锂离子电池高温电解液_尹成果

25120131PROGRESSINCHEMISTRYVol．25No．1Jan．20132012620128*863No．2012AA110203、No．51202047No．LBH-Z11141＊＊[e-mail]*＊＊150001。、、。。。。O646O614.111TQ152A1005-281X201301-0054-06Elevated-TemperatureElectrolytesforLi-IonBatteriesYinChengguoMaYulin＊＊ChengXinqunYinGepingSchoolofChemicalEngineeringandTechnologyHarbinInstituteofTechnologyHarbin150001ChinaAbstractResearchprogressandprospectsofelectrolytesusedatelevated-temperatureforlithium-ionbatteriesaresummarizedinthispaper．Thedeficiencyofcurrentcommercialelectrolytesathightemperatureisclarifiedaccordingtothechemicalstabilityofsolutesandsolvents．Someideasareproposedtodevelopthethermalstabilityoflithiumsaltsionicliquidsandflameretardantadditives．Thedeficienciesofthepresentlithiumsaltscanbeovercomethroughthemodificationoffunctionalgrouporthestructurecompositeandnewkindoflithiumsaltcanbedevelopedforelevated-temperaturelithiumionbattery．Non-carbonicacidestershowedpoorperformancewhenitwasusedaloneionicliquidsshowedpoorcompatibilitywithcommonlyusedanodeandcathodematerials．Themostpossiblewayfortheapplicationofhigh-temperatureelectrolyteistheblendofcarbonatesandflameretardants．Betterflameretardantcanbeachievedbyintroducingflame-retardantelementsintophosphateesterormodifyingpartofthefunctionalgroupwhichwillimprovetheperformanceofelectrolyteinhightemperature．Keywordslithium-ionbatteryelevated-temperatureelectrolytesaltnon-flammablesolventContents1Introduction2Highthermalstabilityelectrolytesalts2.1Boron-basedlithiumsalts2.2Lithiumimides3Non-flammablesolvents3.1Non-flammableorganicsolvents3.2Roomtemperatureionicliquids3.3Flameretardantadditives1·55·4Conclusionandoutlook1、、。55℃。55℃。LiPF6LiPF675℃HF、SEI、。。2、、。。。LiBF4、LiPF6、LiClO4、LiAsF6。。2.1LiBOBLiBC2O42302℃SEIPC1SEI2。LiBF4LiBOBLiODFBLiBF2C2O4LiBF4LiBOB。LiODFB、Al3。Li41mol/LLiODFBEC/PC/DMC1∶1∶3byvol．/LiFePO41mol/LLiPF6EC/PC/DMC1∶1∶3byvol．10092%65℃88%25℃LiPF610045%65℃90%25℃。Fu5EC/PC/EMC1∶1∶3bymassLiPF6LiODFBLi/LiMn2O4LiODFBMn2+LiMn2O4Mn。LiPF6LiODFB25℃10088.4%93.6%60℃79.2%87.5%。18—12Table1Performanceofseverallithiumsalts8—12abbreviationchemicalformuladecompositiontemperature/℃meritshortcomingLiBOBLiBC2O42302easytoformfilmnon-corrosivetoAlhighviscosityhighimpedanceofSEIfilmLiODFBLiBF2C2O4279moderateionconductivityeasytoformSEIfilmnon-corrosivetoAlhighcostLiTFSILiNSO2CF32＞360applicabletovarioustemperaturesandsolventscorrosivetoAlLiBETILiNSO2C2F52＞350slightlycorrosivetoAlthanLiTFSIlowerionconductivityLiFSILiNSO2F2＞200conductivetoformSEIfilmdifficulttopurifyorwillbecorrosivetoAlLiFNFSILiNSO2FSO2C4F9＞220highionconductivityeasytoformSEIfilmnon-corrosivetoAlhighcost2.2LiNSO2CF32LiTFSI360℃LiPF65.0VvsLi+/LiAl6。