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Solid Oxide Fuel Cells
Solid Oxide Fuel Cells
From Electrolyte-Based to Electrolyte-Free Devices
Edited by
Bin Zhu
Rizwan Raza
Liangdong Fan
Chunwen Sun
Editors All books published by Wiley-VCH
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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
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
1
Part I
Solid Oxide Fuel Cell with Ionic Conducting Electrolyte
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.
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

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 O) 3 0 .2
–1.5 0.
7 Ca
2
0.8
7 (Ca 2
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
M2 C 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
2– + (iv)
O Na
+ 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
3+/4+ 3+/4+
Ni :eg Ni :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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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

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do than what I have been doing.”
“Studying, growing accomplished, falling in love, and marrying,”
replied the earl, laughing. “What would you have been doing more?”
“As it happens, sir, all this proves an excellent preparation for my
present business. But I did not know that it would; and I was
perpetually asking myself,—moreover, Letitia was perpetually asking
me,—the end and aim of my employments.”
“That was the secret, I dare say,” said the earl, “of your difficulty in
winning her. Eh, Letitia?”
“Indeed it was,” replied Letitia, blushing. “God knows what difficulty
I found in making it a difficulty; but I dared not at once give up the
calling which nature had sanctified to me, without providing for my
race being served in an equal proportion in some other way. If there
be one note sooner than another to which conscience awakes in
these times, it is to the cry of unserved humanity; and mine, having
been once thus awakened, could not be lulled asleep again; and
even your son could not soothe it till he began to promise that we
should labour together for all, as well as for each other.”
“So you married to be useful;—for no other reason on earth, my
dear?”
“No, no, no. I was useful before. I married ... for the same reason
as your son. But this reason did not make me forget my
responsibilities; that is all.”
“Ah, my dear: you do not know,—highly as you rate your art,—
what you have deprived society of by shutting yourself up here. Why,
—I saw that sot, colonel Bibber, turned into a patriot for full three
hours under your influence; and poor little lord H. that we were
speaking of just now, grew almost magnanimous for the same space
of time. These, and hundreds more, owe to you, my dear, the greater
part of whatever virtue has visited them for the last five years.”
“If so,” said lord F——, “what was the effect on better people?”
“The effect that the fine arts are ordained to produce,” said Letitia.
“They have much to answer for who defame them,—who perceive
nothing in them besides colours, and sounds, and motion,—who put
a kaleidoscope and Raphael’s Transfiguration on a level, and
recognize nothing more in a symphony of Mozart than in an Eolian
harp, and see no matter of choice between a merry Andrew and
Kean in Hamlet. They who perceive not that the fine arts are the
fittest embodiments of truth and beauty are unconscious of the
vastness of the department in which they would have man remain
unserved. Such would wonder or laugh at my view of my profession,
and discredit my hesitating to leave it for lord F——.”
“You were satisfied that you held a commission to serve man, by
means of the fine arts; you were right, my dear, as is proved by your
having made the colonel a patriot, and the little lord a hero.”
“That it was only for three hours at a time,” said Letitia, “was not
my fault, but that of the arrangements by which means and ends are
sometimes separated as far asunder as if the world would be perilled
by their coming together. In this, we might wisely copy from man in
his state of nature. Indian savages have their songs and dances
immediately before their battles; and, as long as prayers imply
devotion, they are everywhere used in senates as a prelude to the
business of the nation. But we go straight from an oratorio to dinner,
from a tragedy to sleep, from the Elgin marbles to shopping in
Regent-street; while, on the other hand, if a great national question
has to be debated, a mighty national achievement to be wrought, the
last thing its conductors would think of would be to spiritualise the
passions, and elevate the emotions, and animate the faculties by the
most appropriate means which Providence has given for that end.—I
know that this union can be only partially effected yet. I know that the
passage of the Reform Bill would have been but little helped by any
such appliances as we can at present exhibit; but it will be different
hereafter, when men have learned the true office of the fine arts, and
the ultimate objects of political reforms. Then, hundreds of years
hence, it may be,—if a new question of national renovation should
be brought forward, the senate to whom it is committed may lay hold,
with one accord, on whatever prior observance may best soothe
down their animosities, and banish their petty self-regards, and
establish their minds in that state of lofty tranquillity which alone
beseems the master-spirits of an empire.”
“In those days,” said lord F——, “there will be an end of the
absurdity of admitting the ennobling influence of the fine arts, and at
the same time holding its professors in contempt.”
