Modeling and Diagnostics of Polymer Electrolyte Fuel Cells

411 Pages·2010·8.628 MB·English

by  Xinyu Huang, Ken Reifsnider (auth.), Chao-Yang Wang, Ugur Pasaogullari (eds.)

MODERN ASPECTS OF
ELECTROCHEMISTRY, No. 49:
MODELING AND
DIAGNOSTICS OF POLYMER
ELECTROLYTE
FUEL CELLS
Forothertitlespublishedinthisseries,goto
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Modern Aspects of
Electrochemistry
SeriesEditors:
RalphE.White
DepartmentofChemicalEngineering
UniversityofSouthCarolina
Columbia,SC29208
ConstantinosG.Vayenas
DepartmentofChemicalEngineering
UniversityofPatras
Patras26500
Greece
ManagingEditor:
MariaE.Gamboa-Aldeco
1107RaymerLane
Superior,CO80027
MODERN ASPECTS OF
ELECTROCHEMISTRY, No. 49:
MODELING AND
DIAGNOSTICS OF POLYMER
ELECTROLYTE
FUEL CELLS
Edited by
Ugur Pasaogullari
UniversityofConnecticut,USA
Chao-Yang Wang
ThePennsylvaniaStateUniversity,USA
123
Editors
UgurPasaogullari Chao-YangWang
UniversityofConnecticut DepartmentofMechanical
CenterforCleanEnergy andNuclearEngineering
Engineering PennStateUniversity
44WeaverRoadU-5233 16802UniversityPark
StorrsCT06269-5233 Pennsylvania
USA 301CReberBldg.
[email protected] USA
[email protected]
SeriesEditors
RalphE.White ConstantinosG.Vayenas
DepartmentofChemical DepartmentofChemical
Engineering Engineering
UniversityofSouthCarolina UniversityofPatras
Columbia,SC29208 Patras26500
Greece
ManagingEditor
MariaE.Gamboa-Aldeco
1107RaymerLane
Superior,CO80027
ISSN0076-9924
ISBN978-0-387-98067-6 e-ISBN978-0-387-98068-3
DOI10.1007/978-0-387-98068-3
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Preface
Polymer electrolyte fuel cells (PEFCs) or proton exchange mem-
brane fuel cells (PEMFCs) have been suggested as alternatives
to replace many existing energy conversion technologies, includ-
inginternalcombustionenginesandbatteries.Themostsignificant
advances in PEFC technology achieved in the last decade have
occurred in areas related to automotive applications, namely cold-
start capabilities, enhanced durability and better understanding of
watermanagementandmasstransportlosses.
This volume of Modern Aspects of Electrochemistry is
intended to provide an overview of advancements in experimental
diagnosticsandmodelingofpolymerelectrolytefuelcells.Chapters
by Huang and Reifsnider and Gu et al. provide an in-depth review
of the durability issues in PEFCs as well as recent developments
in understanding and mitigation of degradation in the polymer
membraneandelectrocatalyst.
Enabling cold start, the startup of PEFC stacks from subzero
temperatures, is a very important capability achieved only within
thelastfewyears.TajiriandWangprovideatutorialoverviewofthe
requirementsforcoldstart,andprovideasummaryofexperimental
diagnosticsandcold-startmodelingstudies.
Chapters 4–6 address specific diagnostic methods in PEFCs.
Martin et al. provide a detailed review of methods for distributed
diagnostics of species, temperature, and current in PEFCs in
Chapter 4. In Chapter 5, Hussey and Jacobson describe the oper-
ationalprinciplesofneutronradiographyforin-situvisualizationof
liquidwaterdistribution,andalsooutlineissuesrelatedtotemporal
and spatial resolution. Tsushima and Hirai describe both magnetic
resonance imaging (MRI) technique for visualization of water in
PEFCs and tunable diode laser absorption spectroscopy (TDLAS)
formeasurementofwatervaporconcentrationinChapter6.
Diffusionmedia(DM)arepronetofloodingwithliquidwater.
Although the DM is an essential component of PEFCs that enable
distributionofspeciesandcollectionofcurrentandheat,littlewas
knownaboutcapillarytransportinDMsuntilrecently.InChapters7
Gostick et al. provide a description of liquid water transport in
porousDMduetocapillarityanddescribeexperimentaltechniques
usedtocharacterizeDMproperties.
v
vi Preface
ThefinaltwochaptersdiscussmodelingofPEFCs.Mukherjee
and Wang provide an in-depth review of meso-scale modeling of
two-phase transport, while Zhou et al. summarize both the sim-
ulation of electrochemical reactions on electrocatalysts and the
transport of protons through the polymer electrolyte using atom-
isticsimulationtoolssuchasmoleculardynamicsandMonteCarlo
techniques.
