Table Of ContentEdited by
Vladislav V. Kharton
Solid State
Electrochemistry II
Related Titles
Kharton,V. V. (ed.)
Solid State Electrochemistry I:
Fundamentals,MaterialsandtheirApplications
2009
ISBN:978-3-527-32318-0
Vielstich, W.,Gasteiger,H.A., Yokokawa, H.(eds.)
Handbook of Fuel Cells
AdvancesinElectrocatalysis,Materials,DiagnosticsandDurability,Volumes5&6
2009
ISBN:978-0-470-72311-1
Endres, F.,MacFarlane, D., Abbott,A. (eds.)
Electrodeposition from Ionic Liquids
2008
ISBN:978-3-527-31565-9
Bard,A.J.,Stratmann,M.,Gileadi,E.,Urbakh,M.,Calvo,E.J.,Unwin,P.R.,Frankel,
G. S.,Macdonald, D., Licht, S.,Schäfer, H.J.,Wilson,G. S.,Rubinstein, I.,Fujihira,
M.,Schmuki, P., Scholz,F.,Pickett, C. J.,Rusling,J. F.(eds.)
Encyclopedia of Electrochemistry
11VolumeSet
2007
ISBN:978-3-527-30250-5
Hamann, C. H., Hamnett,A., Vielstich, W.
Electrochemistry
2007
ISBN:978-3-527-31069-2
Staikov,G. T.(ed.)
Electrocrystallization in Nanotechnology
2007
ISBN:978-3-527-31515-4
Edited by
Vladislav V. Kharton
Solid State Electrochemistry II
Electrodes, Interfaces and Ceramic Membranes
TheEditor AllbookspublishedbyWiley-VCHarecarefully
produced.Nevertheless,authors,editors,and
VladislavV.Kharton publisherdonotwarranttheinformationcontained
UniversityofAveiro inthesebooks,includingthisbook,tobefreeof
CICECO,Dept.ofCeramicsandGlassEngin. errors.Readersareadvisedtokeepinmindthat
3810-193Aveiro statements,data,illustrations,proceduraldetailsor
Portugal otheritemsmayinadvertentlybeinaccurate.
LibraryofCongressCardNo.: appliedfor
BritishLibraryCataloguing-in-PublicationData
Acataloguerecordforthisbookisavailablefromthe
BritishLibrary.
Bibliographicinformationpublishedby
theDeutscheNationalbibliothek
TheDeutscheNationalbibliothekliststhis
publicationintheDeutscheNationalbibliografie;
detailedbibliographicdataareavailableonthe
Internetathttp://dnb.d-nb.de.
#2011Wiley-VCHVerlag&Co.KGaA,Boschstr.
12,69469Weinheim,Germany
Allrightsreserved(includingthoseoftranslationinto
otherlanguages).Nopartofthisbookmaybe
reproducedinanyform–byphotoprinting,
microfilm,oranyothermeans–nortransmittedor
translatedintoamachinelanguagewithoutwritten
permissionfromthepublishers.Registerednames,
trademarks,etc.usedinthisbook,evenwhennot
specificallymarkedassuch,arenottobeconsidered
unprotectedbylaw.
