FUEL CELL FUNDAMENTALS Third Edition RYAN O’HAYRE DepartmentofMetallurgicalandMaterialsEngineering ColoradoSchoolofMines [PhD,MaterialsScienceandEngineering,StanfordUniversity] SUK-WON CHA SchoolofMechanicalandAerospaceEngineering SeoulNationalUniversity [PhD,MechanicalEngineering,StanfordUniversity] WHITNEY G. COLELLA TheG.W.C.WhitingSchoolofEngineering,andTheEnergy,Environment, SustainabilityandHealthInstitute TheJohnsHopkinsUniversity GaiaEnergyResearchInstitute [Doctorate,EngineeringScience,TheUniversityofOxford] FRITZ B. PRINZ R.H.AdamsProfessorofEngineering DepartmentsofMechanicalEngineeringandMaterialScienceandEngineering StanfordUniversity Thisbookisprintedonacid-freepaper.♾ Copyright©2016byJohnWiley&Sons,Inc.Allrightsreserved. PublishedbyJohnWiley&Sons,Inc.,Hoboken,NewJersey. PublishedsimultaneouslyinCanada. 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CONTENTS PREFACE xi ACKNOWLEDGMENTS xiii NOMENCLATURE xvii I FUELCELLPRINCIPLES 1 Introduction 3 1.1 WhatIsaFuelCell? / 3 1.2 ASimpleFuelCell / 6 1.3 FuelCellAdvantages / 8 1.4 FuelCellDisadvantages / 11 1.5 FuelCellTypes / 12 1.6 BasicFuelCellOperation / 14 1.7 FuelCellPerformance / 18 1.8 CharacterizationandModeling / 20 1.9 FuelCellTechnology / 21 1.10 FuelCellsandtheEnvironment / 21 1.11 ChapterSummary / 22 ChapterExercises / 23 v vi CONTENTS 2 FuelCellThermodynamics 25 2.1 ThermodynamicsReview / 25 2.2 HeatPotentialofaFuel:EnthalpyofReaction / 34 2.3 WorkPotentialofaFuel:GibbsFreeEnergy / 37 2.4 PredictingReversibleVoltageofaFuelCellunderNon-Standard-State Conditions / 47 2.5 FuelCellEfficiency / 60 2.6 ThermalandMassBalancesinFuelCells / 65 2.7 ThermodynamicsofReversibleFuelCells / 67 2.8 ChapterSummary / 71 ChapterExercises / 72 3 FuelCellReactionKinetics 77 3.1 IntroductiontoElectrodeKinetics / 77 3.2 WhyChargeTransferReactionsHaveanActivationEnergy / 82 3.3 ActivationEnergyDeterminesReactionRate / 84 3.4 CalculatingNetRateofaReaction / 85 3.5 RateofReactionatEquilibrium:ExchangeCurrentDensity / 86 3.6 PotentialofaReactionatEquilibrium:GalvaniPotential / 87 3.7 PotentialandRate:Butler–VolmerEquation / 89 3.8 ExchangeCurrentsandElectrocatalysis:HowtoImproveKinetic Performance / 94 3.9 SimplifiedActivationKinetics:TafelEquation / 97 3.10 DifferentFuelCellReactionsProduceDifferentKinetics / 100 3.11 Catalyst–ElectrodeDesign / 103 3.12 QuantumMechanics:FrameworkforUnderstanding CatalysisinFuelCells / 104 3.13 TheSabatierPrincipleforCatalystSelection / 107 3.14 ConnectingtheButler–VolmerandNernstEquations(Optional) / 108 3.15 ChapterSummary / 112 ChapterExercises / 113 4 FuelCellChargeTransport 117 4.1 ChargesMoveinResponsetoForces / 117 4.2 ChargeTransportResultsinaVoltageLoss / 121 4.3 CharacteristicsofFuelCellChargeTransportResistance / 124 4.4 PhysicalMeaningofConductivity / 128 4.5 ReviewofFuelCellElectrolyteClasses / 132 CONTENTS vii 4.6 MoreonDiffusivityandConductivity(Optional) / 153 4.7 WhyElectricalDrivingForcesDominateChargeTransport(Optional) / 160 4.8 QuantumMechanics–BasedSimulationofIonConductioninOxide Electrolytes(Optional) / 161 4.9 ChapterSummary / 163 ChapterExercises / 164 5 FuelCellMassTransport 167 5.1 TransportinElectrodeversusFlowStructure / 168 5.2 TransportinElectrode:DiffusiveTransport / 170 5.3 TransportinFlowStructures:ConvectiveTransport / 183 5.4 ChapterSummary / 199 ChapterExercises / 200 6 FuelCellModeling 203 6.1 PuttingItAllTogether:ABasicFuelCellModel / 203 6.2 A1DFuelCellModel / 206 6.3 FuelCellModelsBasedonComputationalFluidDynamics(Optional) / 227 6.4 ChapterSummary / 230 ChapterExercises / 231 7 FuelCellCharacterization 237 7.1 WhatDoWeWanttoCharacterize? / 238 7.2 OverviewofCharacterizationTechniques / 239 7.3 InSituElectrochemicalCharacterizationTechniques / 240 7.4 ExSituCharacterizationTechniques / 265 7.5 ChapterSummary / 268 ChapterExercises / 269 II FUELCELLTECHNOLOGY 8 OverviewofFuelCellTypes 273 8.1 Introduction / 273 8.2 PhosphoricAcidFuelCell / 274 8.3 PolymerElectrolyteMembraneFuelCell / 275 8.4 AlkalineFuelCell / 278 8.5 MoltenCarbonateFuelCell / 280 viii CONTENTS 8.6 Solid-OxideFuelCell / 282 8.7 OtherFuelCells / 284 8.8 SummaryComparison / 298 8.9 ChapterSummary / 299 ChapterExercises / 301 9 PEMFCandSOFCMaterials 303 9.1 PEMFCElectrolyteMaterials / 304 9.2 PEMFCElectrode/CatalystMaterials / 308 9.3 SOFCElectrolyteMaterials / 317 9.4 SOFCElectrode/CatalystMaterials / 326 9.5 MaterialStability,Durability,andLifetime / 336 9.6 ChapterSummary / 340 ChapterExercises / 342 10 OverviewofFuelCellSystems 347 10.1 FuelCellSubsystem / 348 10.2 ThermalManagementSubsystem / 353 10.3 FuelDelivery/ProcessingSubsystem / 357 10.4 PowerElectronicsSubsystem / 364 10.5 CaseStudyofFuelCellSystemDesign:StationaryCombinedHeat andPowerSystems / 369 10.6 CaseStudyofFuelCellSystemDesign:SizingaPortableFuelCell / 383 10.7 ChapterSummary / 387 ChapterExercises / 389 11 FuelProcessingSubsystemDesign 393 11.1 FuelReformingOverview / 394 11.2 WaterGasShiftReactors / 409 11.3 CarbonMonoxideClean-Up / 411 11.4 ReformerandProcessorEfficiencyLosses / 414 11.5 ReactorDesignforFuelReformersandProcessors / 416 11.6 ChapterSummary / 417 ChapterExercises / 419
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