. (b) Photograph of a cell. A logo is a trademark of Pohang University of Science and
Technology (POSTECH) and is protected by copyright; it is used in this figure with permission.
Cross-sectional SEM image of (c) Pt/LSC/YSZ (Inset: magnified view of Pt/LSC), (d)
YSZ/Ni-YSZ/LSTN-YSZ, and (e) LSTN-YSZ contact layer. Source: Kim et al. 2016 [21]. Reproduced
with permission of Springer Nature.
especially below 600 ∘ C [22, 23]. Perovskite-structured oxides, ABO3 , as shown

in Figure 1.6, have been used successfully [24]. La(Mn/Co)O3 based on A-site
and B-site doping by rare earth, alkaline earth, and transition elements are
successful examples of high performance, more durable and comparable with
other SOFC device components.
A-cations are located in every hole, which is created by eight BO6 octahedra,
as shown in Figure 1.6, thus having a 12-fold coordinate site, and the B-cations
in 6-fold oxygen coordination. There are many ABO3 compounds for which
the ideal cubic structure is distorted to a lower symmetry (e.g. tetragonal,
orthorhombic, etc.). Oxygen vacancies can be created by ionic doping within
the perovskite structure, similar with fluorite structure. Ion doping effect
can create an impact on both electron and ion transport. One of the best
perovskite cathodes for low-temperature solid oxide fuel cells (LTSOFCs) is
Ba0.2 Sr0.8 Co0.6 Fe0.4 O3 [25]; its electronic and oxygen ionic conductivities at
600 ∘ C are 200 and 0.1 S cm−1 , respectively.
B
c
C
a b
(a) (b)
Figure 1.6 Perovskite structure oxides for functional LTSOFC cathode catalyst material. In
ABO3 , there are (a) corner-sharing (BO6 ) octahedra with A ions located in 12-coordinated
interstices and (b) B-site cation at the center of the cell. Source: Kan et al. 2016 [24].
Reproduced with permission of Royal Society of Chemistry.
Other types of perovskite structure oxides have been also developed for
LTSOFCs. A typical example is double perovskites, Sr2 FeMoO6 (SFM) [26],
because the unit cell is twice that of perovskite. It has the same architecture
of 12-coordinate A sites and 6-coordinate B sites, but two cations are ordered
on the B site. In the case of Sr2 FeMoO6 , the Fe and Mo atoms are ordered in
a 3D chessboard-type fashion. Also, the ratio between Fe and Mo can make a
significant effect on electrical and catalyst functions. Typically, Sr2 Fe1.5 Mo0.5 O6−𝛿
(SF1.5 M0.5 ) has been reported for remarkable electrical conductivity of 550 S cm−1
in air and 310 S cm−1 in hydrogen at 780 ∘ C, as one of the best redox stable
electrodes for LTSOFCs; this makes it available for both anode and cathode
materials in SOFCs. In the case of SFM0.5 as the anode and cathode to construct
a symmetrical SOFC, the device has achieved a peak power density of over
835 mW cm−2 at 900 ∘ C using H2 as fuel and ambient air as the oxidant [26].
The SFM shows also a good catalyst for oxidation of hydrocarbon fuel opera-
tion, e.g. direct oxidation methanol using the SFM0.5 as the anode and perovskite
and Ba0.5 Sr0.5 Co0.8 Fe0.2 O3 (BSCF) as the cathode based on perovskite ionic elec-
trolyte, La0.8 Sr0.2 Ga0.83 Mg0.17 O3 to construct the all perovskite SOFC device,
in a configuration of SF1.5 M0.5 /La0.8 Sr0.2 Ga0.83 Mg0.17 O3 (electrolyte)/BSCF. This
device obtained a maximum power density of 391 mW cm−2 at 800 ∘ C [27].
In addition to perovskite cathodes, other transition metal oxides are also effi-
cient for low temperature operations, typically nickel oxide, iron oxide, cobalt
oxide and their composites, or lithiated oxides, such as lithiated or Li compound
layer structure oxides, such as Lix M (M = Ni, Fe, Co)O2 . These oxides have shown
much effective catalyst functions due to its great proton conductivity, so far the
best of proton ceramic materials, 0.1 S cm−1 at 500 ∘ C [28], and other unique
advantages, e.g. triple charge carriers of H+ , O2− and e− as shown in Figures 1.7
and 1.8 [29, 30].
10 1 Introduction
H2
LixAl0.5Co0.5O2 LixHyAl0.5Co0.5O2
Figure 1.7 Layer structure reported having the highest proton conductivity 0.1 S cm−1 at
500 ∘ C. Source: Reproduced with permission from Lan and Tao [28]. Copyright 2014, John
Wiley & Sons.
O2(g) O2(g) O2(g)
O(ad) O(ad)
O2(ad) O2(ad) O2(ad) Pure e– conductor
O(ad) e– e– Pure H+ conductor
O(ad) O(ad)
e– O2– O2–
H2O(g) H2O(g) H+ H2O(g) Mixed O2–/e– conductor
H+ H+ H+ H2O evolution point at triple
(a) (b) O2(g)
phase boundary (TPB)
O(ad)
O2(g) O2(ad)
O(ad) H2O(g) e–
O2(ad) H2O(g)
O2–
H2O(g) e–
H+
O(ad) Mixed H+/e– conductor
e- O(ad)
e–
H2O(g) H2O(g) H2O(g) Ternary H+/O2–/e– conductor
H+ H+
H2O evolution point and line
at double phase boundary
(c) (d)
(DPB)
Figure 1.8 Triple charge transfer in LTSOFC cathode and schematic illustrations of the oxygen
reduction and water generation pathways in various cathodes: (a) pure electronic conductor;
(b) mixed O2− /e− conductor (mixed electronic and ionic conductor [MIEC], left) and MIEC
composited with H+ conducting oxide (right); (c) mixed H+ and e conductor (mixed proton
and electron conductor [MPEC]) and (d) triple-conducting (H+ /O2− /e− ) oxides. Source:
Reproduced with permission from Fan and Su [29]. Copyright 2016, Elsevier.
Figure 1.8 displays the layer structure of LiNi0.8 Co0.2 O2 with a triple
(H+ /O2− /e− ) conducting catalyst material. The triple charge conducting material
can speed up the cathodic ORR process, to reduce significantly the cathodic
polarization, thus enhancing the device performance.
1.3 New Electrolyte Developments on LTSOFC

As proposed by Goodenough, new materials need to be developed to replace
YSZ [19] to make SOFC operational at low enough temperatures. This means
Temperature (°C)
1200 1000 800 600
0.0
La
0.8 Sr
0.2 Ga
0.8 Mg (Bi O
–0.5 0.2 O B
3 aTh 2
2 )0.7 (Y
2O )
5
0.9 Gd
0.1 O 3 0.2
5
3
–1.0
Logσ (S cm–1)
(Ceo
(Zro ) (G
2 0.8
(Zr ) (S d 2 O)
La o) 2 0.9
c 3 0
2O )
.2
–1.5 0.
7 Ca
2
0.8
7 (Ca 3 0 .1
O)
0.
7 AI 0.1 (Zr
O 3
o)
–2.0 2.
8 2
0.9 (Y
2 O)
3
0.1
–2.5
–3.0
0.6 0.7 0.8 0.9 1.0 1.1 1.2
3 T–1(K–1)
10
Figure 1.9 Temperature dependence of conductivities for various oxide electrolytes from
High-Temperature Solid Oxide Fuel Cells: Fundamentals, Design, and Applications by S.C. Singhal
and K. Kendall (Eds.). Publisher: Elsevier Science (2004). Source: Reproduced with permission
from Singhal and Kendall [31]. Copyright 2003, Elsevier.
that alternative electrolytes should be designed for low temperatures; commonly

accepted temperature is below 600 ∘ C for LTSOFC. Therefore, new electrolyte
materials should reach an ionic conductivity of 0.1 S cm−1 < 600 ∘ C. Following
this direction, worldwide LTSOFC movement has been conducted to look for
new electrolyte materials. However, no alternative to be good enough to compete
with YSZ on overall requests has not yet been found. Figure 1.9 displays some of
the new electrolyte materials developed in this line.
It can be seen from Figure 1.9 that almost no alternative oxide electrolyte mate-
rials can reach 0.1 S cm−1 below 600 ∘ C. Though Bi2 O2 –Y2 O3 is used at this level,
it could not be used for SOFCs due to its direct reduction to Bi metal in fuel cell
operation, thus the loss of the ionic conduction. Another approach to develop
new electrolyte materials based on surface and interfacial ionic conduction is
also published in Nature in the same year of Goodenough’ structural doping [32].
To obtain the interfacial high ionic conductivity, nano and composite, so-called
nanocomposite, approach has been demonstrated to be more effective. A very
successful case may be exampled by ceria-based two-phase composite materials
[33–36]. Such materials have been found very functional for LTSOFCs between
300 and 600 ∘ C. Figure 1.10 presents a schematic drawing for such a methodology.
Figure 1.10 Combining nano and

