锂离子电池容量衰减机理和副反应翻译个人翻译的外文文献Word文档下载推荐.docx
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锂离子电池容量衰减机理和副反应翻译个人翻译的外文文献Word文档下载推荐.docx
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Lithium-IonBatteries
锂离子电池容量衰减机机理和副反应
PankajAroratandRalphE.White*
作者:
CenterForElectrochemicalEngineering,DepartmentofChemicalEngineering,UniversityofSouthCarolina,Columbia,SouthCarolina29208,USA
美国,南卡罗来纳,年哥伦比亚29208,南卡罗来纳大学,化学工程系,中心电化学工程
ABSTRACT
Thecapacityofalithium-ionbatterydecreasesduringcycling.Thiscapacitylossorfadeoccursduetoseveraldifferentmechanismswhichareduetoorareassociatedwithunwantedsidereactionsthatoccurinthesebatteries.Thesereactionsoccurduringoverchargeoroverdischargeandcauseelectrolytedecomposition,passivefilmformation,activematerialdissolution,andotherphenomena.Thesecapacitylossmechanismsarenotincludedinthepresentlithium-ionbatterymathematicalmodelsavailableintheopenliterature.Consequently,thesemodelscannotbeusedtopredictcellperformanceduringcyclingandunderabuseconditions.Thisarticlepresentsareviewofthecurrentliteratureoncapacityfademechanismsandattemptstodescribetheinformationneededandthedirectionsthatmaybetakentoincludethesemechanismsinadvancedlithium-ionbatterymodels.
Introduction
Thetypicallithium-ioncell(Fig.1)ismadeupofacokeorgraphitenegativeelectrode,anelectrolytewhichservesasanionicpathbetweenelectrodesandseparatesthetwomaterials,andametaloxide(suchasLiCoO2,LiMn2O4,orLiNiO2)positiveelectrode.Thissecondary(rechargeable)lithium-ioncellhasbeencommercializedonlyrecently.Batteriesbasedonthisconcepthavereachedtheconsumermarket,andlithium-ionelectricvehiclebatteriesareunderstudyinindustry.Thelithium-ionbatterymarkethasbeeninaperiodoftremendousgrowtheversinceSonyintroducedthefirstcommercialcellin1990.Withenergydensityexceeding130Wh/kg(e.g.,MatsushitaCGR17500)andcyclelifeofmorethan1000cycles(e.g.,Sony18650)inmanycases,thelithium-ionbatterysystemhasbecomeincreasinglypopularinapplicationssuchascellularphones,portablecomputers,andcamcorders.Asmorelithium-ionbatterymanufacturersenterthemarketandnewmaterialsaredeveloped,costreductionshouldspurgrowthinnewapplications.SeveralmanufacturerssuchasSonyCorporation,SanyoElectricCompany,MatsushitaElectricIndustrialCompany,MoliEnergyLimited,andA&
TBatteryCorporationhavestartedmanufacturinglithium-ionbatteriesforcellularphonesandlaptopcomputers.Yoda1hasconsideredthisadvancementanddescribedafuturebatterysocietyinwhichthelithium-ionbatteryplaysadominantrole.
Severalmathematicalmodelsoftheselithium-ioncellshavebeenpublished.Unfortunately,noneofthesemodelsincludecapacityfadeprocessesexplicitlyintheirmathematicaldescriptionofbatterybehavior.Theobjectiveofthepresentworkistoreviewthecurrentunderstandingofthemechanismsofcapacityfadeinlithium-ionbatteries.Advancesinmodelinglithium-ioncellsmustresultfromimprovementsinthefundamentalunderstandingoftheseprocessesandthecollectionofrelevantexperimentaldata.
Someoftheprocessesthatareknowntoleadtocapacityfadeinlithium-ioncellsarelithiumdeposition(overchargeconditions),electrolytedecomposition,activematerialdissolution,phasechangesintheinsertionelectrodematerials,andpassivefilmformationovertheelectrodeandcurrentcollectorsurfaces.Quantifyingthesedegradationprocesseswillimprovethepredictivecapabilityofbatterymodelsultimatelyleadingtolessexpensiveandhigherqualitybatteries.Significantimprovementsarerequiredinperformancestandardssuchasenergydensityandcyclelife,whilemaintaininghighenvironmental,safety,andcoststandards.Suchprogresswillrequireconsiderableadvancesinourunderstandingofelectrodeandelectrolytematerials,andthefundamentalphysicalandchemicalprocessesthatleadtocapacitylossandresistanceincreaseincommerciallithium-ionbatteries.Theprocessofdevelopingmathematicalmodelsforlithiumioncellsthatcontainthesecapacityfadeprocessesnotonlyprovidesatoolforbatterydesignbutalsoprovidesameansofunderstandingbetterhowthoseprocessesoccur.