Eachchapterinthevolumeisself-contained;thereforetheydo
notneedtobereadinacertainorder.
Special thanks are due to 23 authors who contributed to this
volume.
U.Pasaogullari
UniversityofConnecticut,Storrs,CT,USA
C.-Y.Wang
ThePennsylvaniaStateUniversity,UniversityPark,PA,USA
Contents
Chapter1
DURABILITYOFPEMFUELCELLMEMBRANES
XinyuHuangandKenReifsnider
1. Summary . . . . . . . . . . . . . . . . . . . . . . 1
2. ReviewofPEMFuelCellDegradation
PhenomenaandMechanisms . . . . . . . . . . . . 2
3. MembraneDegradation . . . . . . . . . . . . . . 6
3.1. StressinMembraneandMEAs . . . . . . . . 7
3.2. MechanicalCharacterizationofMembranes . 11
3.3. ChemicalDegradationProcesses . . . . . . . 15
3.4. MechanicalDegradationProcesses . . . . . . 18
3.5. Interactions of Chemical and
MechanicalDegradation . . . . . . . . . . . 26
4. AcceleratedTestingandLifePrediction . . . . . . 31
4.1. AcceleratedDegradationTestingand
DegradationMetrics. . . . . . . . . . . . . . 31
4.2. ProgressiveDegradationModelof
CombinedEffects . . . . . . . . . . . . . . . 35
5. Mitigation. . . . . . . . . . . . . . . . . . . . . . 39
References . . . . . . . . . . . . . . . . . . . . . . . . 42
Chapter2
MODELINGOFMEMBRANE-ELECTRODE-ASSEMBLY
DEGRADATIONINPROTON-EXCHANGE-MEMBRANE
FUELCELLS–LOCALH STARVATIONANDSTART–STOP
2
INDUCEDCARBON-SUPPORTCORROSION
WenbinGu,PaulT.Yu,RobertN.Carter,RohitMakharia,and
HubertA.Gasteiger
1. Introduction . . . . . . . . . . . . . . . . . . . . . 45
2. KineticModel . . . . . . . . . . . . . . . . . . . 49
vii
viii Contents
2.1. ElectrodeKinetics . . . . . . . . . . . . . . . 49
2.2. LocalH StarvationModel . . . . . . . . . . 54
2
2.3. Start–StopModel . . . . . . . . . . . . . . . 57
3. CoupledKineticandTransportModel . . . . . . . 60
3.1. ModelDescription . . . . . . . . . . . . . . 60
3.2. LocalH StarvationSimulation . . . . . . . . 63
2
3.3. Start–StopSimulation . . . . . . . . . . . . . 72
4. Pseudo-CapacitanceModel. . . . . . . . . . . . . 76
4.1. MechanismDescription . . . . . . . . . . . . 76
4.2. ModelDescription . . . . . . . . . . . . . . 78
4.3. ThePseudo-capacitiveEffect . . . . . . . . . 80
5. SummaryandOutlook . . . . . . . . . . . . . . . 82
ListofSymbols . . . . . . . . . . . . . . . . . . . . . 83
References . . . . . . . . . . . . . . . . . . . . . . . . 85
Chapter3
COLDSTARTOFPOLYMERELECTROLYTEFUELCELLS
KazuyaTajiriandChao-YangWang
1. Introduction . . . . . . . . . . . . . . . . . . . . . 89
2. EquilibriumPurgeColdStart. . . . . . . . . . . . 96
2.1. EquilibriumPurge . . . . . . . . . . . . . . . 96
2.2. IsothermalColdStart . . . . . . . . . . . . . 97
2.3. ProtonConductivityatLowTemperature . . . 97
2.4. EffectsofKeyParameters . . . . . . . . . . . 100
2.5. ORRKineticsatLowTemperatures . . . . . 107
2.6. Short-PurgeColdStart . . . . . . . . . . . . 110
3. WaterRemovalDuringGasPurge . . . . . . . . . 112
3.1. Introduction . . . . . . . . . . . . . . . . . . 112
3.2. PurgeCurve . . . . . . . . . . . . . . . . . . 114
3.3. TwoCharacteristicParametersfor
WaterRemoval . . . . . . . . . . . . . . . . 115
3.4. StagesofPurge . . . . . . . . . . . . . . . . 117
