锂离子电池正极材料的结构设计与改性_王兆翔

232/320113PROGRESSINCHEMISTRYVol.23No.2/3Mar.201120109201011*973No.2009CB220100[e-mail]*100190。、。TM912.4TM910.2A1005-281X201102/3-0284-18StructuralDesignandModificationofCathodeMaterialsforLithiumIonBatteriesWangZhaoxiangChenLiquanHuangXuejieLaboratoryforSolidStateIonicsInstituteofPhysicsChineseAcademyofSciencesBeijing100190ChinaAbstractThecathodepositiveelectrodeisthesingleormajordonoroflithiumionsincurrentlithiumionbatteries.Itisbecomingthebottlenecktotheincreaseofenergydensityandthedecreaseofcostoflithiumionbatteries.Thisreviewpresentstheresearchprogressinourlaboratoryinsurfacemodificationandstructuraldesigningofcathodematerialsafterabriefintroductiontothestructurestheperformancefeaturesandthemainproblemsofsometypicalcathodematerials.KeywordslithiumionbatterycathodematerialssurfacemodificationsstructuraldesigningsubstitutionContents1Introductionofcathodematerials1.1Hexagonallayer-structuredLiMO2M=NiCoorMn1.2Hexagonallayer-structuredmulti-transition-metalLiMO21.3Lithium-richcathodematerialsxLi2MO3·1－xLiM′O21.4Spinel-structuredLiMn2O41.5Olivine-structuredLiMPO41.6Boratecathodematerials1.7Otherpolyanioncathodematerials2Structuraldesignandelementalsubstitutionofolivinestructuredcathodematerials2.1Theory-guidedstructuraldesignandelementaldopingtoLiFePO42.2Olivine-structuredphosphatesolidsolutions2.3Summary3Electrolytecorrosionandsurfacemodification3.1Electrolytecorrosiontoelectrodesurfaces3.2Newunderstandingandnewwaysofsurfacemodification3.3Summary4Prospectstohigh-capacitycathodematerials202/3·285·、、、、。。。1。1234567。。。LiCoO2、LiNi0.5Mn0.5O2LiNi1/3Co1/3Mn1/3O2、LiMn2O4、Li1+xMxM′1－xO2+xxLi2MO3·1－xLiM′O2LiFePO4、Li2FeSiO4LiNiVO4。。1.1LiMO2M=NiCoMn1.1.1LiCoO2LiCoO2。LiCoO2274mAh/g130150mAh/g。LiCoO2、。LiCoO2α-NaFeO2R3mLi+Co2+。Li+LiCoO210－1110－12m2/sLi+Li1－xCoO2x1—4。Li1－xCoO2c56。H1→H2x=0.07—0.25c2%Co—Co7—9。。x=0.5。-。c10。LiCoO23.94VH1H24.05V4.17V。LiCoO20.554.4V。、。、LiCoO2。LiCoO2Mn1112Al13—15。AlPO4、Al2O3MgO16—18200mAh/g。LiCoO2。LiCoO2Co、、LiCoO2。1.1.2LiNiO2LiNiO2LiCoO2NiO6Ni—O2.09A4Ni—O1.91A。LiNiO2200mAh/gLiCoO2。Li+Li0.95NiO22×10－11m2/s19。LiNiO2。LixNiO2Ni2+Li+。。NiLi20。LiNiO221。McBreen22400℃Li0.34NiO2O2Li0.24NiO2250℃。·286·23NiLiNiO2MgAl。LiNiO2LiNi1－xMyO2M=CoMnFeCr。。LiNi0.8Co0.15Al0.05O2。LiNiO2。1.1.3LiMnO2LiMnO2Pmmn。LiMnO2。Ohzuku23LiMnO22.0—4.5V190mAh/g。LiMnO2Mn3+J-TC2/m。LiMnO2NaMnO2Mn3+。24LiMnO2Mn3+Mn3+。LiMnO2。1.2LiNi1－x－yCoxMnyO20≤xy≤1x+y≤1LiNiO2。x=y。Ni+2Co+3Mn+4。Mn4+Co3+。Ni+2+4Co3+。150—190mAh/g。LiNi0.5Mn0.5O2LiNiO2。NMRLiNi0.5Mn0.5O2Ni2+/Mn4+。