“Is it, even now, anything more than a nominal contempt?” asked
Letitia. “Do not people mix up the profession and the vices of its
professors together, and then talk of contempt?”
“But those very vices are caused by the treatment of the
profession.”
“True; like all other professional vices,—like all the peculiar failings
of certain classes,—like the avarice of Jews, the romancing of
travellers, the spiritual pride of sectaries, the vanity of authors. When
prejudices are so far surmounted as that no class shall be regarded
with factitious deference or contempt, there will be an end of all
occasion to reproach painters, musicians and actors with their
tendency to self-indulgence, at the same time that proverbs and by-
words against Jews, methodists, travellers, and poets, will fall into
oblivion.”
“In those days,” said lord F——, “perhaps our peerage may
honour itself by taking up the profession of the fine arts. The time is
coming when no class of society may be idle; and if the aristocracy
plumes itself upon its refinement, this seems to be the pursuit most
congenial to its constitution.”
“If you preach your doctrine,—that all must work,—to those of your
own condition,” said the earl, “they will ask you where you got the
notion,—whether you are intimidated by the clamours of the lower
classes.”
“Not intimidated by their clamours, but moved by their condition, I
would tell them, sir; and that I derive my notion from the nature of
man and of society, and not from the dictation of any class whatever.
It is enough to melt a heart of stone to read and hear of such
distresses as have come to my knowledge since I entered office; but
I am convinced that many of the sufferers look in the wrong direction
for the causes.”
“Yet there must be much cause for complaint,” said Letitia, “when
our institutions lead to such an opposition of interests as there now is
between different ranks. They should surely work together....”
“The present opposition of interests, my dear, arises from a
scarcity of the prime necessaries of life. If there were food enough
for our people, their occupations and interests, be they as various as
the minds that adopt them, would assist and promote each other
from end to end of society. If there be a scarcity of food, men will
snatch from one another’s mouths, be they huddled together in our
manufacturing cities, or duly distributed in a Moravian settlement.
Where there is plenty, there will be a harmony,—where there is want,
there will be an opposition of interests; and it is folly to assign co-
operation and competition as the remedy and cause of distress.”
“Nay; but can it be right that starving thousands should bid their
labour against one another for bread? Can it be right that whole
families should, at this moment, be crouching down supperless in
their litter of straw, while we.... O, I am ashamed of our luxuries!...
our mirrors, and harps, and lamps,—and my very dress. I am
ashamed of them all.”
“If we gave them all away this moment, my dear, they would not be
food; and if exchanged for bread, they would only take food from the
mouths of some who want it, to give to those who cannot want it
more. Believe me, the inequality of condition we are complaining of
is rather checked than promoted by competition. Competition
equalizes the profits of industry, and increases instead of lessening
its productiveness.”
“Whence, then, comes all this misery? all this tremendous
inequality?”
“The misery arises from a deficiency of food....”
“Well; whence this deficiency of food?”
“From the tendency of eaters to increase faster than the supply of
food.”
“But if we can raise more food by co-operation than without it....”
“Even supposing we could,—unless co-operation also checked the
increase of numbers, it could prove no more than a temporary
alleviation of our grievances. In my opinion, it would, if it included
equality of condition, leave us in a worse state than it found us, in as
far as it would relax the springs of enterprise and industry, and, in
time, bring the community down into a deplorable state of sameness;
it would, if persevered in, make us into a nation of half-naked potatoe
eaters, and water-drinkers.”
The earl inquired whether anything had been heard lately of the
co-operative society formed in the neighbourhood of Weston.
“O yes!” replied lord F——. “They are enjoying the benefits of
competition to the utmost. They ascribe their prosperity to their co-
operation; but they are, in fact, a large partnership in competition
with smaller ones. They do not see how their relative position would
be altered by their absorbing all their competitors into their firm, with
no check to their numbers, while nature has imposed perpetual
checks upon the growth of their capital.”
“But cannot numbers be checked,—cannot the checks upon the
growth of capital be evaded, while we have such a wide world to
move about in?”
“Certainly, my dear: but there is no need of equality of condition to
help us to do this. Competition is more likely than co-operation to
induce prudence and foresight; and it will quicken our activity in
carrying our surplus numbers to distant fertile lands, or in bringing
the produce of distant fertile lands among our own people, instead of
tempting us to waste more and more of our capital continually in
turning up inferior lands at home, as the co-operatives would have
us do.”