composite approach to develop effective Nano Composite
new functional electrolyte materials for
LTSOFC.
Nanocomposite
12 1 Introduction
On one hand, nanotechnology can create high surface area and active sites
with defects for high ionic transportation thus to enhance the ionic conductivity;
on the other hand, the composite approach can enhance the nanomaterial
stability and further enhance the ionic conduction by the interfacial mechanism.
Therefore, the nanocomposite approach can be very effective to develop high
ionic conductors for LTSOFC electrolyte demands. Ceria has a stable fluorite
structure as YSZ by Ce to replace Zr with a wider range of dopants than that
in zirconia. Using rare earth element doping, e.g. samarium, gadolinium, and
yttrium, doped CeO2 have high expectation to replace YSZ because its O2−
conductivity can reach the same level, 0.1 S cm−1 at 800 ∘ C, i.e. 200 ∘ C lower
than that of YSZ. However, except good ionic conductivity at a lower temper-
ature, many other aspects are not as good as with YSZ. For example, in fuel
cell-reduced atmosphere, Ce4+ can be reduced to Ce3+ , which results in direct
electronic conduction and short-circuiting problem and thus in a significant loss
in device voltage and power output; with Ce4+ to Ce3+ reduction, the big atom
volume change causes microcracking and leads to gas leakage and finally the
device invalid during the fuel cell operation. Even more, 0.1 S cm−1 can occur
only at 800 ∘ C, still not sufficient for LT (<600 ∘ C). These challenges have made
ceria itself not yet successful for the alternative electrolyte and SOFC tech-
nologies. To realize ceria-based electrolytes, a more effective way is to develop
ceria-based composite electrolytes [36] as illustrated in Figure 1.10, which have
been extensively investigated and demonstrated by excellent performances for
SOFCs at LTs. Among various ceria-based composite materials, ceria–carbonate
two-phase composites have been most widely investigated as new electrolytes
with successful applications in LT, 300–600 ∘ C SOFCs [33–37]. Hybrid proton
and oxygen ionic conduction and even triple ions (H+ /O2− /CO=3 ) transport
processes have been studied and reported with excellent fuel cell performances
[36, 38–41].
Figures 1.11 and 1.12 present hybrid and triple ion transport fuel cell devices
based on ceria–carbonate composite electrolytes.
O2–
H+
Figure 1.11 Hybrid H+ /O2− conduction in the ceria-based composite electrolyte. Source: Zhu
2006 [36]. http://www.electrochemsci.org/ESG.htm. Licensed Under CC BY 4.0.
Anode Electrolyte Cathode
O2–
SDC
O2
H+
H2
CO32– CO2
Molten carbonate
Figure 1.12 Triple ion transport mechanism in the ceria–carbonate composite electrolyte.
Source: Reproduced with permission from Xia et al. [39]. Copyright 2009, Elsevier.
The O2− conduction in ceria phase is determined by the oxygen ion vacancies
(a mechanism) in the ceria lattice; H+ conduction may be produced by
the formation of bonding with the carbonate through temporal bonding,
H+ –CO3 = (HCO−3 ) mechanism. Both H+ and O2− conduction can be integrated
into one composite to enhance the system conductivity based on the composite
effect. This effect concerns the ion conduction at interfaces, or interfacial
conduction, as the key. Figure 1.11 presents a schematic for such hybrid proton
and oxygen ion conduction model and depicts also the hybrid/dual H+ /O2−
conduction routes and the conducting chain: H⋅⋅⋅O–H, H–O–H and O–H⋅⋅⋅O
atoms/ions. This refers to an interfacial conducting path/mechanism for the H+
(marked by two small bolls/dots in Figure 1.11) and O2− (larger boll).
In Figure 1.12, a triple ion transport mechanism has been proposed by Xia et al.
[39]. They introduced some CO2 in the ceria–carbonate electrolyte fuel cell and
operated above the carbonate melting point, achieving 1700 mW cm−2 at 650 ∘ C,
the best performance of the ceria–carbonate electrolyte fuel cells. They proposed
triple-charge transport mechanism to interpret such excellent performance, pre-
sented in Figure 1.12.
Because H+ and O2− ions are fuel cell source ions, hybrid H+ /O2− conduction
can enhance the device charge carrier concentration resulting in higher current
and thus power outputs. 1150 mW cm−2 has been achieved at 490 ∘ C [42], while
in triple ionic process, by adding one more source ion of CO2= 3 , the fuel cell
device reached 1700 mW cm−2 at 650 ∘ C. More interestingly, the ceria–carbonate
fuel cell can be developed in various electrochemical operation modes as SOFC,
MCFC, or joint SOFC/MCFC [43].
Successful hybrid ionic conducting composite electrolyte materials for
LTSOFCs may also be highlighted by heterostructure, which can be prepared by
directly using proton and oxide ion-conducting oxides in the composite. Zhu and
Schober first presented such a hybrid system based on BZY (BaZr0.8 Y0.2 O3−d )
proton-conducting perovskite with samarium-doped ceria (SDC), a fluorite
structure with oxide ion conductor composite. This novel composite system com-
posed of the proton and oxide ion-conducting oxides successfully demonstrated
14 1 Introduction
a fuel cell device reaching 250 mW cm−2 at 550 ∘ C [44]. Following this route,
high sintering temperature at 1550 ∘ C was employed for BZY/SDC composite
system, which produced a new perovskite phase of BaCe1.6 Y0.2 Gd0.2 O4.9 (BCYG)
between SDC and BZY phases. As reported such a new phase, BCYG displayed
ionic conductivity higher than that of constituent BZY and SDC materials.
This new composite system was applied as the electrolyte for the fuel cell to
achieve 657 W cm−2 at 700 ∘ C [45]. This system suggests that the BZY–SDC
two-phase composite may be transferred to three-phase by high temperature
heat treatment, while the intermediate phase formed between two constituent
phases still dominated the ionic conductivity and transport in such composite
material. But the ionic transport mechanism is not very clear to demand further
investigation. For example, either H+ or O2− or both may be transported in
this newly formed BCYG phase. The basic phenomenon still belongs to ionic
transport in the composite and heterostructure materials.
Two phases based on proton and oxide ion-conducting oxides may make
several ways for ionic transportation, H+ and O2− transport individually in
respective proton and oxide ion phases, and more significantly, superionic
conduction through interfaces between two constituent materials as ionic
highways, as shown in Figure 1.13.
In order to develop alternative YSZ electrolyte materials with sufficient ionic
(H+ , O2− or hybrid) conductivities, say, 0.1 S cm−1 , the nanocomposite presented
another powerful way by designing interfaces and interfacial superionic conduc-
tion between two phases of the heterostructure composite. Such an approach
called multifunctional nanocomposite for advanced fuel cells (nanocompos-
ites for advanced fuel cells [NANOCOFC], www.nanocofc.com) focusing on
advanced material and functionalities design on interfaces; see Figure 1.14. In
such composite structure, two constituent phases may have moderate ionic
conductivity, or more often with one insulating phase, e.g. an insulating oxide;
O2–
conduction
H+
conduction
Superionic
conduction
Figure 1.13 Proton, oxide ion paths in respective proton and oxide ion conducting phase and
interfacial ionic highways.
700 600 500 400 300 200
0.1
Interface
0.01
σ (cm–1)
PII
1E-3
PI
1E-4
1E-5
Superionic transition
1.0 1.2 1.4 1.6 1.8 2.0

1000/T (K–1)
Figure 1.14 Superionic transition at two constituent phases’ interfaces in the composite
materials.
a much high ionic conductivity with a great enhancement compared to the

constituent phase can be produced between the two-phase contacting regions,
i.e. interfaces. This is so-called interfacial superionic conductivity. It should be
pointed out that such conduction mechanism does not involve any material
structural changes, but only changes in the interface due to microstructures and
interactions between two phases.
A theoretical calculation has been carried out between ceria and carbonate
composite electrolyte indicating the existence of the interfacial ionic highways. A
model presented in Figure 1.15 based on coulombic interaction points out there
are very low activation energies for ionic transport, 0.2 eV for O2− and 0.1 eV for
H+ transport, respectively [46].
According to the Arrhenius relation, 𝜎 = 𝜎 0 exp(−𝜀a /kT), the interfacial ionic
transport design is very favorable to develop superionic conductors because the
interfacial mechanism is favorable by optimizing all parameters to promote high
ionic conductivity from the following aspects:
(i) High mobile ion concentration, n (𝜎 0 ). It is directly proportional to the ionic

