Proton-conducting ceramics : from fundamentals to applied research

440 Pages·2016·14.935 MB·English

by  Marrony, Mathieu

Proton-
Conducting
Ceramics
© 2016 by Taylor & Francis Group, LLC
© 2016 by Taylor & Francis Group, LLC
Pan Stanford Series on Renewable Energy — Volume 2
Proton-
Conducting
Ceramics
From Fundamentals
to Applied Research
editors
Preben Maegaard
Anna Krenz
Wolfgang Palz
edited by
Mathieu Marrony
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© 2016 by Taylor & Francis Group, LLC
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Contents
Foreword
Preface
xi
1. Pr oton H ydration and Transport Properties in Proton- xix
Conducting Ceramics: Fundamentals and Highlights 1
P. Berger, F. Mauvy, J.-C. Grenier, N. Sata, A. Magrasó,
R. Haugsrud, and P. R. Slater
1.1 Thermodynamics of Hydration 2
1.1.1 Formation of Protonic Defects:
Generalities 2
1.1.2 Thermodynamic Parameters 4
1.1.3 Correlation of Thermodynamic and
Physicochemical Parameters 6
1.2 Proton Transport Mechanisms 9
1.2.1 Principles 9
1.2.2 Grain Boundary Resistance and
Space Charge Layer Effects 12
1.2.2.1 The brick-layer model 12
1.2.2.2 Space charge layer: The theory 13
1.2.2.3 Space charge layer model
applied to proton conductors 14
1.3 Characterization Tools 17
1.3.1 Electrochemical Impedance