“But were not you telling me that your rent-roll becomes more
valuable as time passes? Are not landholders’ incomes increasing
perpetually under the present system?”
“They are; but this is the consequence, not of competition, but of
the varying qualities of the land, the tillage of every new grade of
which tends to lower profits and raise rents. No plan for the
distribution of home produce can affect the law by which the returns
to capital are perpetually diminished.”
“But what will be the end of it under the present system?”
“There are two extremes to which the systems of equality and
inequality of distribution respectively tend, in as far as they involve
restriction upon food by using only the produce of our own lands.
Under the equality system, there would be an ultimate scramble for
potatoes, or a worse diet still, if there were such a thing. Under our
present system, the whole produce must in time be in the hands of
the land-owners and tax-takers. Of course, we must change our
system; not, however, by discouraging competition, or abolishing
private property, but by removing all artificial restrictions upon food,
and by regulating our numbers according to our resources. The way
to bring down landlords’ rents, and to increase the profits of
cultivators, is to procure food from some better source than our own
inferior lands; and this I will prove to you by figures, the next time my
steward brings me the accounts of my farms.”
“O, that Moravian village!” exclaimed Letitia. “How often I think of
the day we spent there! There was comfort, there was abundance,
there was mutual assistance and agreement.”
“Are you quite sure, Letitia, that there was nothing in the situation
and peculiarities of the place which called off your attention from the
principle on which the society was constituted? Remember the
sunset, that evening; the golden light on the green hill side, above
the rows of Moravian dwellings. Remember your admiration of the
internal regulations,—of the women’s uniform, of the music in their
church, of the simplicity of their way of life. Remember that all this
has nothing to do with their principle of association.”
“You must no more set the accomplishments of the Moravians to
the account of community of goods, than the absurdities of the
Shakers,” observed the earl. “That some sing beautifully, and others
dance ridiculously, has nothing to do with the distribution of their
wealth.”
“No more than the ordinances of the Harmonites,” continued lord F
——. “Mr. Owen’s followers very properly refuse to be mixed up with
Moravians, Shakers, and Harmonites. Superstition has no part in
their system, either under the form of ritual observance or celibacy.
Yet they are apt to incorporate extraneous matters with their system,
which serve as allurements to a greater extent, I doubt not, than they
intend. They owe more converts than they suppose to their promises
of mansions, pleasure-grounds, coffee, alabaster lamps, and so on.
My wonder is that more are not enticed by descriptions like these,
accompanied with promises of ease, and leisure, and many other
things to be obtained in a short time, which the poor man now sees
little chance of his children’s children ever enjoying.”
“There might be alabaster lamps and damask furniture in every
house under the present system,” observed the earl, “if food enough
could be got to keep the production of capital going at its natural
rate; aye, and ease and leisure too, if our numbers were kept within
bounds. It is not so very long since shoes and stockings were worn
only in courts; and that they are now worn by peasants proves that
our capital has grown under a system of competition. That multitudes
have little ease and no leisure is the fault of over-population, which
would be rather aggravated than lessened under a system whose
very essence it is to cast each man’s burdens upon all. No man need
scruple to have twenty of his children gracing the dinner-table of a
co-operative establishment, till he should find, too late, that not all
the savings caused by extensive association can compensate for the
falling off in the produce of inferior lands, and for the new impulse
given to population. His sons and his sons’ sons must add more and
more labour to the common stock; must give up, first, damask and
alabaster, then broadcloth and glass; then descend to sackcloth and
wooden trenchers, then to tatters, potatoes and water, and then....”
“Then would ensue a scramble; if anything should be left,
competition would come into play again; society would rise by its
means, and might possibly attain once more to a state in which they
might speculate on the universality of damask and alabaster.”
“Well!” exclaimed Letitia, “I shall ask to look at your steward’s
accounts, and to have an explanation of them; for I do not at all like
our present position. We must reach the extreme, you say, of having
our whole produce in the hands of land-owners and tax-takers,
unless we change our system.”
“Yes, my dear: but by change of system, I do not mean convulsion.
All might be set on a safe footing by timely care, the removal of
restrictions, the diffusion of intelligence. There is nothing in all this,
threatening to public dignity or private safety. There is nothing to
lessen the security of property, or to endanger the rights of any
class; but quite the contrary: for property is never so secure as when
it most abounds; and rights are never so well respected as in the
absence of temptation to infringe upon them.”