conductivity value level, while at interface or particle surfaces, high defects
can be created without structural factor limitations. But in structural doping
approach, it is often a limiting factor, e.g. only 8% yttrium allowed to stabilize
cubic fluorite structure, YSZ within zirconia.
(ii) Low activation energy, 𝜀a . The ionic migration activation energy is more
effective to determine conductivity due to ionic conductivity dependence
being a reciprocally exponential function. Interfacial paths have no strong
bond energy to break in order to activate ion mobile, thus requiring much
lower activation energy compared that of the ion mobility in the structure.
16 1 Introduction
M2C Ce
O–
Ce CeO2
bulk
CeO2 CeO2
Ceria bulk bulk
M
O
Carbonate
+ + +
M (Li , Na ) O– O2– CO32–
(a) (b)
Figure 1.15 Interfacial superionic (H+ and O2− ) conducting paths in ceria–carbonate
composite electrolyte. (a) Interactions and potential between the oxygen ions on the ceria
particle and M+ (Li+ , Na+ , or K+ ) cations of the carbonate, and electrical field in the interfaces
between two constituent phase particles. (b) The oxygen ions on the ceria particles and
interactions with cations of the carbonates may essentially consist of conducting
highways/paths at interfaces of the two-phase materials, resulting in interfacial superionic
conduction. Source: Reproduced with permission from Zhu et al. [46]. Copyright 2008, Elsevier.
(iii) Long ionic transport path, L (𝜎 0 ). This effect is again proportional to

conductivity. While ions transport at interfaces, one-step jump distance
is from particle to particle through surface defects. Such jumping step
length is in nanometer level for nanocomposites or even longer. But in
structure design, defects are created within the structure unit cell, which
is in angstrom level, i.e. ions jumping steps between lattice units from
cell to cell in angstrom level, even less, because based on Einstein–Nernst
equation, 1/6 probability is allowed for directional mobility driven by an
external electrical field. In this case, interfacial conduction has no such
limit because three-dimensional interfaces can be constructed on particles,
which can adjust transport paths directed by the driven field.
From the above analyses, we can see the more advanced material design on
interfacial superionic conductivity with all optimized parameters indicated by
Arrhenius relation than that of the ion-doped structural design. Such interfa-
cial approach has demonstrated a great ionic conductivity, 0.1 S cm−1 at 300 ∘ C,
first reported by Wang et al. in a ceria–sodium carbonate core–shell structure
composite; see Figure 1.16 [47].
Wang et al. proposed the “Swing” model to describe proton pathway and
transport process; see Figure 1.17 for the SDC/Na2 CO3 composite system. This
is essentially an interfacial conduction mechanism. Proton can transport in the
carbonate–SDC contact region, i.e. interface, through CO=3 anion bonding to
form temporal HCO−3 , which can be transferred through one carbonate anion to
another.
The interfacial ionic conduction mechanisms have been further investigated
by Shalima and Gulgun [48], who proposed the interfacial ion transport model
shown in Figure 1.18. Core–shell structured SDC particles are connected by car-
bonate networks.
(a) (b)
600 550 500 450 400 350 300 250 200 150 °C
1
0.1
0.01
S (S cm–1)
1E–3
1E–4
1E–5
1E–6
1.2 1.4 1.6 1.8 2.0 2.2 2.4
(c) 1000/T (K–1)
Figure 1.16 Superionic phase transition below 300 ∘ C in core–shell structure of Na2 CO3 –SDC
composite. (a) TEM image and (b) HRTEM image of as-prepared SDC/Na2 CO3 nanocomposite;
(c) temperature dependence of conductivities for as-prepared core–shell SDC/Na2 CO3
nanocomposite inserted by a DSC curve of as-prepared SDC/Na2 CO3 sample. Source:
Reproduced with permission from Wang et al. [47]. Copyright 2008, Elsevier.
This composite approach was further extended to optimize hybrid

ionic–electronic conductivity in two-phase ceria–zirconia composite with
cobalt oxide and Na2 CO3 as suitable additives [50]. Interfacial O2− conduction
was proposed through carbonate intermediate layer between YSZ particles as
shown in Figure 1.19.
Moreover, the heterostructure composite approach has been also applied to
include semiconductor with ceria ionic conductor, e.g. a p-type LiZnO2 semi-
conductor, and reduced ceria as an n-type when in the fuel cell or hydrogen
environment. In this case, a redox reaction can take place between p-LiZnO2 and
n-reduced ceria, as shown in Figure 1.20: i.e. an electron combination process
may occur. The electrons can be transferred from n-ceria particle to p-LiZnO2 ,
resulting in the absence of net electrons to cause electronic conduction within
18 1 Introduction
H+ concentration gradient
H+ O2– Ce4+ C4+ Na+ Hydrogen bond
Figure 1.17 Swing model to describe proton transport through carbonate and ceria interface
from Xiaodi Wang, PhD thesis, KTH. Source: Reproduced with copyright permission.
Figure 1.18 Ceria-carbonate

nanocomposite transport
model. Source: Reproduced
with permission from Wang
SDC et al. [49]. Copyright 2011,
Elsevier.
SDC
SDC
this novel n–p semiconductor–ionic heterostructure. This provides a useful and

novel methodology of electrolytes–nanocomposites for net electron free through
extracting e-conduction by the n–p heterostructure to develop superionic con-
ductors.
In parallel, there have been strong research activities on semiconductor–ionic
heterostructure composites, e.g. semiconductor SrTiO3 (STO) with a fluorite
structure such as in YSZ ionic electrolyte. Several orders of the magnitude for
ionic conductivity enhancement were discovered for such semiconductor–ionic
heterostructure nanocomposite [53]. This has been debated. For example, X.
Guo in a comment on “Colossal ionic conductivity at interfaces of epitaxial
ZrO2 :Y2 O3 /SrTiO3 heterostructures” [54] argued that the observed great
conductivity actually came from the SrTiO3 electronic conduction.
+ +
O
2– Na Na + 2–
Na O
(i)
2– +
O Na
CO2
Na2O Na2CO3
8YSZ
8YSZ
(ii) (iii)
Na2CO3 Na2O
+ 2–
Na O
+
O2– Na (iv)
+ 2–
2– Na O
O + +
Na Na
8YSZ 3TDC
(a) (b)
Figure 1.19 Interfacial ionic conduction is presented in YSZ–carbonate composite system.

(a) Two material particles for 3YSZ and 8YSZ in the composite. (b) Schematic representation of
overall O2 conduction in composites. Solid green lines show the oxygen transporting paths
and red dots represent the electron transporting path. (c) Schematic diagram representing the
oxide ion conduction via hopping through Na+ ions in percolation layer. Source: Reproduced
with permission from Maheshwari and Wiemhöfer [51]. Copyright 2016, Elsevier.
Figure 1.20 Semiconductors Combination e–

n–p heterostructure h Charge transfer
LiZn oxide H2
extraction e-conduction.
second phase
Source: Fan et al. 2014 [52].
Adapted with permission of Ce4+ Ce3+
Royal Society of Chemistry.
Ce
Ceria
Though there is a big debate that it does not affect this new discovery with
a great significance: i.e. interfaces play the key role in ionic conduction in such
ion/semiconductor ZrO2 :Y2 O3 /SrTiO3 heterostructure composite. It has been
highly expected for YSZ/SrTiO3 heterostructure composite as a breakthrough in
the electrolyte research and development with “a profound effect on use in oxide
ion conductors for SOFCs leading to exciting new technologies” [55]. However,
the YSZ/STO has not yet been used as an alternative electrolyte to replace YSZ
though a great ionic conductivity enhancement was indeed observed than that
of YSZ. It may be due to the existence of electronic conduction from the semi-
conductor STO and electronic conduction could not be avoided as commented
by Guo. According to fuel cell science, the electrolyte should have pure ionic
20 1 Introduction
transport, any electronic conduction may cause significant losses in the device
voltage and power.
1.4 Beyond the State of the Art: The Electrolyte-Free