Spectroscopy 17
1.3.1.1 Principles 18
3 .2.3.2 Examples 19
3 .2.3.3 Analysis 20
1.3.2 Nuclear Microprobe 24
1.3.2.1 Principles and apparatus 24
1.3.2.2 Formal hydrogen diffusion
measurements 26
1.3.2.3 Hydrogen transport within
ceramic microstructure 27
1.3.3 Neutron Scattering 28
1.3.3.1 Interaction between proton
and neutron 29
© 2016 by Taylor & Francis Group, LLC
vi Contents
1.3.3.2 Neutron diffraction 32
1.3.3.3 Inelastic neutron scattering 33
1.3.3.4 Quasi-elastic neutron
scattering 35
1.3.4 Thermogravimetric Analysis 37
1.3.4.1 Thermogravimetric analysis
of proton-conducting
ceramics as electrolyte 37
1.3.4.2 Thermogravimetric analysis
of electrode materials 37
1.3.5 Infrared Spectroscopy 43
1.3.5.1 Infrared absorption 44
1.3.5.2 Transmission spectroscopy 46
1.3.5.3 Reflection spectroscopy 47
1.3.6 Raman Investigation of Proton
Insertion in Oxide Ceramics 51
1.3.7 Electronic and Local Structure with
X-Ray Spectroscopic Techniques 55
1.3.7.1 Background methodology 55
2. Proton-Conductin1g. 3O.7xi.2de EMxaatmerpialelss of uses 5783
G. Taillades, J. Rozière, J. Dailly, N. Fukatsu,
A. Magrasó, R. Haugsrud, and P. R. Slater
2.1 Perovskites and Derivatives 74
2.1.1 Structural Characteristics and
Stability of ABO3-Based Simple
Perovskite 74
2.1.1.1 Structural properties 74
2.1.1.2 Formation of proton defects
and proton mobility through
ABO3-based perovskite 77
2.1.1.3 Proton conductivity and
stability of materials:
BaZrO3 against BaCeO3 8 2
2.1.2 Mixed Ce, Zr-Based, and Complex
Perovskite Materials 88
2.1.3 Brownmillerite A2B2O5-Based
Materials 95
2.1.3.1 Structural properties 96
© 2016 by Taylor & Francis Group, LLC
Contents vii
2.1.3.2 Hydration properties 96
2.1.3.3 Conductivity properties 98
2.1.3.4 Stability against CO2 100
2.2 Ortho-Phosphates, Ortho-Niobates, and
Ortho-Tantalates LnBO4 102
2.3 Rare-Earth Tungstates: Proton Conductors
with Fluorite-Related Structures 107
2.3.1 Stoichiometry and Crystal Structure 107
2.3.2 Conducting Properties and Doping
Strategies 109
2.3.3 Chemical Stability and Mechanical
Properties of Lanthanum Tungstate 114
2.4 (Other) Fluorite- and Pyrochlore-Related
High-Temperature Proton Conductors 115
2.5 Other Components 121
2.5.1 Acceptor-Doped Corundum (Alumina) 121
2.5.1.1 Proton conduction in
acceptor-doped alumina:
a short history 122
2.5.1.2 Location of movable
proton in crystal lattice 124
2.5.1.3 Drift mobility of proton 125
2.5.1.4 Electrochemical properties 126
2.5.2 Composite Oxides/Oxyacid Salts: The
“Intermediate” Proton Conductors 128
2.5.3 Mixed Protonic Electronic Conductors 135
2.5.3.1 Introduction 135
2.5.3.2 Trivalent doped perovskites 137
2.5.3.3 New class of proton
conductors 140
2.5.3.4 Multivalent component–
doped proton conductors 142
3. Synthesis and Pro2c.e5s.s3i.n5g MNie–tXh ocedrsm: Leotw m Caotestr i als 146
and Easy Industrial? 173
G. Taillades, P. Briois, J. Dailly, M. Marrony, and N. Sata
3.1 Synthesis Methods 174
3.1.1 Solid Route 174
3.1.1.1 Solid-state reaction 174
© 2016 by Taylor & Francis Group, LLC
viii Contents
3.1.1.2 Solid-state reactive sintering 176
3.1.1.3 Mechanosynthesis of
nanopowders of proton-
conducting electrolyte
materials 180
3.1.2 Sol–Gel Methods 181
3.1.2.1 The Pechini method 181
3.1.2.2 Hydrogelation of acrylates 182
3.1.3 Coprecipitation 184
3.1.3.1 Oxalate precipitation route 184
3.1.3.2 Carbonates and hydroxide as
precipitants 186
3.1.4 Combustion Synthesis 187
3.1.4.1 Glycine or urea solution
combustion 190
3.1.4.2 Citrate–nitrate
autocombustion 192
3.1.5 Other Wet-Chemical Routes 194
3.1.5.1 Reverse micelle method 194
3.1.5.2 Spray pyrolysis 196
3.2 Processing Routes 198
3.2.1 Pressing/Copressing Methods 198
3.2.1.1 Principle 198
3.2.1.2 Compaction defects 201
3.2.1.3 Isostatic compaction 202
3.2.1.4 Mechanics of pressing 203
3.2.1.5 Sintering step 204
3.2.2 Plasma Techniques 205
3.2.2.1 Magnetron sputtering 205
3.2.2.2 Thermal spraying 232
3.2.3 Humid Routes 245
3.2.3.1 Tape-casting method 245
3.2.3.2 Screen-printing method 257
3.2.3.3 Case of coating methods
on an anode tubular support 260
3.2.4 Other Routes 262
3.2.4.1 Single crystal 262
3.2.4.2 Pulsed laser deposition 264
3.2.4.3 Epitaxial growth 268
3.2.4.4 Super lattice and multilayers 270
© 2016 by Taylor & Francis Group, LLC
Contents ix
4. Typical Applications of Protonic Ceramic Cells:
A Way to Market? 291
M. Marrony, H. Matsumoto, N. Fukatsu, and M. Stoukides
4.1 Proton-Conducting Material: An
Electromotive Force 292
4.1.1 Components in Fuel Cell Devices 292
4.1.1.1 Electrochemical
performance 292
4.1.1.2 Influence of parameter keys
on protonic ceramic cell
performance: fuel quality
and operating conditions 308
4.1.1.3 Reliability assessment 310
4.1.1.4 Toward the protonic
ceramic cell scaling-up 316
4.1.2 Membrane Signals (Hydrogen
Sensors) 322
4.1.2.1 Open-circuit voltage of
galvanic cell based on
proton-conducting ceramics 322
4.1.2.2 Design of hydrogen sensor
considering the use and the
properties of materials 328
4.1.2.3 Performance and reliability
of hydrogen sensor for
practical use 332
4.2 Proton-Conducting Material:
An Electrochemical Hydrogen Transport 337
4.2.1 Membrane Separators 337
4.2.1.1 Type of materials and
mechanisms for hydrogen
separation 337
4.2.1.2 Hydrogen pumps 341
4.2.1.3 Electrode materials and
activity correlating with
electrolyte 343
4.2.1.4 Mixed conducting membrane 346
4.2.2 Electrolyte in Steam Electrolysis 352
4.2.2.1 Basic principle 352
© 2016 by Taylor & Francis Group, LLC
x Contents
4.2.2.2 Performance and reliability
of proton-conducting
ceramic cell in steam
electrolysis 356
4.3 Proton-Conducting Material as Membrane
Reactors 361
4.3.1 Introduction, Operation Modes,
and Designs of a PCCR 361
4.3.2 Applications of PCCR: Methods and
Techniques Used 364
4.3.2.1 Selective conduction of ions 364
4.3.2.2 Electrochemical promotion
of catalytic reactions 365
4.3.2.3 Chemical cogeneration 366
4.3.2.4 Methane conversion to C2
hydrocarbons 368
4.3.2.5 Other reactions of methane
activation 373
4.3.2.6 Decomposition of alcohols 373
4.3.2.7 Reactions of alkanes and
alkenes 374
4.3.2.8 Forward and reverse water
gas shift 374
x
4.3.2.9 Decomposition and
reduction of NO 374
4.3.2.10 Reactions of sulfur
compounds 375
4.4 Proton-Conducting Material as
Electrocatalyst in Solid-State Ammonia
Synthesis 377
4.4.1 Introduction: Catalytic vs.
Electrocatalytic NH3 Synthesis 377
4.4.2 Solid-State Ammonia Synthesis in
Proton-Conducting Cell Reactor:
Methods and Materials Tested 378
4.4.3 Electrochemical Promotion during
General Conclusion SSAS 383
Index 405
413
© 2016 by Taylor & Francis Group, LLC