PresentLithium-IonBatteryModels
Thedevelopmentofadetailedmathematicalmodelisimportanttothedesignandoptimizationoflithiumsecondarycellsandcriticalintheirscale-up.Westdevelopedapseudotwo-dimensionalmodelofasingleporousinsertionelectrodeaccountingfortransportinthesolutionphaseforabinaryelectrolytewithconstantphysicalpropertiesanddiffusionoflithiumionsintothecylindricalelectrodeparticles.Theinsertionprocesswasassumedtobediffusionlimited,andhencecharge-transferresistanceattheinterfacebetweenelectrolyteandactivematerialwasneglected.LaterMaoandWhitedevelopedasimilarmodelwiththeadditionofaseparatoradjacenttotheporousinsertionelectrode.Thesemodelscoveronlyasingleporouselectrode;
thus,theydonothavetheadvantagesofafull-cell-sandwichmodelforthetreatmentofcomplex,interactingphenomenabetweenthecelllayers.ThesemodelsconfinethemselvestotreatinginsertionintoTiS2withthekineticsfortheinsertionprocessassumedtobeinfinitelyfast.SpotnitzaccountedforelectrodekineticsintheirmodelfordischargeoftheTiS2,intercalationcathode.
Thegalvanostaticchargeanddischargeofalithiummetal/solidpolymerseparator/insertionpositiveelectrodecellwasmodeledusingconcentrated-solutiontheorybyDoyle.Themodelisgeneralenoughtoincludeawiderangeofseparatormaterials,lithiumsalts,andcompositeinsertionelectrodes.Concentrated-solutiontheoryisusedtodescribethetransportprocesses,asithasbeenconcludedthationpairingandionassociationareveryimportantinsolidpolymerelectrolytes.Thisapproachalsoprovidesadvantagesoverdilutesolutiontheorytoaccountforvolumechanges.Butler-Volmer-typekineticexpressionswereusedinthismodeltoaccountforthekineticsofthecharge-transferprocessesateachelectrode.ThepositiveelectrodeinsertionprocesswasdescribedusingPick'
slawwithaconstantlithiumdiffusioncoefficientintheactivematerial.Thevolumechangesinthesystemandfilmformationatthelithium/polymerinterfacewereneglectedandaverysimplisticcaseofconstantelectrodefilmresistanceswasconsidered.Long-termdegradationofthecellduetoirreversiblereactions(sidereactions)orlossofinterfacialcontactisnotpredictableusingthismodel.
Fullerdevelopedageneralmodelforlithiumioninsertioncellsthatcanbeappliedtoanypairoflithium-ioninsertionelectrodesandanybinaryelectrolytesystemgiventherequisitephysicalpropertydata.Fullerworkdemonstratedtheimportanceofknowingthedependenceoftheopen-circuitpotentialonthestateofchargefortheinsertionmaterialsusedinlithium-ioncells.Theslopesofthesecurvescontrolthecurrentdistributioninsidetheporouselectrodes,withmoreslopedopen-circuitpotentialfunctionsleadingtomoreuniformcurrentdistributionsandhencebetterutilizationofactivematerial.OptimizationstudieswerecarriedoutfortheBellcoreplasticlithium-ionsystem.Themodelwasalsousedtopredicttheeffectsofrelaxationtimeonmultiplecharge-dischargecyclesandonpeakpower.
Doylemodifiedtheduallithium-ionmodeltoincludefilmresistancesonbothelectrodesandmadedirectcomparisonswithexperimentalcelldatafortheLiC6-LiPF6,ethylenecarbonate/dimethylcarbonate(EC/DMC),KynarFLEX-ILiyMn2O4system.Comparisonsbetweendataandthenumericalsimulationssuggestedthatthereisadditionalresistancepresentinthesystemnotpredictedbypresentmodels.Thedischargeperformanceofthecellswasdescribedsatisfactorilybyincludingeitherafilmresistanceontheelectrodeparticlesorbycontactresistancesbetweenthecelllayersorcurrent-collectorinterfaces.OneemphasisofthisworkwasintheuseofthebatterymodelforthedesignandoptimizationofthecellforparticularapplicationsusingsimulatedRagoneplots.
Thermalmodelingisveryimportantforlithiumbatteriesbecauseheatproducedduringdischargemaycauseeitherirreversiblesidereactionsormeltingofmetalliclithium,ChenandEvanscarriedoutathermalanalystsoflithiumionbatteriesduringcharge-dischargeandthermalrunawayusinganenergybalanceandasimplifieddescriptionoftheelectrochemicalbehaviorofthesystem.Theiranalysisofheattransportandtheexistenceofhighlylocalizedheatsourcesduetobatteryabuseindicatedthatlocalizedheatingmayraisethebatterytemperatureveryquicklytothethermalrunawayonsettemperature,abovewhichitmaykeepincreasingrapidlyduetoexothermicsidereactionstriggeredathightemperature.PalsandNewmandevelopedamodeltopredictthethermalbehavioroflithiummetal-solidpolymerelectrolytecellsandcellstacks.Thismodelcoupledanintegratedenergybalancetoafullcell-sandwichmodeloftheelectrochemicalbehaviorofthecells.Bothofthesemodelsemphasizedtheimportanceofconsiderationsofheatremovalandthermalcontrolinlithiumpolymerbatterysystems.
VerbruggeandKochdevelopedamathematicalmodelforlithiumintercalationprocessesassociatedwithacylindricalcarbonmicrofiber.Theycharacterizedandmodeledthelithiumintercalationprocessinsingle-fibercarbonmicroelectrodesincludingtransportprocessesinbothphasesandthekineticsofchargetransferattheinterface.Theprimarypurposeofthemodelwastopredictthepotentialasafunctionoffractionaloccupancyofintercalatedlithium.Theoverchargeprotectionfo
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