Fuel Cell (EFFC)
SOFC electrolytes have been developed for a long time, some alternatives have
emerged, but still the original YSZ material dominates commercial development
of SOFC. A well-justified question is if a SOFC could be realized by an alternative
way. A commonly chosen approach has been to reduce the electrolyte thickness.
Another intriguing approach may be to eliminate the traditional electrolyte
and replace it with something more innovative. The single-component/layer
fuel cells or the electrolyte-free fuel cell (EFFC) may be an example of such
development demonstrated for the first time in 2011. Zhu et al. made the first
single-component EFFC invention [56–59] shown in Figure 1.21.
This development is the major focus of Part II of this book. Recently, many pub-
lications have supported the single-component fuel cell devices using semicon-
ductors of perovskite or layer-structured transition metal oxides as the functional
layer in a single layer fuel cell configuration. The fuel cell functionality is realized
through novel semiconductor ionic materials (SIMs).
A joint effort involving 15 organizations including industries from Europe
and Asia has been initiated [60]. LiCoAlO2 [28], SmNiO3 [61], and LaSrCaTiO3
[62] semiconductor materials undergo a protonic conducting phase transition
under fuel cell operation and perform as good as a conventional electrolyte.
Being different from the conventional electrolyte design by ion substitution to
create oxygen vacancies or defects, new properties arise from strong correlations
Electron
flow
Electrolyte-free
Load
Electrolyte
Anode Cathode
zone zone
Figure 1.21 From electrolyte based on electrolyte layer-free fuel cell device.
between electron and electron or electron band and ion. To develop ionic
properties through semiconductors has effectively extended the electrolyte and
electrode material selections for advanced LTSOFCs and certainly explored
the new fundamental understanding of research and development on fuel cell
materials and technologies.
Based on extensive research and development in this single-component/layer
or EFFCs, new functional materials have been discovered based on the
semiconductor or semiconductor–ionic properties. Semiconductors and
semiconductor–ionic heterostructure materials could play an important role
in advanced LTSOFCs as well as in realizing the device functions. Three cate-
gories of the semiconductor–ionic materials may be identified: (i) single-phase
semiconductors, e.g. perovskite and layered structured oxides, SmNiO3 , SrTiO3,
and LiCoAlO2 , LiNiFeO2 , LiNiCoO2, etc (ii) semiconductor–ionic two phase
composite materials (iii) insulating type wide bandgap semiconductors. More
semiconductor oxides, e.g. ZnO, have been also discovered very lately to be
transformed to semiconductor–ionic functions. In transition metal semiconduc-
tor oxides, strong electron correlations can induce some special properties, e.g.
metal–insulation transition, i.e. Mott transition materials. SmNiO3 perovskite
is a typical example of such correlated transition of electrical conduction. Zhou
et al. [61] prepared a thin film of metal conducting SmNiO3 (SNO) with an initial
electrical conductivity of 1000 S cm−1 , which can be applied as an electrolyte
in LTSOFCs below 500 ∘ C (Figure 1.22). They prepared an SOFC device based
on 1.5 μm thick SNO electrolyte. With Pt electrodes, this device delivered
an open-circuit voltage (OCV) of 1.03 V and a maximum power density of
225 mW cm−2 at 500 ∘ C (Figure 1.22d). They proposed a high proton-conducting
H-SNO material transformed from SNO in fuel cell operation, thus resulting in
good fuel cell performance. They also found the low ionic activation energy, Ea
for the H-SNO compared to the other best O2− and H+ conducting electrolytes,
as shown in Figure 1.22e.
The transition from the electronic conductor to extrinsic proton/ionic con-
ductor, which is also reported in other works [28, 52, 61, 63] to be promising
electrolyte materials for LT-SOFCs. These semiconductors have shown a
common property: i.e. in fuel cell operations they can experience a transi-
tion from semiconductor electronics to ionic conduction. Most commonly,
semiconductor–ionic materials are developed based on two-phase materials
consisting of one semiconductor and one ionic material, so-called semiconduc-
tor and ionic heterostructure composites. In this case, both electron and ionic
conduction may coexist in the material. Interestingly, such mixed electronic
and ionic conduction materials can replace the electrolyte to build the fuel cell
devices, so-called semiconductor–ionic membrane fuel cells (SIMFCs) [64, 65].
Though significant electronic conduction, which is often comparable to or
higher than that of the ionic one, exists in SIMFCs, no short-circuiting nor
power output loss was observed. These phenomena are obviously conflicted
with conventional SOFC science and technology. Therefore, Part II deals with
this especially unusual topic.
22 1 Introduction
(a) Electron itinerant (b) Electron localized
eg U eg
Electron doping
Mott transition
t2g t2g
Ni3+ Ni2+
(c) SNO H-SNO
H2
Pt
Anode
e–
O
H-SNO TPB H
Elecrolyte
SNO
+
H
e–
Cathode e–
O2 H2O
(d) (e) Temperature (°C)

550 500 450 400 350 300
250
Highly textured
Power density (mW cm–2)
1.0 Epitaxial H-SNO

–2 BZY film
Cell 1 200
0.8
logσ (S cm–1)
Voltage (V)
150 –3 Pt/H-SNO/Pt
0.6
0.4 Cell 2 100

BZY
–4 GDC
0.2 50
Cell 3 LSGM
YSZ
0 0 –5
0 400 800 1200 1600 1.2 1.4 1.6 1.8
Current density (mA cm–2)
1000/T (K–1)
Figure 1.22 (a, b) Mott transition makes highly electronic conductive SmNiO3 (SNO) to
insulator; (c) In situ fuel cell operation makes hydrogenation of the SNO to proton-conducting
electrolyte H-SNO; (d) the fuel cell performance; (e) proton conductivity of H-SNO compared
to other existing proton conductors, showing excellence. Source: Reproduced with permission
from Zhou et al. [61]. Copyright 2016, Springer Nature.
1.4.1 Fundamental Issues

In the long history of the fuel cell, fundamental understanding and scientific prin-
ciples play an important role in research and development. In the first inventions,
Grove had speculated that the action occurred in his gas battery at the point
of contact between electrode, gas, and electrolyte, but hard to be experimen-
tally proved due to experimental constraints. Later, researchers’ work on physical
properties and chemical reactions solved the puzzle of Grove’s gas battery. Any-
way, his exploration of the underlying chemistry of fuel cells laid the groundwork
for later fuel cell researchers and science fundamentals. As a fact, argument and
debate may be more important than the actual processing details. The gas battery
invented by Grove in the nineteenth century spurred research and the testing
of theories. While the understanding of the basic science improved, no practi-
cal device emerged despite several attempts. Work on the science of fuel cells
continues, but today’s work is more about developing better materials, concrete
technique details with engineering, and more efficient designs, rather than dis-
covering the basic laws and principles of science. With greater understanding of
fuel cell science came attempts to make practical fuel cells. After such a long his-
tory of the fuel cell since 1839, does this mean that we do fully understand the fuel
cell science and that the scope of improvements is limited? The answer to this is
that there is still a need for improvements and we are not yet in line with the devel-
opment work [66]. There is still a need for strong fundamental research in SOFC,
especially, when shifting to lower temperatures <600 ∘ C, and a new fundamental
issue arise to overcome the sluggish electrode reaction at these temperatures.
Typically, cathode ORR process is a determining factor to develop high perfor-
mance at low temperatures. Tailoring microstructures can significantly improve
the SOFC cathodic performance, thus device power output [67]; this involves
improvement of electron and ion pathways and triple-phase boundaries (TPB)
and speed up the ORR dynamic process. The TPB is important because it is
where electrons, ions, and reactants meet and electrochemical reactions occur.
It is very similar to that suggested by Grove in his gas battery (fuel cell) that the
action occurred at the point of contact between electrode, gas, and electrolyte.
Figure 1.23 displays tailoring of the cathodic microstructure by introduction of
O2 O2 O2 O2 O2
O2 O2 O2 O2 O2
OO TPB
Cu-enhanced Interfacial
(oxygen
TPB O transfer
Cu Oads Oads vacancy)
LSCF-50GDC O
2– O2– O2–
Cu
Figure 1.23 Loading suitable metal (Cu) promoter can enhance TPB and surface oxygen
vacancies and enhance more oxygen paths ways to enter the cathode, thus improving the
ORR process and enhancing the device performance. Source: Guo et al. 2015 [68].
https://www.mdpi.com/2073-4344/5/1/366. Licensed under CC BY 4.0.
24 1 Introduction
low-cost transition metal promoters, e.g. Cu, Ni, and Co. But the mechanism
of metal promotion has not been fully understood, so both positive and nega-
tive promotion factors exist in literature. The loading level of transitional metal
oxides has an optimum above which the interfacial oxygen transfer can be nega-
tively influenced as the promoting nanoparticles start to obstruct the interaction
sites of interfacial O with the cathode surface oxygen vacancies [68, 69].
A suitable loading of metal Cu can promote the interfacial oxygen transfer,
which also enhanced TPB sites to increase O2− entering the cathode and thus
speed up the ORR and fuel cell performance. Otherwise, overloading or insuffi-
cient loading of Cu promoter can all make a negative effect on the device perfor-
mance.
To further improve device performance to overcome critical polarization
losses at the electrode side of the electrode/electrolyte interface, online redox
electrode process was also proposed. Online redox process takes advantage
from reduced nanometal particles, typically, Ni from nickel oxide electrodes.
The fresh nanoparticles formed from the fuel cell on-site operation can possess
high catalyst function, to speed up electrode redox reactions, HOR, and ORR in
anode and cathode, thus significantly enhancing the fuel cell performance.
In addition, to explore SOFC multi-fuel advantage, development of
redox-stable anode and cathode materials and new reaction mechanism is
another important issue for multi-fuel operation and long durability of SOFCs
in addition to the microstructure tailoring properties. Tao and Irvine [70] first
reported redox-stable perovskite oxide, La0.75 Sr0.25 Cr0.5 Mn0.5 O3 , used for SOFC
anode achieved comparable performance compared to conventional Ni–YSZ
anode. In this case, it can overcome the SOFC Ni–YSZ anode instability to
affect long durability problem in the steam environment because the SOFC
operation produced water in the anode side. A new approach toward the SOFC
configuration can be achieved with the use of amphoteric semiconductor oxides,
where the same oxide will simultaneously serve the function of the cathode and
anode (Figure 1.24). The latter approach is widely termed symmetrical solid
oxide fuel cell (SSOFC). Some redox-stable oxides, La0.75 Sr0.25 Cr0.5 Mn0.5 O3 d
(LSCM) [71, 72], (La,Sr)(Ti1−x Fex) O3−d [73], and Sr2 Fe1.5 Mo0.5 O6−d [26], have
been reported. In this case, no anode and cathode layers were constructed
Fuel/H2 +
Electrolyte O2– O2– O2– O2–
–
Oxidant/air
Figure 1.24 The SOFC device constructed by the same electrode materials named as
symmetrical SOFC (SSOFC).
physically by materials, but the side supplied by fuel (e.g. H2 ) or oxidant (air)
determines the anode or cathode functions.
Moving to the EFFC involves science beyond very much the existing fuel
cell technologies. In recent years, physical exploration of the underlying elec-
trochemistry of EFFCs has become a fundamental field in fuel cells. The new
scientific principles and fundamentals of EFFC are gradually established through
the physics of semiconductors, energy bands, and semiconductor junction
device technologies. The EFFC represent a disruptive fuel cell technology, which
differs from the incumbent fuel cell thinking, which sometimes causes criticism
toward this new technology. In this book, we shed new light on understanding
the electrolyte-free or non-electrolyte technologies.
Traditional fuel cells are built around three basic components, anode, elec-
trolyte and cathode, in which the electrolyte plays a key role for ionic transport
and separating electrodes to block the electrons passing through the electrolyte,
thus preventing the fuel cell of short-circuiting. A common doubt with EFFC or
single-layer device is that it may be electronically short-circuited. Also, a device
without a separate ionic electrolyte layer must possess a lower OCV and lower
power output compared to a fuel cell with an electrolyte. In this book, we pro-
vide evidence and background understanding that EFFC can actually reach high
OCVs and enhanced power output.
The fuel cell technology is, however, still subject to material and technology
challenges accompanied by high costs. New material systems with very much
enhanced ionic conductivity than those from the ionic designed system, e.g. YSZ
and SDC, has been proposed combining ionic and semiconducting materials or
semiconductors as in EFFC or deficit oxygen-defect oxides, which may achieve
high power density already at temperatures well below 600 ∘ C, thus easing
the materials and device problems. To assist and promote the SOFC solutions
on challenges and commercialization, we contribute this book to give a new
solution to combine the conventional SOFC technological and engineering
excellence and its great advantages with new functions of the materials and
devices/technologies, to speed up SOFC commercialization in a new path
through.
1.5 Beyond the SOFC