“By change, then, you mean progression, without fear of
subversion.”
“Just so; the progression of society from an advanced into a higher
state. What is there in such progression that is not as beautiful in
theory as it is found to be necessary in practice?”
From this hour, the progression of society, of which Letitia had
long dreamed, on which she had often speculated, began to assume
distinctness in her mind, and to form a large part of her conversation
when she happened to be with those to whom she could speak most
of what was most in her thoughts. Whenever she heard of misery
and crime on a large scale, she satisfied herself that the national
demand of progression had not yet been sufficiently attended to.
When she heard that her lord’s rents ought to be more, but were,
from the difficulty of collecting them, less than formerly, she sighed
for the time when an unrestricted provision of food (unrestricted by
state-laws) should check the rise of rents. Whenever she sat down
by her husband’s side to hear curious tales of the doings of large
speculators or eminent merchants, or of the sufferings of large
classes of agricultural or manufacturing labourers, she learned
something that made her wonder and lament, that, while the natural
laws of production and distribution work out evenly their balance of
results, the tendency of legislation thus far seems to be to clog and
thwart them, and delay the progression in intelligence and comfort
which must arise out of their unobstructed operation. She saw that, if
the universal interest of society was allowed to be the moving spring
of the social economy, all would be served; and that if many yet
remain unserved, it is on account of other movements being made to
interfere with it—the petty springs of narrow and mistaken interests;
so that partial protection brings on general hardship, and arbitrary
stimulus, a condition of general suffering.
Before going down to Weston, Letitia had become prepared to
make her way with the steward, the co-operating workmen in the
village, and all who could throw light on the past and present state of
property in the place. Many a conversation and calculation had she
also gone through with Thérèse on the subject of shop-keeping in
Paris; and all that Maria told of Waldie’s business went to the same
account of information. It made poor Maria smile sometimes in the
midst of a fit of anxiety to find that her children’s babble savoured of
political economy, when they had been spending a morning with their
aunt. They were more ready then than at other times to wonder why
they had dolls in the nursery, and picture-books in the parlour, and a
shell-grotto in the garden, when many other little children had no
playthings; and why poor Ned who swept the crossing was so much
more ragged than their errand boy, when Ned worked the hardest of
the two, and was often out in the cold and the rain besides. Almost
babies as they were, they could sometimes find out very sage little
reasons for these things, when put on the right scent by aunt Letitia
or her pupil Thérèse.
Chapter IV.
MORE NOVELTY.
At length came September, with its utter dulness in town, and its
busy brightness in the country. No parliament, no ministry, no court,
with whose proceedings to diversify the daily papers; but instead, a
reporting of the progress of certain noble lords and patriotic
gentlemen from one country seat to another, with accurate
calculations of the quantity of game bagged by each. Now were
expresses hurrying to and fro in search of the runaway men in
power. Now were ancient ladies proudly leaning on the arms of sons,
who were happy in being allowed breathing time to watch the
autumn sunsets from the terraces of their stately castles. Now were
the young heirs of rank and wealth initiated by playful papas into the
mysteries of riding and sham shooting. Many a little lord was now
mounted on his pony to adventure forth as far as the park gates,
while mamma and sisters waved their handkerchiefs from afar, and
careful grooms waited to lead him back safe. Many such a little
rogue carried his mimic fowling-piece into the stubble, and learned
not to wink or flinch when papa brought down a bird, or coaxed the
gamekeeper to lend him a brace or two to carry when they should
come in sight of home and the girls. Many a tenant now put himself
in the way of a greeting from his landlord, resting on a stile, or pacing
his way slowly through a field. Many a state secret, that the public
would fain have known, was dismissed for some such freak as
snatching at a high hazel twig, or leaping a gate. Many a fair family
group of riders was seen threading green lanes, or cantering over
downs, or appearing and disappearing in the clumpy drives of a
park,—graceful boys, and high-born girls, leading their father in
search of some new beauty which it turns out he discovered in like
manner, when he was a pleasure-loving youth instead of a
statesman. Now, in the golden noon, was the boat seen to unfurl its
snowy sail, and glide in rivalship of grace with the swans which
diverged on either hand to let the vessel have its way without
disturbing their serenity. He who has guided, or may guide, the helm
of the state, now condescends to steer a less majestic bark on a
calmer element; and instead of the prayers, threats and blessings of
an empire, bends his ear to the prattle of his little ones, or to the
rustling of a startled deer, bounding from the thicket as the vessel
nears the shore. Not now too busy to observe whether rain or
sunshine be without, the recreated statesman finds in either case
equal pleasure and repose. His lady’s nursery and boudoir, his sons’
classics, his daughters’ music, his library, his billiard table, and withal
some peculiar and long relinquished pet pursuit, give him as much
pleasure on a rainy day, as the flower-garden, the fish-pond and
poultry-yard when the sky is blue overhead. He sighs over his past
toils, reminds his spouse of their wedding sojourn at Chamouni, and
at intervals quotes Virgil to the lad behind his chair, and whispers
Pope to the little lady netting at his elbow. Statesmanship should
have pleasures worthy of its toils; and so thought Letitia when her
husband first mutely pointed out to her the woods of Weston.