Typesetting ThomsonDigital,Noida,India
PrintingandBinding betz-druckGmbH,Darmstadt
CoverDesign Grafik-DesignSchulz,Fußgönheim
PrintedintheFederalRepublicofGermany
Printedonacid-freepaper
ISBNPrint:978-3-527-32638-9
ISBNoBook:978-3-527-63556-6
ISBNePDF:978-3-527-63558-0
ISBNePub:978-3-527-63557-3
ISBNMobi:978-3-527-63559-7
V
Contents
Preface XV
List of Contributors XIX
1 IonicMemoryTechnology 1
AnChen
1.1 Introduction 1
1.2 IonicMemorySwitchingMechanisms 4
1.2.1 Cation-BasedResistiveSwitchingMechanism 4
1.2.2 Anion-BasedResistiveSwitchingMechanism 6
1.3 MaterialsforIonicMemories 8
1.3.1 MetalSulfideSolidElectrolytes 9
1.3.2 Ge-BasedChalcogenideSolidElectrolytes 9
1.3.3 OxideSolidElectrolytes 10
1.3.4 MiscellaneousOtherSolidElectrolytes 11
1.4 ElectricalCharacteristicsofIonicMemories 12
1.4.1 IonicMemoryDeviceCharacteristics 12
1.4.2 IonicMemoryArrayCharacteristics 18
1.4.3 ComparingIonicMemorywithOtherMemories 19
1.5 ArchitecturesforIonicMemories 20
1.5.1 CMOS-IntegratedArchitecture 20
1.5.2 CrossbarArrayArchitecture 21
1.5.3 CMOS/HybridArchitecture 21
1.6 ChallengesofIonicMemories 22
1.6.1 OverprogrammingandOvererasing 22
1.6.2 RandomDiffusionofMetalIonsandAtoms 22
1.6.3 ThermalStability 23
1.6.4 SwitchingSpeed 23
1.6.5 DegradationofInertElectrodes 24
1.7 ApplicationsofIonicMemories 24
1.7.1 Stand-AloneMemory 25
1.7.2 EmbeddedMemory 25
1.7.3 StorageClassMemory 25
VI Contents
1.8 Summary 26
References 26
2 CompositeSolidElectrolytes 31
NikolaiF.Uvarov
2.1 Introduction 31
2.2 InterfaceInteractionsandDefectEquilibriain
CompositeElectrolytes 32
2.2.1 DefectThermodynamics:FreeSurfaceofan
IonicCrystal 33
2.2.2 DefectThermodynamicsinComposites:Interfaces 37
2.2.3 ThermodynamicStabilityCriteriaandSurfaceSpreading 39
2.3 NanocompositeSolidElectrolytes:GrainSizeEffects 42
2.4 IonicTransport 50
2.5 OtherProperties 55
2.6 ComputerSimulations 56
2.7 DesignoftheCompositeSolidElectrolytes:General
ApproachesandPerspectives 58
2.7.1 VaryingChemicalNatureoftheIonicSalt–OxidePair 58
2.7.2 ChangingthePhysicalStateofIonicSalt 60
2.7.3 ChangingthePhysicalStateofthe‘‘Inert’’Component 61
2.7.4 AlterationoftheInertComponentMorphology:
TheGeometricAspects 61
2.7.5 MetacompositeMaterialsandNanostructuredSystems 62
2.7.6 AchievingtheNanoscaleLevel 62
2.8 CompositeMaterialsOperatingatElevatedTemperatures 64
2.9 Conclusions 65
References 66
3 AdvancesintheTheoreticalDescriptionofSolid–Electrolyte
SolutionInterfaces 73
OrestPizioandStefanSoko»owski
3.1 Introduction 73
3.2 TheoreticalApproaches 74
3.2.1 Background 74
3.2.2 InhomogeneousElectrolyteSolutions:Generalities 77
3.2.3 IntegralEquationsforSolid–ElectrolyteSolutionProblems 80
3.2.4 DensityFunctionalTheories 88
3.3 ComputerSimulations 100
3.3.1 SummationofLong-RangeForces 101
3.3.2 SimulationsofSimpleModelsforElectricDoubleLayer 104
3.3.3 SolventEffectsonElectricDoubleLayer:SimpleModels 109
3.3.4 SolventEffectsonElectricDoubleLayer:ModelsofWater 112
3.3.5 Summary 116
References 118
Contents VII
4 DynamicalInstabilitiesinElectrochemicalProcesses 125
IstvánZ.Kiss,TimeaNagy,andVilmosGáspár
4.1 Introduction 125
4.2 OriginandClassificationofDynamicalInstabilitiesin
ElectrochemicalSystems 126
