量子化学方法在锂离子电池电解液研究中的应用

*10008129。。*[e-mail]9732009CB2201002010-01-292010-05-18、/。ApplicationofQuantumChemistryMethodinStudyofLi-ionBatteryElectrolyteYangChunweiWuBorongWuFeng*ZhangCunzhongCollegeofChemicalEngineeringandEnvironmentalBeijingInstituteofTechnologyBeijing100081AbstractTheresearchdevelopmentsofquantumchemistrymethodonLi-ionbatteryelectrolyteindecadesweresummered.Theimportantfunctionsofquantumchemistryoninvestigatingnovellithiumsaltanalyzingtheaffectionoffunctionaladditivesandexploringtheformationprocessoftheinterfacebetweenelectrodeandelectrolytewereclarified.Theapplicationprospectswhichdealingwithfunctionalmoleculardesignsbyquantumchemistrywereproposed.KeywordsQuantumchemistryElectrolyteLithium-ionbattery、。、。/。Hartree-FockHF、DFTMP2。HOMO、LUMO、、。1Li+、、。、。·868·201010http//、HOMO。Klopman1HOMO。Li+HOMO。LiBCBLiSCBLiBSB3。。3BSB－HOMOLiBSB2。Barthel3HOMO。Xu4LiBOBPCHOMO。。。。Kita5LiPF6-nCFnPF4CF3－2PF3CF3－3PF5CF3－PF－6。LiPF3CF33LiPF4CF32LiPF5CF3LiPF6。0.1mol/L/PC∶12-DMELiPF4CF32LiPF64.4mS/cm。PCLiPF4CF32LiPF6。LiPF4CF32LiPF6。HOMO1。1HOMOTab.1TheHOMOenergyofthelithiumsaltanionBOB－BCB－SCB－BSB－PF3CF3－3PF4CF3－2PF5CF3－PF－6HOMO/eV－4.712－6.845－6.044－5.638－3.72－4.30－3.99－4.262。LUMOSEI。Xu6B3LYP6-31+GdpEC、PC、EMC13-PS14-BSPS、BSLUMO。PS、BSSEI。Wang7ECVC。VCEC。ECVCSEI。Ken8HFEC、PC、VC、VEC、THFVVC、VCECPCVVCVVCSEI。9BSPCBS。BS、PCBSLUMOPCBS。·968·http//。Ken1112--4LiPF6、。3//。4SEI。1ECPCVC12Fig.1Film-formingreactionequationofECPCandVC12Ken12EC、PC、γ-、DMC、EMCDECSEI。VC2SEI。ECPCECSEIPC。1EC、PCVC。·078·201010http//。。。。1.--.1987.2ZMXueYZDingCHChen.Electrochim.Acta200753990～997.3RGPearson.ChemistryinBritain1991275444～447.4WXuAJShustermanRMarzkeetal.J.Electrochem.Soc.20041514A632～638.5JKitaHSakataAKawakami.J.PowerSources200197-98581～583.6MQXuWSLiXXZuoetal.J.PowerSources2007174705～710.7YXWangSNakamuraKTasakietal.J.Am.Chem.Soc.20021244408～4421.8KTasakiKKandaTKobayashietal.J.Electrochem.Soc.200615312A2192～A2197.9.200728293～296.10KTasakiSNakamura.J.Electrochem.Soc.20011489A984～A988.11KTasaki.JElectrochem.Soc.20021494A418～A425.12KTasaki.J.Phys.Chem.B20051092920～2933.·178·http//