Sweet was the leisure of the first afternoon, which gave promise of
what should be done at future intervals of leisure;—intervals not
likely to be too frequent to retain their charm. His lordship had
brought his business and its apparatus with him; but for this day all
was laid aside. Within half an hour after alighting from the carriage,
and while dinner was being served up, my lord and lady were in the
rosery, observing on what must have been its beauty a few weeks
before, and the one pointing out and the other following with eager
eyes the tracts among the hanging woods which had to be explored,
the points of view which must be visited, one at sunrise, one in the
glowing noon, another in the still evening. As soon as dinner was
over, they were out again, that Letitia might see the ruins of the old
abbey before the sunlight should have departed. Her heart melted
within her when she saw the long shadows of the lofty arch extended
on the velvet turf, motionless except when a bird took wing from
among the ivy, and set its boughs dancing. The rooks sailed in
circles above the stately ruin, and the thrush piped from the
evergreen covert which shut in the retired nook in which it stood. The
sun-dial also marked the silent lapse of time, although there was
usually none to lay the lesson to heart.
“This is the place, love,” said lord F——.
“And you would have had me come without you,” said Letitia, after
a long pause.
“We have some weeks yet, to be sure, to enjoy it. This is the last
spot that looks desolate as winter comes on. No leafless trees, no
strewn blossoms! The wall-flowers there on the pinnacle flourish late;
and all is green and bright till the snow falls.”
“And after, surely,” said Letitia. “I should like to see icicles
glistening on these arches, springing grey from the sheeted snow. I
should like to see the ivy sprays bending under their white burden, or
shaking it off in a shower of sparkles at the breeze’s bidding. O let us
come here at Christmas!”
“If we do, you may chance to see another sight. You will see tracks
of small feet in the snow, and catch some little girl, in her red cloak,
stealing from the Wishing-Well.”
“The Wishing-Well! O where?”
“It springs from under an old stump behind this wall. Have you any
wishes?”
“I will make some for the superstition’s sake.”
And immediately Letitia might be seen unbonneted, kneeling on
the consecrated stone, and drinking the draught her husband had
filled for her. Thus was she seen, as presently appeared. A voice
reached them from one side, praying that her ladyship’s wishes
might come to pass, be they what they might, as they must be for
good and no harm to the people under her. Letitia sprang up,
laughing, and her husband replaced her hat, calling to the well-
wisher to show himself. He did so, not in the shape of a hardy
labourer, with his farming or gardening tools on his shoulder; nor yet
of a picturesque old man bending beneath his faggot. Such might
better have beseemed the place: but this was a middle-aged,
shrewd-looking little man, whom one would have guessed to be
town-bred. He came forward, saying that he had a message for her
ladyship from his wife;—my lord knew his wife.
“Not I,” said his lordship. “I did not know you had a wife.”
“May be not, my lord; but you know the woman. She that keeps
the grocery shop, as you turn the corner in the village, your lordship
remembers.”
“What! Nanny Sweet? So you have taken her to wife since I saw
you last.”
“Yes, my lord. She has a very good business, or had before the
equality folks set up a store against us. I don’t like equality, not I. But
my wife sends word, my lady....”
“You do not like equality!” interrupted Letitia. “If there was equality,
you know, you would not need to mind who set up a store, and what
came of your wife’s grocery business.—And do not you like this
place too,—these woods, and the deer, and the lake?”
White lauded the grandeur and beauty of Weston.
“Well; this place would be as much yours as ours if there was
equality. You might fish on the lake, and shoot in the preserves,
and....”
“And lie down to sleep in the sun here beside the well,” continued
lord F——; “and all without asking anybody’s leave.”
