三元正极材料LiNiCoMnO2的研究进展

—。俞会根，王恒，盛军102602、。Recentprogressincobalt/nickel/manganeseoxidesaspositiveelectrodematerialsYUHui-gen,WANGHeng,SHENGJun(ElectricalPowerTrainDepartment,BeijingElectricvehicleCo.Ltd.,Beijing102602,China)2001Ohzuku[1]、LiNi0.5Mn0.5O2。。Li[Ni-Co-Mn]O2Li-CoO2、LiNiO2LiMnO2Co[2]NiMn。EV、HEV。、2015180Wh/kg150Wh/kgLiFePO4LiMnO2。1。

 
LiCoOLiNiOLiMnOLiMnOLiFePOLiNiCoO 1980198519961983200119971992/(gc)2.3.02.42.62.22.42.22.42.03.01.01.7/(mAhg)274274286148280170275/(mAhg)14015019021010015010012015522090160170/V4.03.83.03.83.83.23.8!#50050050030002000$%&’(()*)*+()*+(,-./00+1+1+1’112%34435656+4789:;=;=?=?=;=@?=?=@AB?=Li[Co1/3Ni1/3Mn1/3]O21。Li[Ni-Co-Mn]O2LiCoO2α-NaFeO2XRD2Li3aNi、CoMn3bO6c。Li。KoyamaY[3]Li[Ni1/3Co1/3Mn1/3]O2[]R30°(－0.17eV)1(a)(0.06eV)1(b)。[4]。。TanakaILi1－x[Co1/3Ni1/3Mn1/3]O2Li+0x1/3Ni2+/Ni3+1/3x2/3Ni3+/Ni4+2/3x1Co3+/Co4+[5]。W.S.YoonCo3+/Co4+4.6VCo[6]。。rNi2+=0.069nmrLi+=0.076nm“”[7]。rCo3+=0.55nmNi2+Li+3a。Mn4+、。[8-9]。。Li[Ni1/3Co1/3Mn1/3]O2333Li[Ni0.5Co0.2Mn0.3]O2523。Li[Ni0.8Co0.1Mn0.1]O2811Li[Ni0.6Co0.2Mn0.2]O2311Li[Ni0.4Co0.2Mn0.4]O2424。Li-CoO2。、、。。。、。Hyun-SooKim[10]Li[Ni1/3Co1/3Mn1/3]O21%0.2C5C153.4132.0mAh/g3%5C0.2C90.0%。He[11]Li[Li0.2Ni0.13-Co0.13Mn0.54]O22.5～4.6V153mAh/g1C5097%。SEI。HF。Jiang[12]Li[Ni1/3Co1/3Mn1/3]O2Al(OH)355℃2.8～4.3VAl(OH)3Li[Ni1/3Co1/3Mn1/3]O2166mAh/g4596%。LiuJ[13]Li[Li0.2Ni0.13Co0.13Mn0.54]O220s5C157mAh/g。Al。AlZnO、ZrO2、Li2ZrO3、AlF。33?°33?CPS7060504030202?
/()。S.J.Shi[14]LiFLi[Ni1/3Co1/3Mn1/3]O2。2.5～4.5V0.1C60℃1C5097.5%93.5%10C137mAh/g0℃1C－20℃(0.1C)124.4、85.6mAh/g。LiFLi[Ni1/3Co1/3Mn1/3]O2。。。。LiMn2O4、。HidekiK[15]Li1.1Mn1.9O4Li[Ni0.4Co0.3Mn0.3]O2Li[Ni0.4Co0.3Mn0.3]O2。LiCoO2Li[Ni-Co-Mn]O2LiCoO2。、、。、、-、。。。/、。ZhangL[16]Li2CO3、NiO、CoO3MnO2nLi∶n(Ni+Co+Mn)=1∶1Li[Ni1/3Co1/3Mn1/3]O22.8～4.4V0.5C148.5mAh/g4094.88%。-、。。Sol-gel、。。DingYH[17]Li、Ni、Co、MnpH8～9-100～300nmLi[Ni1/3Co1/3Mn1/3]O2。3.0～4.3V0.2C、2C162.82135.18mAh/g。-、。sol-gel、。。ZhangChuan-fu[18]NiCl2、CoCl2MnCl2LiOH900℃20～50nmLi[Ni1/3Co1/3Mn1/3]O2。2.75～4.30V2.75～4.50V159.7196.9mAh/g(0.1C)2C121.8mAh/g5098.2mAh/g98.3％。。。。[19]。JungHyunKin[20]Ni、Co、MnLi2CO3700℃3h。15%2.8～4.6V0.2C174mAh/g、。。。2008GSEH66Ah67.1Wh/kg114.3Wh/L。2009SAMSUNGLi[Ni0.5Co0.2Mn0.3]O2186502200mAh。2012Boston-Power5.34.4Ah18650Pack。。。20105ENAXCENAT3.7V26.0Ah164Wh/kg－20～55℃。LiFePO4。Ni∶Mn1∶1Co3M。NiCoLi[Ni0.35Co0.35Mn0.30]O23M。、。Ni、Co。Ni、Co、、。。[1]OHZUKUT,MATOBAN,SAWAIK.Directevidenceonanoma-lousexpansionofgraphitenegativeelectrodesonfirstchargebydilatometry[J].JournalofPowerSources,2001,10(5):97-98.