The fuel cell development has a long history starting from the fuel cell inven-
tion in 1838. The base material of SOFC, YSZ, was discovered over 100 years
ago. Though many lessons can be learned from this arch of development, this
book intends to provide different ideas and new solutions beyond the existing
knowledge and raise a fundamental question: are there other ways to realize the
fuel cell or even not having to be the fuel cell as long as that device can realize
the fuel-to-electricity conversion? Could we learn from other fields of science
to bring new thinking into fuel cells? For example, the solar cell field is expe-
riencing a highly interesting phase of development from physical p–n junction
devices to electrochemical dye-sensitized and perovskite solar cells, which may
complement the traditional semiconductor p–n junction-based silicon solar cell
26 1 Introduction
e– Figure 1.25 A fuel cell generates

H2 A O2 electricity from the chemical energy
of H2 and O2 and a
photoelectrochemical cell produce
H2 and O2 from solar radiation.
H+
H2 O2
MSx e MOx
H+
3
Photons Reduction
– Reduction
CB
e–
2
e–
hv ≥ Ebg
3
2 h+
+ VB
Oxidation h+
Oxidation
SC A SC B
(a) (c)
H2
e–
e–
e–
e–
H2O
H+
H+
O2– H2 O2(Air)
O2
O2–
e– H 2O H2O
e–
(b) (d)
Current collector
Figure 1.26 (a, c) For photoelectrolysis realized by semiconductor band designs and the
efficiency by band structure and alignment; (b) single component electrolyte-free fuel cell
(EFFC) and (d) double layer EFFC devices, which are driven by the similar semiconductor
principles to be described in Part II. Source: (b) Zhu et al. 2011 [57]. Reproduced with
permission of Elsevier. (d) Zhu et al. 2011 [74]. Reproduced with permission of Royal Society of
Chemistry.
Energy
Energy
Energy
Mn3+/4+:eg Mn3+/4+:eg Mn3+/4+:eg
Co:eg Co:eg Co:eg
Mn:t2g Mn:t2g Mn:t2g
EF1
Ni2+/3+:eg EF2 Ni2+/3+:eg Ni2+/3+:eg
Ni3+/4+:eg Ni3+/4+:eg Ni3+/4+:eg
EF3
Co3+/4+:t2g Co3+/4+:t2g Co3+/4+:t2g
Ni:t2g Ni:t2g Ni:t2g
O2–:2p6 O2–:2p6 O2–:2p6
N(E) N(E) N(E)

Discharge state Half discharge Charge state
(a) x(Li) = 1.0 (b) x(Li) = 0.5 (c) x(Li) = 0.0
Figure 1.27 The energy vs. density of states showing the relative Fermi level of the Ni4+ /3+
and Co4+ /3+ redox couples for Lix Niy MnyCo1−2y O2 during the charge, for three states of charge
determined by the Li concentration x: (a) x = 1; (b) x = 0.5; (c) x = 0. Source: Julien et al. 2014
[77]. https://www.mdpi.com/2304-6740/2/1/132. Licensed Under CC BY 4.0.
e– e–
Electrolyte
Cu Al
Li
(𝜇)A –𝜇C
VOC =
e
Li
Anode Cathode
(graphite) Separator (LiCoO2)
(a)
Energy
LUMO
EF (Li) E E
Voltage window
EF LUMO EF(Li)
3+/ 4+ EMF
Co Co Li: 2s
Co: 3d
HOMO EF
LiCoO2 HOMO
N(E) O:2p N(E)
O2–:2p6
(b) (c) Anode Electrolyte Cathode

Density of states N(ε )
Figure 1.28 (a) Semiconductor band structure vs. lithium battery electrochemical cell
electromotive forces (EMFs). Li battery electrochemical cell. (b) Described from semiconductor
energy band structures. (c) Band energy and Li battery electrochemical EMFs. Source:
Reproduced with permission from Liu et al. [76]. Copyright 2016, Elsevier.
28 1 Introduction
in the future. Another example may be photoelectrolysis or splitting water with

photons, which were developed around the photoelectrochemical cell in the past,
but today photoelectrolysis using semiconductors and band structures can be
realized. Such new developments may also help fuel cells further (Figure 1.25),
where similarity is shown between the fuel cell and the photoelectrochemical
cells. Both are electrochemical cells. But today photoelectrolysis, semiconductor
heterostructure materials are employed, in which energy band and semiconduct-
ing physics play an important role as shown in Figure 1.26. The basic mecha-
nism and process of photocatalysis are focused on two strategies: (i) energy band
modification to broaden the light absorption and (ii) surface modification (sur-
face sensitization, semiconductor combinations, and noble metal deposition) to
increase the lifetime of the carrier. All in all, the suitable band structure is the
key for visible light harvesting and effective separation of the carrier of semicon-
ductor photocatalyst. In the same way, in novel EFFCs or SLFCs, what we need
is the same on charge creation, separation, transport, and reaction (“closing the
circuit”), which also requires suitable band alignment. Key charges are h+ /e− on
electrodes and H+ as charge transporter. The same principle is also in EFFC.
Another good example from electrochemistry to employ very much today
semiconductor band and physics is lithium battery field, which has made this
field growing with a new hot area. Electrochemical performance and material
properties have been now described and understood very much from semicon-
ductor properties and band theories [75–77]. Figure 1.27 shows such an example
to understand lithium battery cathode (positive) materials from semiconductor
and Figure 1.28 for electrochemical cell described by band structure and physics.
The traditional electrolyte has served both as an ion conductor and as an
insulator against electrons preventing short-circuiting of a fuel cell. But the
short-circuiting problem could also be solved through energy band align-
ments and design, which have been successfully demonstrated in solar cells
and photoelectrolysis, thus paving the way for the single-component EFFC.
Semiconductor band and physics have made the conventional electrochemical
lithium battery understood by new aspects, which have to depend on the
scientific understanding and pushed the electrochemical crosslink to physics
and semiconductors. Perhaps we need to look forward more openly and envision
a wider range of energy applications from the new science discoveries working
across the different disciplines of materials, technology, engineering, physics,
and chemistry. This is a cross-thinking and philosophy beyond the fuel cell to
stimulate more innovations and creations not only for future fuel cell research
and development but also widely to support new advanced energy applications.
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32 1 Introduction
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62 Dong, W., Yaqub, A., Janjua, N.K. et al. (2016). All in one multifunctional per-
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63 Lan, R. and Tao, S. (2015). High ionic conductivity in a LiFeO2 -LiAlO2 com-
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35
Solid-State Electrolytes for SOFC