“I thank you kindly, my lord; but I like sleeping in my bed, if I sleep
at all, unless it be dozing over my pipe, while Jack is reading the
news at the Duke’s Head. The only time I went fishing, I fell into the
water; so you’ll not soon find me in a boat again. My wife and I like a
chicken now and then, on Sundays; so a share of your poultry-yard
would be welcome perhaps; and, as for the deer and game, I leave it
to other folks to get out of their warm beds for the sake of it. It would
not answer to me to be laid by with the rheumatism for such a cause,
you see.”
“But there would be no poaching if there was equality,” said Letitia,
laughing. “Cannot game be shot in the daytime?”
“By none but gentlemen, my lady, as I have always heard.
However, the equality folks have no more game, as far as I know,
than other people. The most they pretend to is to have plenty of
butcher’s meat.—What I pretend to, and Nanny too, is to get our
bread honestly; and so, my lady, she bade me tell you that she has
laid in a new stock, hearing your ladyship was coming, and has lost
already by its being September instead of June. Light ginghams for
morning wear....”
“I thought your wife was a grocer.”
“Grocer and draper, my lady. If your ladyship should find the
mornings chilly, as they will be soon, perhaps you would look at her
stuffs;—a very pretty variety of browns, as you will see, my lady. And
her tea and sugar is of the best; and as for her snuffs....”
“O, I must make acquaintance with her snuffs, of course. Have you
a pinch about you?”
“And what is your occupation now, White?” inquired lord F——.
“The last thing I had to do, my lord, was lining your lordship’s pew
at church, and covering the hassocks.”
“And what did your priest say to that?”
“Lord, sir, I cleared scores with the priest long ago; ever since I
was employed to white-wash the Baptist chapel.”
“Were you once a Catholic?” inquired Letitia.
“Yes, my lady. There was carving work to do at Sir William’s
chapel, and I got a good long job.”
“And were a Catholic while it lasted, and a Baptist after white-
washing the meeting-house?”
“To be sure, my lady; I took a part in the week-day meetings after
that.”
“Till you were employed to line my pew; and now, I dare say, you
are a very good churchman?”
“I hope to be so, my lord. Your lordship may laugh, but I know what
manners is. I wouldn’t be so unhandsome as to take work at one
place, and attend at another.”
“So your interest has nothing at all to do with it, White; only
manners. But I wonder now what you think your religion is worth, if
you can change and change again as you have done?”
“Why, my lord, I think religion is a very good thing, as long as it
does not come in one’s way: but one must make sacrifices to duty,
as all the clergy tell us; and is it not my duty to get my living the best
way I can?”
“Well, White; tell your wife I will step down to see her stock, some
day soon. I do not at present take snuff; but whenever I do, I will be
her customer.”
Thérèse and her mistress kept one another waiting this night. The
housekeeper, who was much amused with Thérèse’s broken English
and unbroken simplicity, invited her out to a turn in the shrubberies
when tea was sent in, and she was sure of not being wanted for an
hour or two. When they came in again, they found that their master
and mistress had once more wandered forth, tempted by the rising of
the clear full moon behind the woods. After sitting nearly an hour in
the dressing-room, Thérèse put faith in the housekeeper’s prophecy
that her master would stay abroad till after midnight, like a child as
he always was, or one that lived on air, the first few days after his
coming down from town. Thérèse looked out and longed for another
ramble. The dressing-room lamp shed a pearly light through the
room; but a golden planet hung over the opposite beechen grove: a
small bright fire burned in the grate; but it was less cheering than the
bracing evening air: the time-piece ticked drowsily amidst the
silence; but it was less soothing than the coming and going of the
night-breeze among the elms in the green walk. Thérèse could not
resist. Once more she ran out, promising herself that she would be
back in ten minutes,—long before her mistress should be ready for
her. In an hour, startled by the striking of the village clock, she
returned, and found Letitia, half undressed, still gazing from the
window.
“Ah, madam!” cried Thérèse, terrified; “I am very, very wrong....”
As she hastened, with trembling hands, to throw off her cloak, and
arrange the toilet-table, appealing the while to the moon and other
temptations, Letitia, under a sudden impulse, ran and kissed the
astonished Thérèse, crying, “O Thérèse, how happy we shall be
here!” Thérèse returned the kiss again and again before she stopped
to consider what she was about. As soon as Letitia could repress her
inclination to laugh, she observed that they seemed all to have set
aside common rules to-day, and to have their heads turned alike by
coming into the country. After this, Thérèse would be in waiting at the
proper hour, and she herself....