4.2.1 ClassificationBasedonEssentialSpecies 127
4.2.1.1 ‘‘Truly’’or‘‘Strictly’’PotentiostaticSystems 128
4.2.1.2 NegativeDifferentialResistanceSystems 128
4.2.2 ClassificationBasedonNonlinearDynamics 131
4.3 Methodology 136
4.3.1 ExperimentalTechniques 136
4.3.1.1 TechniquesforTemporalDynamics 136
4.3.1.2 TechniquesforSpatialDynamics 136
4.3.2 DataProcessing 138
4.3.2.1 DigitalSignalProcessing 139
4.3.2.2 AnalysisofTimeSeriesDatawithToolsofNonlinear
Dynamics 140
4.4 Dynamics 142
4.4.1 Bistability 143
4.4.2 Oscillations 144
4.4.3 Chaos 150
4.4.4 Bursting 151
4.4.5 DynamicsofCoupledElectrodes 153
4.4.6 DynamicsofPatternFormation 158
4.5 ControlofDynamics 159
4.5.1 IRCompensation 160
4.5.2 PeriodicForcing 160
4.5.3 ChaosControl 162
4.5.4 DelayedFeedbackandTracking 163
4.5.5 AdaptiveControl 163
4.5.6 SynchronizationEngineering 165
4.5.7 EffectofNoise 167
4.6 TowardApplications 167
4.7 SummaryandOutlook 171
4.7.1 ElectrochemistryofSmallSystems 172
4.7.2 DescriptionofLarge,ComplexSystems 172
4.7.3 EngineeringStructures 172
4.7.4 IntegrationofElectrochemicalandBiologicalSystems 173
References 173
5 FuelCells:AdvancesandChallenges 179
SanPingJiangandXinWang
5.1 Introduction 179
5.1.1 PrincipleandClassificationofFuelCells 180
5.1.2 FuelsforElectrochemicalCells 183
VIII Contents
5.1.2.1 Hydrogen,Methanol,FormicAcid,andLiquidFuels 183
5.1.2.2 Methane,Hydrocarbons,andBiomass-DerivedRenewable
Fuels 185
5.2 AlkalineandAlkalineMembraneFuelCells 187
5.2.1 AlkalineFuelCells 187
5.2.1.1 HistoricDevelopmentandProspects 188
5.2.1.2 GasDiffusionCathode,ElectrolyteCarbonation,
andCorrosion 188
5.2.2 AlkalineMembraneFuelCells 190
5.2.2.1 AlkalineAnionExchangeMembranes 190
5.2.2.2 ElectrocatalystsinAlkalineMedium 192
5.3 PolymerElectrolyteMembraneFuelCells 194
5.3.1 TechnologyDevelopmentofPEMFCs 194
5.3.1.1 NafionandOtherPerfluorinatedMembranes 195
5.3.1.2 Pt,PtRu,andNonpreciousMetalCompositeElectrocatalysts 196
5.3.1.3 Self-HumidificationandElectrodeStructureOptimization 199
5.3.1.4 BipolarPlatesandStackDesign 200
5.3.1.5 Heat,WaterManagement,andModeling 202
5.3.1.6 DurabilityandDegradationofElectrocatalysts,
MembraneandCellPerformance 203
5.3.2 PEMFCswithLiquidFuels 204
5.3.2.1 DirectMethanolFuelCells 205
5.3.2.2 DirectFormicAcidFuelCells 208
5.3.2.3 DirectEthanolFuelCells 210
5.4 PhosphoricAcidFuelCellsandMoltenCarbonateFuelCells 211
5.4.1 PhosphoricAcidFuelCells 211
5.4.1.1 Electrocatalysts,Electrolyte,andGasDiffusionElectrode 212
5.4.1.2 SustainabilityandChallenges 213
5.4.2 MoltenCarbonateFuelCells 213
5.4.2.1 NiOCathode 214
5.4.2.2 Anode,StabilityandRetentionofElectrolyte,Corrosion
ofSeparatePlate,andComponentStability 215
5.4.2.3 DirectInternalReformingMCFCs 216
5.5 SolidOxideFuelCells 217
5.5.1 DevelopmentofKeyEngineeringMaterials 218
5.5.1.1 Anode 218
5.5.1.2 Cathode 222
5.5.1.3 Electrolytes 225
5.5.1.4 Interconnect,Sealing,andBalanceofPlant 228
5.5.2 SOFCStructuresandConfigurations 230
5.5.2.1 CellStructures 230
5.5.2.2 StackDesignandConfigurations 231
5.6 EmergingFuelCells 232
5.6.1 ProticIonicLiquidElectrolyteFuelCells 232
5.6.2 MicrobialFuelCells 232
Contents IX
5.6.3 BiofuelCells 235
5.6.4 MicrofluidicFuelCells 237