Liangdong Fan*
Shenzhen University, College of Chemistry and Environmental Engineering, Department of New Energy Science
and Technology, Nanhai Avenue 3688, Guangdong, Shenzhen 518060, China
2.1 Introduction
The key components of the solid oxide fuel cells (SOFCs) has three parts: two
porous electrode layers (anodic and cathode) and one sandwiched electrolyte
layer. As the heart of the SOFCs, the electrolyte plays an important role in single
cells and performance since it determines the fuel cell running temperature and
the corresponding other cell components [1–4]. The electrolyte used in SOFC
could be an oxygen ionic conductor or proton conductor, or a mixed oxygen ionic
and proton conductor; the cell structures based on the above various electrolyte
materials are shown in Figure 2.1, respectively. The electrode reactions for each
cell configuration are highly dependent on the applied electrolyte materials. Ide-
ally, the electrolyte should be a pure ionic conductor and an electronic insulator, a
dense separator for the oxidative and reductive gases as well as the half-reactions.
Desirable prerequisites for electrolyte materials to work efficiently in fuel cell
stakes and system are as follows [5, 6]:
1) High ionic conductivity (∼0.01 S cm−1 at the operating temperature [7]) with
an ionic transport number close to or equate to 1;
2) Gas-tight to maintain sufficient voltage efficiency and ensure safety;
3) Thermal expansion matching and chemical compatibility with adjacent cell
components;
4) Thermal/chemical stability at high temperature and oxidative and reductive
atmosphere, i.e. severe fuel cell operational condition;
5) Possessing reliable mechanical properties;
6) Using inexpensive raw materials and easy handling fabrication.
Up to date, due to the rigorous requirement for electrolyte, only a few
of ionic conducting materials have been truly put into application even
though versatile ionic conducting materials, such as Bi2 O3 -based materials
[8], Y2 O3 /Sc2 O3 -doped zirconia [9], doped ceria [10], Ca12 Al14 O33 [11], doped
*fanld@szu.edu.cn
Solid Oxide Fuel Cells: From Electrolyte-Based to Electrolyte-Free Devices,

First Edition. Edited by Bin Zhu, Rizwan Raza, Liangdong Fan, and Chunwen Sun.
© 2020 Wiley-VCH Verlag GmbH & Co. KGaA. Published 2020 by Wiley-VCH Verlag GmbH & Co. KGaA.
36 2 Solid-State Electrolytes for SOFC
H2O Air H2 O Air

H+ O2–
e– e– e– e–
H2O H2O
H+ O2–
H2O + H2 H2O + N2 H2O + H2 N2
(a) (b)
H2O Air
H+
e– e–
H2O H2O
H2O + H2 O2– H2 O + Air
(c)
Figure 2.1 Schematic illustration of cell configurations of a solid oxide fuel cell with different
ionic conducting electrolyte materials: (a) proton conductor, (b) oxygen ionic conductor, and
(c) mixed ionic conductor.
LaGaO3 perovskite-type oxide [12], Ln10 (SiO4 )6 O3 (Ln = La, Nd, Sm, Gd and Dy)
[13], and La2 Mo2 O9 -based fast oxide ion conductor [14], have been developed,
proposed, and extensively studied in the past decades for SOFC application.
Among them, oxygen ionic conductors of the stabilized zirconia, acceptor-doped
ceria, La0.9 Sr0.1 Ga0.8 Mg0.2 O3−𝛿 (LSGM), and proton conductors of barium cerate
and barium zirconate are the common choices for fuel cell academic and indus-
trial deployment. The yttrium-stabilized zirconia (YSZ) is the state-of-the-art
choice because of sufficient ionic conductivity at high temperature (≥700 ∘ C) and
wide oxygen partial pressure range. However, its ionic conductivity is not highly
enough for low temperature operation, whereas other electrolyte materials, such
as the nowadays widely academically adopted doped ceria, and perovskite LSGM
oxide, always suffer from the intrinsic drawbacks, like the reduction-induced
internal short circuit for the former case and high reactivity with the com-
monly used electrode materials for LSGM electrolyte. Other electrolytes
including the recently developed rare-earth ortho-niobates and tantalates [15],
Sr1−x Nax SiO3−0.5x [16], and Na0.5 Bi0.5 TiO3 [17] still need more and in-depth stud-
ies before they can be widely used like the abovementioned electrolyte materials.
There are worldwide research and industrial efforts to reduce the SOFC
operational temperature from ≥700 ∘ C to intermediate and low temperature
below 600 ∘ C. The reduced temperature allows extended material and system
lifespan and enables investment reduction, which are two major concerns
for product penetration into the market. While the operational temperature
is reduced from 800–1000 ∘ C to 300–700 ∘ C, the ohmic resistance of the
electrolyte should be minimized. Two major strategies are adopted. One is
the development of new electrolyte materials with high ionic conductivity as
mentioned above. The second is the reduction of the thickness of electrolyte
from the current millimeter level to micrometer level, even the nanometer level,
because the ohmic resistance is directly proportional to the thickness of the
electrolyte layer according to the Ohmic laws. Another interesting phenomenon
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The Project Gutenberg eBook of Charles
Dickens and other Victorians
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Title: Charles Dickens and other Victorians
Author: Arthur Quiller-Couch
Release date: December 21, 2023 [eBook #72466]
Language: English
Original publication: New York: G. P. Putnam's Sons, 1925
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*** START OF THE PROJECT GUTENBERG EBOOK CHARLES

DICKENS AND OTHER VICTORIANS ***
By Sir Arthur Quiller-Couch
On the Art of Writing

On the Art of Reading
Studies in Literature
(first series)
Studies in Literature
(second series)
Adventures in Criticism
Charles Dickens and
Other Victorians
Charles Dickens
And Other Victorians
Charles Dickens
And Other Victorians
By
Sir Arthur Quiller-Couch, M.A.
Fellow of Jesus College
King Edward VII Professor of English Literature
in the University of Cambridge
G.P. Putnam’s Sons

New York & London
The Knickerbocker Press
1925
Copyright, 1925
by
Sir Arthur Quiller-Couch
The
Knickerbocke
r
Press
New York
Made in the United States of America

PREFACE
ALL save one of the papers here collected were written as lectures
and read from a desk at Cambridge; the exception being that upon
Trollope, contributed to The Nation and the Athenaeum and
pleasantly provoked by a recent edition of the “Barsetshire” novels.
To these it almost wholly confines itself. But a full estimate of
Trollope as one of our greatest English novelists—and perhaps the
raciest of them all—is long overdue, awaiting a complete edition of
him. His bulk is a part of his quality: it can no more be separated
from the man than can Falstaff’s belly from Falstaff. He will certainly
come to his own some day, but this implies his coming with all his
merits and all his defects: and this again cannot happen until some
publisher shows enterprise. The expensive and artificial vogue of the
three-volume-novel did wonders for Trollope in one generation, to kill
him for another: since no critic can talk usefully about books to many
of which his hearers have no access. But we shall see Trollope
reanimated.
The papers on Dickens and Thackeray attempt judgment on
them as full novelists. Those on Disraeli and Mrs. Gaskell merely
take a theme, and try to show how one theme, taking possession,
will work upon two very different minds. Much more could have been
said generally upon both authors, and generically upon the “idea” of
a novel.
As usual, with a few corrections, I leave these lectures as they
were written and given, at intervals and for their purpose. They
abound therefore with repetitions and reminders which the reader
must try to forgive.
ARTHUR QUILLER-COUCH.
January 5, 1925.
CONTENTS
PAGE
Preface v
Dickens
I 3
II 24
III 42
IV 62
V 81
Thackeray
I 100
II 119
III 137
The Victorian Background 158
Disraeli 180
Mrs. Gaskell 199
Anthony Trollope
The Barsetshire Novels 219
Index 235
Charles Dickens
and Other Victorians
DICKENS (I)
I
IF anything on this planet be great, great things have happened in
Westminster Hall: which is open for anyone, turning aside from
London’s traffic, to wander in and admire. Some property in the oak
of its roof forbids the spider to spin there, and now that architects
have defeated the worm in beam and rafter it stands gaunt and clean
as when William Rufus built it: and I dare to say that no four walls
and a roof have ever enclosed such a succession of historical
memories as do these, as no pavement—not even that lost one of
the Roman Forum—has been comparably trodden by the feet of
grave men moving towards grave decisions, grand events.
The somewhat cold interior lays its chill on the imagination. A
romantic mind can, like the spider, spin its cobwebs far more easily
in the neighbouring Abbey, over the actual dust to which great men
come—
Here the bones of birth have cried—