LiTFSIAl1·56·25AlLiBF4、LiODFB72TFSI－—SO2CF3。—C2F5—FLiTFSI—CF3LiBETILiNSO2C2F52LiFSILiNSO2F2。LiBETI350℃LiTFSI8Al9。LiFSI200℃LiPF64.2VAl10。Han11/LiCoO21mol/LLiFSIEC/EMC3∶7byvol．120mAh/gLiCoO2507%LiPF615%。—F—C4F9LiTFSI—CF3LiFNFSILiNSO2FSO2C4F9。LiTFSI220℃Al。Han12/LiCoO21mol/LLiPF6LiFNFSIEC/EMC3∶7byvol．25℃120mAh/gLiCoO210023%11%60℃LiPF62050%LiFNFSI10037%。1。、。3DMC90℃EMCPC13。。123。3.1、。GBLγ-204℃、101℃、200℃GBLSEI14。15GBL16。Kinoshita17VC、1mol/LLiBF4GBL/LiCoO2。5wt%100130mAh/gLiCoO2。60℃110mAh/g。。。Isken181mol/LLiBF4/EC1∶1bymass0—5V149℃LiNi1/3Mn1/3Co1/3O250364mAh/g1C140mAh/gC/2。LiCoO21mol/LLiTFSI/EC1∶1byvol．98mAh/g19。EMS、TMS。EMS240110℃TMS285166℃5V20LiMn2O4LiNi0.5Mn1.5O4。Abouimrane211mol/LLiPF6EMSLi4Ti5O12/LiNi0.5Mn1.5O4110mAh/gLiNi0.5Mn1.5O4100。EMSTMS3528℃。Xiang22LiTFSITMS5%160℃50360mAh/g。Watanabe23EA1mol/LLiBF4TMS/EA1∶1byvol．+2%VCLiNi0.5Mn1.5O430110mAh/g。γ-、1·57·。γ-、。3.2、、、、300℃24。SEI25。。。3.2.1EMI1--3-1.0V26。EMI27。Li4Ti5O121.55VEMI。EMI-BF4Al28EMI-TFSIEMI-BF4Al29EMI-BF4。Garcia30Li4Ti5O12/LiCoO21mol/LLiTFSIEMI-TFSI1mol/LLiBF4EMI-BF425℃1C132mAh/gLiCoO2200106mAh/g。31。Seki32—CH31--3-2DMPIm12--3-LiCoO2C/2130mAh/g。3.2.2、、、33。TFSI－TFSI－BF4－PF6－34。Reale35Li4Ti5O12LiFePO40.2mol/LLiTFSIPy24-TFSI40℃SEI。PP13-TFSIN--N-Li+/Li36。Xiang370.3mol/kgLiTFSIPP13-TFSILiCoO20.1C10145mAh/g。、。PP13TFSI1molLiPF6EC/DEC1∶1byvol．2wt%LiBOB38。3.3。H39。、、、、、。。、、、、40。2。2TPP41、CDP42、TCEP43、44—46TMP47、TEP48、DMMP49、、、、50、DPOF51、TMPi52。Shim53DPOF0—4.95V1.15mol/LLiPF6EC/EMC3∶7byvol．5wt%DPOFDSC215℃231℃MCMB/LiCoO21C119mAh/gLiCoO2·58·25125mAh/g1002%。Nam545wt%DPOFMCMB/LiCoO240℃308%。SEI55。Yao56LiPF6EC/DEC1∶1byvol．10%TMPiTMP180℃TMPLi/LiNi0.8Co0.2O2TMPi40140mAh/g。FSEI57。Xu50TDP222--、BMP-222--TFP-222-1mol/LLiPF6EC/EMC1∶1bymassBMPTFP20wt%TDP0.3VTFP。DMMPDMMPDMMP10%FECLiBOB。240—57Table2Performanceofcommonflameretardants40—57abbreviationchemicalformulaflameretardantabilitycompatibilitywithcarbonanodeimpacttotheionicconductivityofelectrolytecomprehensiveevaluationTMPCH3O3POcommonnonoimpactcommonTEPC2H5O3POcommonnoslightlyreducecommonDMMPCH3CH3O2POcommonnonoimpactcommonTPPC6H5O3POcommonyesreducecommonCDPC7H8OC6H5O2POcommonyesreducecommonDPOFC8H17C6H5O2POcommonyesnoimpactgoodTMPiCH3O3PcommonyesnoimpactgoodTDPCF3CH2OCH3O2POcommonyesslightlyreducegoodBMPCF3CH2O2CH3OPOgoodyesslightlyreducecommonTFPCF3CH2O3POgoodyesslightlyreducegoodTCEPClC2H4O3POgoodyesnoimpactcommonHMPNCH3O6P3N3g