[2]ZHUGuang-yan,LIUXue-sheng,PANLei,etal.InvestigationsofLi[Ni1/3Co1/3Mn1/3]O2cathodematerialforpowerlithium-ionbatteries[J].JournalofPowerSources,2009,33(7):547-551.[3]KOYAMAY,TANAKAI,ADACHIH,etal.Crystalandelectronicstructuresofsuper-structuralLi1－x[Co1/3Ni1/3Mn1/3]O2(0≤x≤1)[J].JournalofPowerSources,2003,119:644-648.[4]WHITFIELDAPS,DAVIDSONAIJ,CRANSWICKLM,etal.In-vestigationofpossiblesuperstructureandcationdisorderinthelithi-umbatterycathodematerialLi[Co1/3Ni1/3Mn1/3]O2usingneutronandanomalousdispersionpowderdiffiraction[J].SolideStateIonics,2005,176(5/6):463-471.[5]TANAKAI,KOYAMAY,YABUUCHIN,etal.Solid-stateche-mistryandelectrochemistryofLi[Co1/3Ni1/3Mn1/3]O2foradvancedlithium-ionbatteriesI.First-principlescalculationonthecrystalandelectronicstructure[J].JElectrochemSoc,2004,151(10):A1545-A1551.[6]YOONWS,BALASUBRAMANIANM,CHUNGKY,etal.Inves-tigationofthechargecompensationmechanismontheelectroche-micallyLi-iondeintercalatedLi1－x[Co1/3Ni1/3Mn1/3]O2electrodesy-stembycombinationofsoftandhardX-rayabsorptionspectroscopy[J].JAmChemSoc,2005,127(49):17479-17487.[7]JOUANNEAUS,EBERMANKW,KRAUSELJ,etal.Synthesis,characterization,andelectrochemicalbehaviorofimprovedLi-[NixCo1－2xMnx]O2(0.1≤x≤0.5)[J].JElectrochemSoc,2003,150(12):A1637-A2642.[8]HWANGBJ,TSAIYW,CHENCH,etal.InfluenceofMncon-tentonthemorphologyandelectrochemicalperformanceofLi-[Ni1－x－yCoxMny]O2cathodematerials[J].JMaterChem,2003,13:1962-1968.[9]XIAOJ,CHERNOVANA,WHITTINGHAMMS.InfluenceofmanganesecontentontheperformanceofLi[Ni0.9－yMnyCo0.1]O2(0.45≤y≤0.60)asacathodematerialforLi-ionbatteries[J].ChemMater,2010,20(3):1180-1185.[10]KIMHS,KIMK,MOONSI,etal.Studyoncarbon-coatedLi-[Ni1/3Co1/3Mn1/3]O2cathodematerialforlithiumsecondarybatteries[J].JSolidStateElectrochem,2008(12):867-872.[11]HEZhen-jiang,WANGZhi-xing,GUOHua-jun,etal.Asimplemethodofpreparinggrapheme-coatedLi[Li0.2Mn0.54Ni0.13Co0.13]O2forlithium-ionbatteries[J].MaterialsLetters,2013,91:261-264.[12]JIANGSB,KANGSH,AMINEK,etal.SynthesisandimproveelectrochemicalperformanceofAl(OH)3-coatedLi[Ni1/3Co1/3Mn1/3]-O2cathodematerialsatelevatedtemperature[J].ElectrochimActa,2005,50:4168-4173.[13]LIUJ,REEJA-JAYANB,ARUMUGAMM.ConductivesurfacemodificationwithaluminumofhighcapacitylayeredLi[Li0.2Ni0.13-Co0.13Mn0.54]O2cathode[J].JournalofPhysicsandChemistry,2010,114:9528-9533.[14]SHISJ,TUJP,TANGYY,etal.EnhancedelectrochemicalofLiF-modeifiedLi[Ni1/3Co1/3Mn1/3]O2cathodematerialsforLi-ionbatteries[J].