“Though gods they were, as men they died.”
Here are sands, ignoble things
Dropt from the ruin’d sides of kings.
But in the Abbey is finis rerum, and our contemplation there the
common contemplation of mortality which, smoothing out place
along with titles, degrees and even deeds, levels the pyramids with
the low mounds of a country churchyard and writes the same moral
over Socrates as over our Unknown Soldier—Vale, vale, nos te in
ordine quo natura permittet sequamur. In Westminster Hall (I am
stressing this with a purpose) we walk heirs of events in actual play,
shaping our destiny as citizens of no mean country: in this covered
rood of ground have been compacted from time to time in set conflict
the high passions by which men are exalted to make history. Here a
king has been brought to trial, heard and condemned to die; under
these rafters have pleaded in turn Bacon, Algernon Sidney, Burke,
Sheridan. Here the destinies of India were, after conflict, decided for
two centuries. Through that great door broke the shout, taken up,
reverberated by gun after gun down the river, announcing the
acquittal of the Seven Bishops.
II
So, if this tragic comedy we call life be worth anything more than
a bitter smile: if patriotism mean anything to you, and strong opposite
wills out of whose conflict come great issues in victory or defeat, the
arrest, the temporary emptiness of Westminster Hall—a sense of
what it has seen and yet in process of time may see—will lay a
deeper solemnity on you than all the honoured dust in the Abbey.
But, as men’s minds are freakish, let me tell you of a solitary
figure I see in Westminster Hall more vividly even than the ghosts of
Charles I and Warren Hastings bayed around by their accusers: the
face and figure of a youth, not yet twenty-two, who has just bought a
copy of the Magazine containing his first appearance in print as an
author. “I walked down to Westminster Hall,” he has recorded, “and
turned into it for half an hour, because my eyes were so dimmed with
joy and pride that they could not bear the street and were not fit to be
seen there.”
Now the paper which opened the fount of these boyish tears
(here, if you will, is bathos) was entitled A Dinner at Poplar Walk.
You may find it to-day under another title, “Mr. Minns and his Cousin”
among Sketches by Boz: reading it, you may pronounce it no great
shakes; and anyhow you may ask why anyone’s imagination should
select this slight figure, to single it out among the crowd of ghosts.
Well, to this I might make simple and sufficient answer, saying that
the figure of unbefriended youth, with its promise, a new-comer
alone in the market-place, has ever been one of the most poignant in
life, and, because in life, therefore in literature. Dickens himself, who
had been this figure and remembered all too well the emotion that
choked its heart, has left us a wonderful portrait-gallery of these lads.
But indeed our literature—every literature, all legend, for that matter
—teems with them: with these youngest brothers of the fairy-tales,
these Oedipus’s, Jasons, these Dick Whittingtons, Sindbads,
Aladdins, Japhets in search of their Fathers; this Shakespeare
holding horses for a groat, that David comely from the sheepfold with
the basket of loaves and cheeses. You remember De Quincey and
the stony waste of Oxford Street? or the forlorn and invalid boy in
Charles Lamb’s paper on The Old Margate Hoy who “when we
asked him whether he had any friends where he was going,” replied,
“he had no friends.” Solitariness is ever the appeal of such a figure;
an unbefriendedness that “makes friends,” searching straight to our
common charity: this and the attraction of youth, knocking—so to
speak—on the house-door of our own lost or locked-away ambitions.
“Is there anybody there?” says this Traveller, and he, unlike the older
one (who is oneself), gets an answer. The mid-Victorian Dr. Smiles
saw him as an embryonic Lord Mayor dazed amid the traffic on
London Bridge but clutching at his one half-crown for fear of pick-
pockets. I myself met him once in a crowded third-class railway
carriage. He was fifteen and bound for the sea: and when we came
in sight of it he pushed past our knees to the carriage window and
broke into a high tuneless chant, all oblivious of us. Challenge was in
it and a sob of desire at sight of his predestined mistress and
adversary. For the sea is great, but the heart in any given boy may
be greater: and
these things are life

And life, some think, is worthy of the Muse.
III
But I am a Professor, and ought to have begun by assuring you
that this figure in Westminster Hall has a real historical interest in
connexion with your studies “on the subject of English Literature.”
Well, then, it has. The date of the apparition is New Year’s Day,
1834, and by New Year’s Day, 1838, Charles Dickens was not only
the most popular of living authors, but in a fair way to become that
which he remained until the end in 1870—a great National
Institution.
I use no exaggerated term. Our fathers of the nineteenth century
had a way (and perhaps not altogether a bad way) of considering
their great writers as national institutions; Carlyle was one, Ruskin
another. It was a part of their stout individualism, nowadays derided.
And it was, if you will consider, in the depths of its soul [say, if you
will, its Manchester Soul] a high-polite retort upon such a sworn
enemy as Ruskin. “Curse us, Sir: but we and no Government make
you a demigod.” You will never understand your fathers, Gentlemen,
until you understand their proud distrust of Government save by
consent. Take a favourite term of theirs—say “The Liberty of the
Press.” By that they meant liberty from interference by Government.
We, using that term to-day, should mean nothing of the sort. We
should mean “liberty from control by capitalists.”
I interrogate my youthful memories and am confident that, in a
modest country household these men—Carlyle, Ruskin—were, with
decent reverence, though critically, read for prophets. Tennyson, too,
and Browning had their sacred niches; and Darwin and Huxley, and
Buckle, who perished young attempting a History of Civilisation in
Europe: John Stuart Mill, also, and Kingsley, Maurice, George Eliot,
and Thackeray. These names leap to memory as names of
household gods. A few weeks ago, rummaging over some family
papers I came upon the following entry:
1848, June 20. I received a visit from Mr. Alfred Tennyson,

the Poet. He came into Cornwall along the North Coast, and
from about Camelford crossed over to Fowey, where I called on
him on the 19th. He came to Polperre in a boat, with Mr. Peach
and others; and after viewing our scenery in all directions and
taking tea at our house, they all rowed back to Fowey late in the
evening. I find him well-informed and communicative. I believe a
good Greek scholar with some knowledge of Hebrew. His
personal appearance is not prepossessing; having a slouch in
his gait and rather slovenly in his dress tho’ his clothes were new
and good. He confesses to this. He admired the wildness of our
scenery, deprecated the breaking in of improvements, as they
are termed. He enquired after traditions, especially of the great
Arthur: his object in visiting the County being to collect materials
for a poem on that Chief. But he almost doubted his existence.
He show’d me a MS. sketch of a history of the Hero: but it was
prolix and modern.
You see, hinted in this extract from a journal, how our ancestors, in
1848 and the years roundabout, and in remote parts of England,
welcomed these great men as gods: albeit critically, being
themselves stout fellows. But above all these, from the publication of
Pickwick—or, to be precise, of its fifth number, in which (as Beatrice
would say) “there was a star danced” and under it Sam Weller was
born—down to June 14, 1870, and the funeral in Westminster
Abbey, Dickens stood exalted, in a rank apart. Nay, when he had
been laid in the grave upon which, left and right, face the
monuments of Chaucer, Shakespeare and Dryden, and for days
after the grave was closed, the stream of unbidden mourners went
by. “All day long,” wrote Dean Stanley on the 17th, “there was a
constant pressure on the spot, and many flowers were strewn on it
by unknown hands, many tears shed from unknown eyes.”
Without commenting on it for the moment, I want you to realise
this exaltation of Dickens in the popular mind, his countrymen’s and
countrywomen’s intimate, passionate pride in him; in the first place
because it is an historical fact, and a fact (I think) singular in our
literary history; but also because, as a phenomenon itself unique—
unique, at any rate, in its magnitude—it reacted singularly upon the
man and his work, and you must allow for this if you would
thoroughly understand either.
IV
To begin with, you must get it out of your minds that it resembled
any popularity known to us, in our day: the deserved popularity of Mr.
Kipling, for example. You must also (of this generation I may be
asking a hard thing, but it is necessary) get it out of your minds that
Dickens was, in any sense at all, a cheap artist playing to the gallery.
He was a writer of imperfect, or hazardous, literary education: but he
was also a man of iron will and an artist of the fiercest literary
conscience. Let me enforce this by quoting two critics whom you will
respect. “The faults of Dickens,” says William Ernest Henley,
were many and grave. He wrote some nonsense; he sinned

repeatedly against taste; he could be both noisy and vulgar; he
was apt to be a caricaturist where he should have been a
painter; he was often mawkish and often extravagant; and he
was sometimes more inept than a great writer has ever been.
But his work, whether good or bad, has in full measure the
quality of sincerity. He meant what he did; and he meant it with
his whole heart. He looked upon himself as representative and
national—as indeed he was; he regarded his work as a universal
possession; and he determined to do nothing that for lack of
pains should prove unworthy of his function. If he sinned, it was
unadvisedly and unconsciously; if he failed it was because he
knew no better. You feel that as you read....
He had enchanted the public without an effort: he was the
best beloved of modern writers almost from the outset of his
career. But he had in him at least as much of the French artist as
of the middle-class Englishman; and if all his life he never
ceased from self-education, but went unswervingly in pursuit of
culture, it was out of love for his art and because his conscience
as an artist would not let him do otherwise.
Now let me add this testimony from Mr. G. K. Chesterton:
Dickens stands first as a defiant monument of what happens