5.6.5 High-TemperatureProtonExchangeMembraneFuelCells 238
5.6.5.1 HT-PEMFCsBasedonPhosphoricAcid-DopedPBIPEM 238
5.6.5.2 HT-PEMFCsBasedonInorganicandCeramicPEM 239
5.6.6 Single-ChamberSolidOxideFuelCells 241
5.6.7 MicrosolidOxideFuelCells 242
5.6.8 DirectCarbonFuelCells 246
5.7 ApplicationsofFuelCells 247
5.8 FinalRemarks 249
References 252
6 ElectrodesforHigh-TemperatureElectrochemicalCells:
NovelMaterialsandRecentTrends 265
EkaterinaV.TsipisandVladislavV.Kharton
6.1 Introduction 265
6.2 GeneralComments 266
6.3 NovelCathodeMaterialsforSolidOxideFuelCells:
SelectedTrendsandCompositions 267
6.4 OxideandCermetSOFCAnodes:RelevantTrends 286
6.5 OtherFuelCellConcepts:Single-Chamber,Micro-,
andSymmetricalSOFCs 301
6.6 AlternativeFuels:DirectHydrocarbonandDirect
CarbonSOFCs 309
6.7 ElectrodeMaterialsforHigh-TemperatureFuelCellswith
Proton-ConductingElectrolytes 312
6.8 Electrolyzers,Reactors,andOtherApplicationsBasedon
OxygenIon-andProton-ConductingSolidElectrolytes 317
6.9 ConcludingRemarks 321
References 322
7 AdvancesinFabrication,Characterization,Testing,andDiagnosis
ofHigh-PerformanceElectrodesforPEMFuelCells 331
JinfengWu,WeiDai,HuiLi,andHaijiangWang
7.1 Introduction 331
7.2 AdvancedFabricationMethodsforHigh-PerformanceElectrodes 333
7.2.1 ConventionalHydrophobicPTFE-BondedGasDiffusion
Electrode 334
7.2.1.1 CatalystLayerCoatingontoGasDiffusionLayer 334
7.2.1.2 NafionImpregnation 335
7.2.1.3 MEAAssembly:HotPressing 336
7.2.2 Thin-FilmHydrophilicCatalystCoatedMembraneMethod 336
7.2.2.1 ScreenPrintingMethod 337
7.2.2.2 ModifiedDecalMethod 338
7.2.2.3 InkjetPrintingTechnology 338
X Contents
7.2.2.4 DirectSprayCoating 339
7.2.3 AdvancedFabricationMethodsforLowPtLoadingElectrodes 340
7.2.3.1 ElectrophoreticDeposition 340
7.2.3.2 PulseElectrodeposition 342
7.2.3.3 Electrospray 345
7.2.3.4 PlasmaSputtering 345
7.2.3.5 Sol-GelMethod 346
7.2.4 FabricationofGasDiffusionMedia 347
7.2.4.1 FabricationofGasDiffusionLayer 347
7.2.4.2 FabricationofMicroporousLayer 347
7.3 CharacterizationofPEMFuelCellElectrodes 348
7.3.1 SurfaceMorphologyCharacteristics 348
7.3.1.1 OpticalMicroscopy 348
7.3.1.2 ScanningElectronMicroscopy 349
7.3.1.3 ScanningProbeMicroscopy 352
7.3.2 MicrostructureAnalysis 354
7.3.3 PhysicalCharacteristics 356
7.3.3.1 Porosimetry 356
7.3.3.2 PermeabilityandGasDiffusivity 357
7.3.3.3 Wetting 358
7.3.3.4 Conductivity 360
7.3.4 CompositionAnalysis 361
7.3.4.1 EnergyDispersiveSpectrometry 361
7.3.4.2 ThermalGravimetricAnalysis 362
7.4 TestingandDiagnosisofPEMFuelCellElectrodes 364
7.4.1 ElectrochemicalTechniques 364
7.4.1.1 PolarizationCurves 364
7.4.1.2 CurrentInterrupt 365
7.4.1.3 ElectrochemicalImpedanceSpectroscopy 366
7.4.1.4 OtherElectrochemicalMethods 369
7.4.2 PhysicalandChemicalMethods 371
7.4.2.1 SpeciesDistributionMapping 371
7.4.2.2 TemperatureDistributionMapping 373
7.4.2.3 CurrentDistributionMapping 374
7.5 FinalComments 377
References 378
8 NanostructuredElectrodesforLithiumIonBatteries 383
RicardoAlcántara,PedroLavela,CarlosPérez-Vicente,
andJoséL.Tirado
8.1 Introduction 383
8.2 PositiveElectrodes:Nanoparticles,Nanoarchitectures,
andCoatings 384
8.2.1 LayeredOxides:LiMO 384
2
8.2.2 SpinelCompounds 385
