汽车用锂电池研究（英文）

LithiumBatteryResearchforVehicleTechnologyatBrookhavenNationalLab.X.Q.Yang,K.W.Nam,X.J.Wang,Y.N.Zhou,H.S.Lee,O.Haas,L.Wu,andY.ZhuBrookhavenNationalLab.Upton,NY11973,USAH.Li,X.HuangandL.ChenInstituteofPhysics,ChineseAcademyofSciences,Beijing,ChinaTobepresentedat2009InternationalForumonLi-ionBatteryTechnology&IndustrialDevelopmentBeijing,China,October16-18,2009CenterforFunctionalNano-materialsatBNLNSLSexperimentalfloorCombininginsitusynchrotronXASandXRDtechniquestododiagnosticstudiesofbatterymaterialsandcomponentsatornearoperatingconditionsInsitucellMonochromaticX-raysIOITIRefIonizationDetectorsReferencemetalfoilInsitucellMonochromaticX-raysIOITIRefIonizationDetectorsReferencemetalfoilPositionsensitivedetector(PSD)InsitucellIncidentX-raysDiffractionpatternPositionsensitivedetector(PSD)InsitucellIncidentX-raysDiffractionpatternXASsetupXASsetupXRDsetupXRDsetupMylarsheetBoltholesX-raywindowGasketSeparatorCucurrentcollectorAlcurrentcollectorActivematerialLifoilInsitucellInsitucellMylarsheetBoltholesX-raywindowGasketSeparatorCucurrentcollectorAlcurrentcollectorActivematerialLifoilInsitucellInsitucellX19A&X18B(XAS)andX14A&X18A(XRD)atNationalSynchrotronLightSource(NSLS)4SynchrotronbasedX-raydiffractionandabsorptionspectroscopyduringheatingStudiesonthermaldecomposition(thermalabusetolerance)ofcathodematerialsCombinationofthesetechniqueswillclearlyprovidevaluableinformationaboutthermalstabilityofvarioustypesofcathodesmaterialsandhelpdesigningcathodematerialswithsuperiorthermalabusetolerance!!3.SoftX-rayabsorptionspectroscopystudyofchargedcathodematerialsIncidentsoftX-ray(500~1000eV)HeatingChargedcathodeUltrahighvacuum(bulkinformation)Fluorescentdetector(surfaceinformation)ElectronyielddetectorElectronicstructuralinformationatthesurface(~50Å)andinthebulk(~3000Å)inelemental-selectivewayduringheating3.SoftX-rayabsorptionspectroscopystudyofchargedcathodematerialsIncidentsoftX-ray(500~1000eV)HeatingChargedcathodeUltrahighvacuum(bulkinformation)Fluorescentdetector(surfaceinformation)ElectronyielddetectorIncidentsoftX-ray(500~1000eV)HeatingChargedcathodeUltrahighvacuum(bulkinformation)Fluorescentdetector(surfaceinformation)ElectronyielddetectorIncidentsoftX-ray(500~1000eV)HeatingChargedcathodeUltrahighvacuum(bulkinformation)Fluorescentdetector(surfaceinformation)ElectronyielddetectorElectronicstructuralinformationatthesurface(~50Å)andinthebulk(~3000Å)inelemental-selectivewayduringheating1.Time-resolvedXRDstudyofchargedcathodematerialsSamplesincapillarySamplesincapillaryHeatingAveragestructuralinformation(longrangeorder)duringheating1.Time-resolvedXRDstudyofchargedcathodematerialsSamplesincapillarySamplesincapillaryHeatingSamplesincapillarySamplesincapillarySamplesincapillarySamplesincapillaryHeatingAveragestructuralinformation(longrangeorder)duringheating2.HardX-rayabsorptionspectroscopystudyofchargedcathodematerialsIncidenthardX-ray(6~10keV)HeatingChargedcathodeIoItLocalstructuralandelectronicstructuralinformation(bulk)inelemental-selectivewayduringheating2.HardX-rayabsorptionspectroscopystudyofchargedcathodematerialsIncidenthardX-ray(6~10keV)HeatingChargedcathodeIoItIncidenthardX-ray(6~10keV)HeatingChargedcathodeIoItLocalstructuralandelectronicstructuralinformation(bulk)inelemental-selectivewayduringheating535.536.036.537.0Phase22(121)(311)Phase3Phase135.536.036.537.037.52(=1.54)T(121)T(311)H(121)H(311)C-LiFePO4C-LiMn1/4Fe1/4Co1/4Ni1/4PO4TwophasereactionNosignificantsolidsolutionregionExistenceofsolidsolutionregionsAppearanceofIntermediatephaseInsituXRDofC-LiFe1/4Mn1/4Co1/4Ni1/4PO4duringfirstchargeComparisonwithpureC-LiFePO467InsituXASofC-LiFe1/4Mn1/4Co1/4Ni1/4PO4duringfirstcharge0204060801001201401601803.54.04.55.0Capacity(mAhg-1)Voltage(Vvs.Li/Li+)(III)(II)(I)26mAhg-160mAhg-1insituXASK.W.Nam,X.Q.Yangetal,ElectrochemistryCommunication,inpress(2009).71107120713071400.00.51.01.52.06540655065600.00.51.01.52.07710772077300.00.61.21.8832083308340835083600.00.51.0Normalizedintensity(a.u.)Beforecharge8mAhg-117mAhg-126mAhg-135mAhg-153mAhg-170mAhg-188mAhg-1168mAhg-1FeK-edgeBeforecharge22mAhg-131mAhg-140mAhg-148mAhg-157mAhg-175mAhg-193mAhg-1163mAhg-1MnK-edgeEnergy(eV)Beforecharge22mAhg-141mAhg-160mAhg-170mAhg-179mAhg-199mAhg-1137mAhg-1166mAhg-1CoK-edgeBeforecharge36mAhg-165mAhg-193mAhg-1126mAhg-1142mAhg-1151mAhg-1171mAhg-1180mAhg-1NiK-edgeEdgeshifttowardhigherenergypositionincreaseinoxidationstateThreevoltageplateausat~3.6,4.2and4.7VRedoxreactionsofFe2+/Fe3+,Mn2+/Mn3+andCo2+/Co3+.Voltageplateauover~4.9VMostlyelectrolytedecomposition.Electronicstructuralchangesfollowingthelithiumextractionquitewelltobalancetheelectricalneutrality.Cut-offvoltage:~5.0V,C/7rate8ExperimentalSetupatX7B(NSLS)withImagePlateDetector(IPD)andinsitucell10203040Twotheta(=0.92255A)MylarsheetBoltholesX-raywindowGasketSeparatorCucurrentcollectorAlcurrentcollectorCathodeAnodeinsitucellThermalstabilitystudyoflayeredcathodematerials(safetyrelatedissue)Whenx=0.5(50%ofSOC)inLixMO2Li0.5M(3.5+)O2(layered,R-3m)Li0.5M(3.5+)1.0O2(disorderedspine