Li0.4Ni0.5Mn0.5O2Li+Ni。188mAh/g、4.5V。。。21CoLiNi0.5Mn0.5O2LiNi0.5Mn0.5O2。0—0.5。Co。。NiMn。Co。MnLiMnxCo0.2Ni0.8－xO2。MnNiONi+3+2Mn+4。MnLiMnxCo0.2Ni0.8－xO2。LiNi0.5Co0.2Mn0.3O2175mAh/g。25Ni1－x－yCoxMnyOH2、。LiNi1－x－yCoxMnyO2。LiNi0.8Co0.1Mn0.1O2Ni2+Ni3+。O2186mAh/g168mAh/g。LiNi1－x－yCoxMnyO2。。DSC。MITCeder26LiNi1/3Co1/3Mn1/3O22/3·287·。LiNi1/3Co1/3Mn1/3O2。27XXANESLiNi1/3CO1/3Mn1/3O2Mn、Co、NiKNi—OLi1－xNi1/3Co1/3Mn1/3O2NiNi2+/Ni3+Ni3+/Ni4+Ni2+/Ni4+3.6—3.9VMnCoMn4+Co3+。NiCoMn。。Ni—ODebye-WallerJ-TNi3+。Mn-MNi-MDebye-WallerNi2+Mn4+。。Shin28Chen29LiNixCo1－2xMnxO21/3≤x≤1/2x。PatouxDoeff30900℃LiNi1/3CO1/3O2。Reddy31850℃900℃LiNO3+LiCl4.0%2.5%。32LiNi1/3Co1/3Mn1/3O2FTIRSEI。FTIR。。4.9V1MLiPF6/EC+DMCLiPF6SEI。。SEISEI。FTIRSEI。SEI4.9V。、。。LiNi1/3Co1/3Mn1/3O2。Sony2005。。。1.3xLi2MO3·1－xLiM′O2Li2MnO3C2/m33。Li2MnO3LiLi1/3Mn2/3O2Li+Mn4+MLi6MnOLiMnLiLi2MO3。LiMnO2286mAh/g。Thackeray34—36Li2MnO3Li2O·MnO2Li2OLi2－2xMnO3－xMnO2·1－xLi2MnO3。Li2－2xMnO3－xxLiMnO2·1－xLi2MnO3.Li2MnO3LiMnO2。ZrLi2MnO3MnxMnO2·1－xLi2Mn1－yZryO3。Li2TiO3LiMn0.5Ni0.5O20.05Li2TiO3·0.95LiMn0.5Ni0.5O2175mAh/g37。Li2MO3xLi2MO3·1－xLiM′O2M=MnTiZrM′=MnCoNi200mAh/g。。。。4.5VLiM′O2Li+Li2MO3LiLi。Li2MO3Li。·288·234.5VLi2MnO3LiMnO2MO2Ni4+O2Li2O。40—100mAh/g38。、。。1.4LiMn2O4LiMn2O4、、、、。LiMn2O4Fd3m32e。16d1/88a。。10－14—10－12m2/s。LiMn2O4148mAh/g140mAh/g。40x0.1Li+Aγ-MnO20.1x0.5ABLi0.5Mn2O44.15Vx0.5Li+CLiMn2O4B4.03—3.9V。4V。Li+16cLi2Mn2O43.0V。Li+3V/Mn3+Jahn-Teller。LiMn2O43.0V。LiMn2O4。。Jahn-Teller。Eriksson39Mn3+。Li2Mn2O4Mn3.5。Mn。Mn、。LiMn2O4AlLiAlO2Al2O3。Lee40AlMnLiMn2O44V。LiAlO2LiMn2－xAlxO4。LiMn2O4LiMn2O4、41。AlLiMn2O4。、LiMn2O4。1.5LiFePO4LiMPO4M=FeNiMnCo1997Goodenough42LiFePO4。LiFePO4、、、、、、、。LiFePO4Pmnb4LiFePO4。LiFePO4a=4.6922Ab=10.3324Ac=6.0105A。LiFePO4P、FeO6PO4。FeO64FeO6。Fe—OPO4PO4FeO6FeO6PO4。2/3·289·LiFePO46.81%2.59%。PO3－4Li+LiFePO4。Prosini43GITT1.8×10－16—2.2×10－14cm2/s。LiFePO4～10－9S/cm。LiFePO4170mAh/g3.4V。LiFePO4。LiFePO4170mAh/g。Goodenough4244XRDLi+LiFePO4/LiFePO4-FePO4。Li+LiFePO4FePO4、LiFePO4LiFePO4/FePO4。LiFePO4、FePO4。Thomas45Li+/Mosaic。。Goodenough。。P5+PO43－。DSC147J/g250—360℃LiFePO4。LiFePO4。LiFePO4、、、、LiFePO4。Croce461%CuAg-LiFePO4。LiFePO4。Ravet471%80℃1C160mAh/g。Huang48LiFePO4/CLiFePO4100—200nm。49RuO2LiFePO4。LiFePO4LiCoPO4LiMnPO4Li2VPO4。1.6BO3－358.8PO3－495.0。LiMBO3M=FeMnCoLiFeBO3220mAh/g。2001Guyomard50LiMBO3M=MnFeCoLiFeBO3LiMBO3M=MgMnCoZn。0.04。LiFeBO3Fe2+/Fe3+3.1—2.9V。2002Allen51LiMBO3LiFeBO370%。LiMnBO3。LiFeBO32.6VFe2+/Fe3+。200752Li2O-Fe2O3-B2O3LiFeBO32.3V91.8mAh/g。。2008Li2CO3H3BO3FeC2O42H2OLiFeBO3535mA/g125.8mAh/g。50mA/g88.6mAh/g。LiFeBO5%。