when a great literary genius has a literary taste akin to that of the
community. For the kinship was deep and spiritual. Dickens was
not like our ordinary demagogues and journalists. Dickens did
not write what the people wanted. Dickens wanted what the
people wanted.... Dickens never talked down to the people. He
talked up to the people. He approached the people like a deity
and poured out his riches and his blood. He had not merely
produced something they could understand, but he took it
seriously, and toiled and agonised to produce it. They were not
only enjoying one of the best writers, they were enjoying the best
he could do. His raging and sleepless nights, his wild walks in
the darkness, his note-books crowded, his nerves in rags, all this
extraordinary output was but a fit sacrifice to the ordinary man.
“The good, the gentle, high-gifted, ever-friendly, noble Dickens,”

wrote Carlyle of him, on hearing the news of his death,—“every inch
of him an honest man.” “What a face it is to meet,” had said Leigh
Hunt, years before; and Mrs. Carlyle, “It was as if made of steel.”
V
I shall endeavour to appraise with you, by and by, the true worth
of this amazing popularity. For the moment I merely ask you to
consider the fact and the further fact that Dickens took it with the
seriousness it deserved and endeavoured more and more to make
himself adequate to it. He had—as how could he help having?—an
enormous consciousness of the power he wielded: a consciousness
which in action too often displayed itself as an irritable
conscientiousness. For instance, Pickwick is a landmark in our
literature: its originality can no more be disputed than the originality
(say) of the Divina Commedia. “I thought of Pickwick”—is his
classical phrase. He thought of Pickwick—and Pickwick was. But just
because the ill-fated illustrator, Seymour—who shot himself before
the great novel had found its stride—was acclaimed by some as its
inventor, Dickens must needs charge into the lists with the hottest,
angriest, most superfluous, denials. Even so, later on, when he finds
it intolerable to go on living with his wife, the world is, somehow or
other, made acquainted with this distressing domestic affair as
though by a papal encyclical. Or, even so, when he chooses (in
Bleak House) to destroy an alcoholised old man by “spontaneous
combustion”—quite unnecessarily—a solemn preface has to be
written to explain that such an end is scientifically possible. This
same conscientiousness made him (and here our young novelist of
to-day will start to blaspheme) extremely scrupulous about
scandalising his public—I use the term in its literal sense of laying a
stumbling-block, a cause of offence. For example, while engaged
upon Dombey and Son, he has an idea (and a very good idea too,
though he abandoned it) that instead of keeping young Walter the
unspoilt boyish lover that he is, he will portray the lad as gradually
yielding to moral declension, through hope deferred—a theme which,
as you will remember, he afterwards handled in Bleak House: and he
seriously writes thus about it to his friend Forster:
About the boy, who appears in the last chapter of the first
number—I think it would be a good thing to disappoint all the
expectations that chapter seems to raise of his happy
connection with the story and the heroine, and to show him
gradually and naturally trailing away, from that love of adventure
and boyish light-heartedness, into negligence, idleness,
dissipation, dishonesty and ruin. To show, in short, that common,
every day, miserable declension of which we know so much in
our ordinary life: to exhibit something of the philosophy of it, in
great temptations and an easy nature; and to show how the
good turns into the bad, by degrees. If I kept some notion of
Florence always at the bottom of it, I think it might be made very
powerful and very useful. What do you think? Do you think it
may be done without making people angry?
George Gissing—in a critical study of Dickens which cries out for

reprinting—imagines a young writer of the ’nineties (as we may
imagine a young writer of to-day) coming on that and crying out upon
it.
What! a great writer, with a great idea, to stay his hand until
he has made grave enquiry whether Messrs. Mudie’s
subscribers will approve it or not! The mere suggestion is
infuriating.... Look at Flaubert, for example. Can you imagine him
in such a sorry plight? Why, nothing would have pleased him
better than to know he was outraging public sentiment! In fact, it
is only when one does so that one’s work has a chance of being
good.
All which, adds Gissing, may be true enough in relation to the

speaker. As regards Dickens, it is irrelevant. And Gissing speaks the
simple truth; “that he owed it to his hundreds of thousands of readers
to teach them a new habit of judgment Dickens did not see or begin
to see.” But that it lay upon him to deal with his public scrupulously
he felt in the very marrow of his bones. Let me give you two
instances:
When editing Household Words he receives from a raw
contributor a MS. impossible as sent, in which he detects merit. “I
have had a story,” he writes to Forster, “to hack and hew into some
form this morning, which has taken me four hours of close attention.”
“Four hours of Dickens’ time,” comments Gissing, “in the year 1856,
devoted to such a matter as this!—where any ordinary editor, or
rather his assistant, would have contented himself with a few
blottings and insertions, sure that ‘the great big stupid heart of the
public,’ as Thackeray called it, would be no better pleased, toil how
one might.”

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Solid Oxide Fuel Cells From Electrolyte Based To Electrolyte Free Devices Bin Zhu All Chapter

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Solid Oxide Fuel Cells: From

From Electrolyte-Based to Electrolyte-Free Devices

Print ISBN: 978-3-527-34411-6

Typesetting SPi Global, Chennai, India

Printed on acid-free paper

10 August 2019 Bin Zhu, Rizwan Raza, Liangdong Fan,

Part I Solid Oxide Fuel Cell with Ionic Conducting

2 Solid-State Electrolytes for SOFC 35

2.4.4 Ionic Conduction Mechanism Studies of Ceria–Carbonate

3 Cathodes for Solid Oxide Fuel Cell 79

4 Anodes for Solid Oxide Fuel Cell 113

5 Design and Development of SOFC Stacks 145

5.2.2 Variations of Cell Output Performance Under 2D Contact Mode 147

Part II Electrolyte-Free Fuel Cells: Materials, Technologies,

6 Electrolyte-Free SOFCs: Materials, Technologies, and Working

7 Ceria Fluorite Electrolytes from Ionic to Mixed Electronic and

8 Charge Transfer in Oxide Solid Fuel Cells 239

9 Material Development II: Natural Material-based Composites

9.3.2.1 Hematite–LSCF 295

10 Charge Transfer, Transportation, and Simulation 319

11 Electrolyte-Free Fuel Cell: Principles and Crosslink

Part III Fuel Cells: From Technology to Applications 377

12 Scaling Up Materials and Technology for SLFC 379

13 Planar SOFC Stack Design and Development 415

14 Energy System Integration and Future Perspectives 447

14.5.1 Activation Loss 457

Solid Oxide Fuel Cell with Ionic Conducting Electrolyte

1.1 An Introduction to the Principles of Fuel Cells

Solid Oxide Fuel Cells: From Electrolyte-Based to Electrolyte-Free Devices,

Water Figure 1.1 Sketch of William

Sulfuric acid solution

The three-component MEA technology requires a complex FC structure and

1.2 Materials and Technologies

O2– ion Host cation (4+)

Dopant Cation Vacancy

LSTN–YSZ top view LSTN –YSZ top view

(a) (b) (c)

NIO–YSZ, YSZ targets LSC target Pt target

(d) (e) (f)

Figure 1.4 Schematics of the fabrication process of micro-SOFC supported on LSTN–YSZ/STS

especially below 600 ∘ C [22, 23]. Perovskite-structured oxides, ABO3 , as shown

1.3 New Electrolyte Developments on LTSOFC

that alternative electrolytes should be designed for low temperatures; commonly

Figure 1.10 Combining nano and

Anode Electrolyte Cathode

700 600 500 400 300 200

1.0 1.2 1.4 1.6 1.8 2.0

a much high ionic conductivity with a great enhancement compared to the

(i) High mobile ion concentration, n (𝜎 0 ). It is directly proportional to the ionic

(iii) Long ionic transport path, L (𝜎 0 ). This eﬀect is again proportional to

This composite approach was further extended to optimize hybrid

H+ O2– Ce4+ C4+ Na+ Hydrogen bond

Figure 1.18 Ceria-carbonate

this novel n–p semiconductor–ionic heterostructure. This provides a useful and

Figure 1.19 Interfacial ionic conduction is presented in YSZ–carbonate composite system.

Figure 1.20 Semiconductors Combination e–

1.4 Beyond the State of the Art: The Electrolyte-Free

Anode Electrolyte Cathode

(a) Electron itinerant (b) Electron localized

(d) (e) Temperature (°C)

1.0 Epitaxial H-SNO

0.4 Cell 2 100

1.4.1 Fundamental Issues