3.5. EffectofKeyParameters . . . . . . . . . . . 118
3.6. HFRRelaxation . . . . . . . . . . . . . . . . 124
4. ConcludingRemarks . . . . . . . . . . . . . . . . 126
References . . . . . . . . . . . . . . . . . . . . . . . . 127
Contents ix
Chapter4
SPECIES,TEMPERATURE,ANDCURRENTDISTRIBUTION
MAPPINGINPOLYMERELECTROLYTEMEMBRANEFUEL
CELLS
JonathanJ.Martin,JinfengWu,XiaoZiYuan,
andHaijiangWang
1. Introduction . . . . . . . . . . . . . . . . . . . . . 129
2. SpeciesDistributionMapping . . . . . . . . . . . 130
2.1. SpeciesandPropertiesofInterest . . . . . . . 130
2.2. MethodologyandResults . . . . . . . . . . . 132
2.3. DesignImplications . . . . . . . . . . . . . . 149
3. TemperatureDistributionMapping. . . . . . . . . 152
3.1. MethodologyandResults . . . . . . . . . . . 153
3.2. DesignImplications . . . . . . . . . . . . . . 155
4. CurrentDistributionMapping . . . . . . . . . . . 156
4.1. MethodologyandResults . . . . . . . . . . . 156
4.2. DesignImplications . . . . . . . . . . . . . . 165
5. ConcludingRemarks . . . . . . . . . . . . . . . . 166
References . . . . . . . . . . . . . . . . . . . . . . . . 167
Chapter5
HIGH-RESOLUTIONNEUTRONRADIOGRAPHYANALYSIS
OFPROTONEXCHANGEMEMBRANEFUELCELLS
D.S.HusseyandD.L.Jacobson
1. Introduction . . . . . . . . . . . . . . . . . . . . . 175
2. NeutronRadiography FacilityLayout
AndDetectors . . . . . . . . . . . . . . . . . . . 177
2.1. NeutronSourcesandRadiographyBeamlines 177
2.2. NeutronImagingDetectors . . . . . . . . . . 181
3. WaterMetrologywithNeutronRadiography . . . 184
3.1. NeutronAttenuationCoefficientof
Water,μ . . . . . . . . . . . . . . . . . . . 184
w
x Contents
3.2. SourcesofUncertaintiesinNeutron
Radiography . . . . . . . . . . . . . . . . . . 187
4. RecentInSituHigh-ResolutionNeutron
RadiographyExperimentsofPEMFCs. . . . . . . 195
4.1. Proof-of-PrincipleExperiments . . . . . . . . 195
4.2. InSitu,Steady-StateThrough-Plane
WaterContent . . . . . . . . . . . . . . . . . 196
4.3. Dynamic Through-Plane Mass
TransportMeasurements . . . . . . . . . . . 197
5. Conclusions . . . . . . . . . . . . . . . . . . . . . 198
References . . . . . . . . . . . . . . . . . . . . . . . . 199
Chapter6
MAGNETICRESONANCEIMAGINGANDTUNABLEDIODE
LASERABSORPTIONSPECTROSCOPYFORIN-SITU
WATERDIAGNOSTICSINPOLYMERELECTROLYTE
MEMBRANEFUELCELLS
ShohjiTsushimaandShuichiroHirai
1. Introduction . . . . . . . . . . . . . . . . . . . . . 201
2. MagneticResonanceImaging(MRI):As
aDiagnosticToolforIn-SituVisualization
ofWaterContentDistributioninPEMFCs . . . . . 202
2.1. BasicPrincipleofMRI . . . . . . . . . . . . 202
2.2. MRISystemHardwareforPEMFC
Visualization . . . . . . . . . . . . . . . . . 206
2.3. MRISignalCalibrationforWater
ContentinPEM . . . . . . . . . . . . . . . . 209
2.4. InSituVisualizationofWaterin
PEMFCUsingMRI . . . . . . . . . . . . . . 209
3. Tunable Diode Laser Absorption
Spectroscopy(TDLAS):AsaDiagnostic
ToolforIn-SituDetectionofWaterVapor
ConcentrationinPEMFCs . . . . . . . . . . . . . 213
3.1. BasicPrincipleofTDLAS . . . . . . . . . . 213
3.2. TDLASSystemHardwareforWater
VaporMeasurement . . . . . . . . . . . . . . 214