“And you, madam ...” said Thérèse, half-smiling. “You will not
make me forget that there is one in this country who loves me as
some love me at home; but this will redouble my respect, madam.”
“I hope it will, Thérèse; for I need to be reminded now and then.... I
was not always lady F——, you know; and a moon-light night makes
me forget these things sometimes. We are all equal in reality, except
when ignorance, and all that comes of ignorance, separates us from
one another; so there may be friendship,—there is friendship
between you and me, Thérèse.”
“The knowledge which you have given me, madam, will make this
friendship my secret treasure. No one will know it who cannot also
be your friend.—But many ladies put confidence in their maids, and
tell them such things as I have never heard from you. Mrs. Philips....”
“Mrs. Philips, I suspect, Thérèse, had much more to tell than she
ever was told; at least, her secrets were of a kind that will never be
known to come from me. Your confessor shall never have to warn
you against me,—unless, indeed, it be my heresy. I would not spoil
you, my dear; and that is the reason why I keep you so much with
me. It would be hard if I did not love you and let you love me. Now
go to bed; and when the sun shines, instead of the moon, we must
forget all the wild things we have done this first day.”
“I shall never be fit to be a countess,” was her confession to lord F
——; “I kissed my maid last night.”
“What, Philips!”
“O no, no. That would be idiotcy. Philips is at Brighton, you know,
where lady Frances spoils her by a more pernicious familiarity than
mine with Thérèse. But really this girl wins one’s heart as if she had
been born one’s younger sister.”
“I dare say she is some countess, or countess’s daughter in
disguise; or so some romantic ladies might fancy.”
“Ladies who think that nobility is only hereditary. There is disguised
nobility in Thérèse; but her patent is sealed with an impress which
there are few to recognize, and it is deposited where not many
trouble themselves to look for it.”
“Side by side with yours, love. Happily, your nobility of that better
kind needs be disguised no more than the lesser which you have
acquired. This was the chief satisfaction I had in giving you the
lesser.”
“We will look among the equality folks, as White calls them, for
specimens of natural nobility. According to their theory, such always
assumes its rank among them, does it not?”
“This is one of the professed objects of their system; but it is not
fair to look for its fulfilment in such small societies as they have yet
been able to form. Master minds are thinly sown.”
“There needs not equality of outward condition,” observed Letitia,
“to make the best minds master minds. Those who, by virtue of a
patent of mental nobility, have held sway over the national mind,
have been of all ranks.”
“And will so continue to be; for, as long as men are unlike one
another, there will be a distinction of ranks, though the distinction
may be maintained by a better principle than heritage. Rank and
wealth will, I trust, be in time distributed according to natural laws;
but degrees of rank and wealth there will always be; and the
advocates of a system of equality would greatly promote their cause
by a frank recognition of this truth. While all evidence from which a
judgment can be formed is before them, and they come to a
conclusion in direct opposition to the evidence, I cannot, however
much I may respect them on some accounts, think them wise and
safe guides of the people. The necessity of inequality of condition
may be established thus.”
“But first tell me whether their favourite principle of co-operation
necessarily involves equality of condition.”
“They would tell you ‘yes.’ I say ‘no.’ They hold that competition is
both the cause and effect of inequality of condition; whereas certain
advocates of co-operation in another country hold, (and I think
wisely,) that their principle stands a better chance where a gradation
of rank and property is allowed. I so far agree with these last as to
believe the time to be discernible when co-operation, in a certain
sense, shall prevail,—meaning thereby, when all interests shall be
harmonized instead of opposed; but that this includes equality of
condition, I cannot allow, since varieties of character seem to me to
forbid such equality.”
“There must be an inequality of physical and mental powers, at all
events.”
“Surely; and therefore an inequality in the produce of individual
labour. No one labours, or ever will labour, without a view to the
fruits; and those fruits, however appropriated, are property. If a giant
produces ten times as much as a dwarf, and each is allowed the
same middle portion of the fruits, for his maintenance and
enjoyment, is it to be supposed that the giant will trouble himself
henceforth to produce more than the dwarf?”
“He will be more likely to seize some of the dwarf’s portion.”
“Certainly; and hence it is clear that the only security of society lies
in awarding to all their rights, and enforcing upon all their duties; and
what are rights but a man’s exclusive power over his own produce?
What are his duties but allowing to others the possession of their
produce?”
