高安全长寿锂电池技术

0602872010/11(MCL/ITRI)Asthedevelopmentofmarketinlithium-ionbattery,thesafetyissueandcyclelifeofbatteriesbecomemoreimportant.Thebatterymanufactoriespaymuchattentiontothesafetydesignofbatteryanditshightemperatureperformance.Throughthisarticle,thepatentmapofseparator,techniquesoflithiumionbatterysafetyandlongcyclelifetechnologyathightemperaturehavebeensystematicallyintro-ducedandanalyzed./KeyWords(Lithium-ionBattery)(Separator)(LongCycleLifeatHighTemperature)3C2006(DELL)(SONY)(NOKIA)IBM(Separator)0612872010/11(Microporous)(ThermalRunaway)(Permeability)(Wettability)(InternalShortCircuit)(MicroporousPolymerMembrane)(InorganicCompositeMembrane)(Non-wovenFabricMats)(Polyolefin)PPPEPP/PEHDPEUHMWPEPEPPPEPPAl2O3MgOPVDF-HFP30~50µm(a)(b)0622872010/11(60~80%)(20~50µm)(GelPolymerElectrolyte;GPE)20%AsahiPPPEAl2O3TiO2(PVDF)(PVA)AsahiHipore®CelgardPPPE(ThermalShutdown)Celgard0632872010/11:PECelgardPE/PPPP/PE/PPPE/PP/PEPP/PE/PPPE/PP/PE(PunctureStrength)PPAsahiCelgardPPPEDegussaSeparion®(AlZrSi)(PET)PET(210°C)Matsushita(HeatResistantLayer;HRL)AlMgTiZrSiAsahiKaseiCelgardLLCDegussaMatsushitaBatteryIndustrialLGChem/CPISamsungSDIInventionofSeparatorforBatterySafetyPorousheat-resistantlayercoatingonseparatorMultilayeredpolyolefinmembraneassemblyPolymericnonwovenhavingceramiccoatingPorousheat-resistantlayerprovidebetweenseparatorandelectrodeGelpolymercoatingonseparatorSeparatorincludingorganicandinorganiccompoundAltertheMworcompositionofmicroporouspolyolefinMicroporousmembranecoatingonseparatorOrganic/InorganiccompositeseparatorCeramiclayercoatingonelectrodeMultilayeredpolyolefinmembraneassemblyAltertheMworcompositionofmicroporouspolyolefinNonwovenseparatorcoatingwithshutdownparticleModificatethesurfaceofseparatorGelpolymercoatingonseparatorModificatethesurfaceofseparatorModificatethesurfaceofseparatorPublicationNumberJP2007095668JP2009026733JP2006321841JP8138644JP2008254288US2007207376EP1507299US20070221567US20070134548EP1482578US20050084761US20060166085US20060003230US20050255769US20050084761US20080020190US20080190841CN100495804EP1768202US20060222940US20060051663EP1912274EP1768209EP1631998US20090311589US20090111026US20080292968CN1938881WO0034384CN100428557CN101459232US20080299461EP2101368US2002019256US20030118895*2000.01~2009.120642872010/11(PAN)LGSamsungSDILGPVDFPEGPCPAN40~60%SamsungSDI(PolyacrylatePolymethacrylateAcrylate-methacrylateCopolymer)SiO2Al2O3TiO2Argonne(Life)(Power)(Energy)(Safe)(LiFePO4)(LiMn2O4)(LNCM)(LNCA)(LiCoO2)ArgonneLTFOPSEIJetPropulsionLaboratory(JPL)CeramicMaterialPETNon-wovenMatDegussaSeparion®CoupleLifePowerEnergySafetyNCA/CarbonMnSpinel/CarbonFePhosphate/CarbonNMC/CarbonPFFFFOOOOLi–+:LTFOP0652872010/11·(1-x)LiMO2LNCALNCM(111)(DifferentialScanningCalorimeter;DSC)(Al2O3)(TriethylPhosphate)(TriphenylPhosphate)(TributylPhosphate)140°CSTOBASTOBAPTCCIDSTOBASTOBA55°C1.HFLiPF6LiPF6PF5LiFPOF3HFHFCN101409342AlTiZrLaZnMgAlTiZrLaZnMgTiO2ZrO2Al2O3La2O3ZnOMgOAl2O3Al2O3LiNi0.8Co0.2O20662872010/11°C60°C100Al2O3Al2O360°CAl2O3(Polypyrrole;PPy)LiFePO4/CLiFePO4/C-PPy55°C5CC-rate(5C)50055°C200SEM(a)LiFePO4/CSEM(b)LiFePO4/C-PPySEMC-rate(5C)200LiFePO4/CLiPF6HFLiFePO4/C-PPy2.LiPF6(EC)(PC)(EMC)DirectlyPourinAl(NO3)3SolutionHeatedintheAirLiNi0.8Co0.2O2ParticlesAl(OH)3onLiNi0.8Co0.2O2SurfaceAl2O3CoatedLiNi0.8Co0.2O2Al2O3LiNi0.8Co0.2O22001601208040Capacity(mAh/g)01020304050CycleNumbers60708090100BareCoated(a)2001601208040Capacity(mAh/g)01020304050CycleNumbers60708090100BareCoated(b)(a)25°C(b)60°C1000672872010/11(DEC)(DMC)(SEI)(FEC)(VC)(PS)(LithiumBis(oxalato)Borate;LiBOB)(LithiumDifluoroOxalateBorate;LiDFOB)CN1016353791~10%LiDFOB3~10%78~90%1~10%Argonne2010(LithiumTetrafluoroOxalatoPhosphate;LTFOP)1~3wt%LiPF6ECEMCLi1.1(Ni1/3Co1/3Mn1/3)0.9O2(MCMB)55°C1C2003wt%LTFOP97%2wt%92%1wt%87%80%(a)1601401201006080402000100200300400500600CycleNumberCapacity(mAh/g)PPy-LiFePO4/CLiFePO4/C55°C5C(a)LiFePO4/C(b)LiFePO4/C-ppy55°C200SEM10080604004080120160200CycleNumberNormalizedCapacity(%)3~4.0V,1C@55°CPristine2wt%LTFOP3wt%LTFOP1wt%LTFOP1201008060050100150200CycleNumberSpecificCapacity(mAh/g)55°C1C0682872010/11(LTFOP)(SEI)(b)55°C200LTFOPLTFOPSTOBASTOBA1.AsahiKasei,JP20070956682.AsahiKasei,JP20090267333.AsahiKasei,JP20063218414.AsahiKasei,JP20082542885.CelgardLLC,TW2694746.CelgardLLC,US20021369457.CelgardLLC,US20072073768.CelgardLLC,EP15072999.CelgardLLC,US2007022156710.Degussa,US2006016608511.Degussa,US2006000323012.Degussa,US2008002019013.Degussa,US2005025576914.MatsushitaElectric,CN10049580415.MatsushitaElectric,EP176820216.MatsushitaElectric,US200605166317.LGChem,EP163199818.LGChem,US2009031158919.SamsungSDI,CN10042855720.SamsungSDI,CN177695521.SamsungSDI,CN10145