“You do not think then that the giant and the dwarf would be alike
contented with having everything they could want or wish for
administered to them in return for a certain portion of their labour.
You do not look forward to the lion dandling the kid.”
“I should be afraid the lion would be dandling the kid when he
ought to be out in quest of food. If there was no inducement to giants
to produce more than dwarfs, there would soon be little to administer
to anybody. The consumption of giants would soon have to be
provided for by the labour of a community of dwarfs.”
“The giants would foresee this, and then....”
“Instead of working harder for no recompense, they would
withdraw,—the mightiest first, and then the next strongest, and so
on, till the weakest of the dwarfs would be left to shift for themselves
as they best might.”
“And then would come the days of potatoes and wooden
trenchers, of which you were speaking one day.—But this is
supposing men to have the same passions and desires that they
have now; whereas they are to be educated into a better state.”
“With all my heart: but the utmost that education can do is to
extend man’s views, to exalt his aims, to strengthen and vivify his
powers,—not to change his nature. His nature involves inequality of
powers; and this decree of Providence can never be set aside, or its
operation neutralized by any decree of man that the fruits of those
powers shall be equally divided.”
“Certainly not; for such a decree of man involves injustice. If the
giant feels it to be unjust that he must give to others the fruits of his
labour, the dwarf may also complain that he enjoys no more than the
giant, though he works ten times as hard.”
“The dwarf’s complaint would thus be against Providence, and the
giant’s against man; but both show that equality is an arbitrary state,
good neither for each nor for all. Nothing but compulsion would
retain the giant in it long; and thus it is clear that, where there is
liberty, there cannot be equality.”
“What becomes of the old cry of Liberty and Equality?”
“It relates, I imagine, to an equality of rights. It means an open field
and fair play to every one. This kind of equality I am doing all I can in
my office to procure, by doing away with the protection to some
which imposes burdens upon others. By the same principle I am
bound to oppose that arbitrary equality which enriches the weak with
the fruits of the strongman’s labours.”
“But there is no force used. All who bind themselves to equality do
it voluntarily.”
“Certainly. The only applicable force is force of argument, and the
opposition I bring is an opposition of reasons. If these should not
prevail, a little experience will soon finish the business. I am only
sorry that any should be dazzled with a delusive prospect of ease
and luxury, when their efforts should be guided in another direction
for the relief of their grievous burdens. At a time when every one
should be bent on regulating the labour market, providing for the
utmost permanent growth of capital, and lessening the burdens of
taxation, we cannot spare any from these grand objects to be urging
on the increase of capital at the expense of a much greater increase
of population, and amusing themselves with visions of what can
never be achieved by the means they propose. Man must and will be
better served as the world grows older; but it will be by giving the
eternal laws of society fair play, and not by attempting to subvert
them. I shall be surprised if you hear anything from our neighbours in
the village which will not bear the construction I have put upon the
system as laid down by its originators.”
“Suppose I make myself popular among them at once by telling
them my tale of last night.”
“There is no need, my dear. I trust they do us the justice to believe
that our affections graduate according to a truer scale than that of
hereditary rank.”
“You have shown that they do by marrying me.”
“All people show it in the most important circumstances of their
lives,—in their attachments. Alas for man, if the movements within
must correspond with the outward state! Whom then would kings
love?”
“And (what is more important) how should the poverty-stricken
look up through the ranks above him, and say, with hope in his eye
and assurance in his voice, ‘I am a brother?’ How else should the
stirring thought be kept alive in him that his rights will not be for ever
overlaid, his claims not be for ever incompatible with those of his
brethren? Natural affinities are ever acting, even now, in opposition
to circumstance. They will in time direct us to the due control of
circumstance. Meanwhile, let no class imagine that any other class
denies the existence of these affinities, or resists their workings.—I
will go and see how they are acting in the village.—Shall I bring you
some of Mrs. White’s snuff?”
“Why, thank you, I am not aware of any affinity between a rappee
canister and my nostrils. But the old sexton is a snuff-taker. Call
upon him by all means, and show him that you understand his
likings. He will gratify some of yours, if you find him in a talkative
mood.”

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Solid Oxide Fuel Cells From Electrolyte Based To Electrolyte Free Devices Chunwen Sun 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

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

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

Solid Oxide Fuel Cell with Ionic Conducting Electrolyte

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

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

M+ (Li+, Na+) O– O2– CO32–

(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–