锂离子电池基础科学问题(9)_非水液体电解质材料

3320145EnergyStorageScienceandTechnologyVol.3No.3May2014——100190Li+doi10.3969/j.issn.2095-4239.2014.03.012O646.21A2095-4239201403-262-21Fundamentalscientificaspectsoflithiumionbatteries()——NonaqueouselectrolytematerialsLIUYaliWUJiaoyangLIHongInstituteofPhysicsChineseAcademyofSciencesBeijing100190ChinaAbstractTheelectrolyteisaveryimportantcomponentinlithiumionbatteries.Practically,itisquitedifficulttofindanoptimizedelectrolytecompositiontosatisfydifferentrequirementsforvariousapplications.Inthisarticle,thenonaqueouselectrolytes,includinghistory,basicproperties,solvents,lithiumsalts,additives,ionicliquids,gelpolymerelectrolytesandhighvoltageelectrolytesaresummarizedbriefly.SeveralproblemsneedstobesolvedinthefutureImprovingthesafetyoftheelectrolyte,extendingvoltagerangeandtemperatureranges,prolongingthecyclelifeandservicelife,loweringthecost.Keywordslithiumionbatteriesnonaqueousorganicliquidelectrolyteionicliquidsgelpolymerelectrolytehighvoltageelectrolyte1958Tobias[1]LiClO4PCPCPC49.2241.7132                                                             2014-03-312014-04-11513252069732012CB9329001987—[e-mail][e-mail]+[2][1]PC[3]Sony[4]PCLiCoO2EC[5]SEILi2CO3ROCO2LiLiFPEO-LiEC2633EC1994Guyomard[6][7]DMCECDMCECDECEMCMPC[8]EC[9]2080THF88%[10]2-MeTHF)96%[11]DEE98%[12][13]2070LiLiAsF6LiClO4LiAsF6[14]AsLiAsF6LiAsF6LiBF42060LiPF6[15]LiPF6[17]LiPF6[16]1990SonyLiPF6LiPF6CLiC(CF3SO2)3LiCH(CF3SO2)2LiC(CF3SO2)3LiCH(CF3SO2)2NLiN(CF3SO2)2[18]LiPF63.6VBLiBOB3204.5V1.8Vvs.Li+/Li[19]2011Zhou[20]LiFNFSI22060/LiCoO2KishidaChemicalBYD1Li+solidelectrolyteinterphaseSEI(1)eiiinuz1niuizii(2)26420143bdRS2dRbSArrhenius[21]aexpEART3EaTARln1/TEa/RlnAEaA[22]Vogel-Tamman-FulcherVTF[23]01/2expBATTT4ABEaAT0ttransferencenumberLi+Li+Li+Li+Li+Li+SEII0IsLi+tLi+(5)[24]sLi0ItI5Li+BruceVincent[25]s00Li0ss()()IVIRtIVIR6VR0RsNyquistRctRSEI(6)Li+LitLi//LiRtotal10100mVLi+RDC=V/IDCLi+Lit=Rtotal/RDCCV[26-27]CVCV6CVSEI2653HOMOLUMO[28]PP13TFSI117cP[29]1cP=103Pa·sDMC0.59cPStokes-Einstein16iir7iri121.2Vvs.Li+/LiSEISEILi2CO3LiFLi2OLiOHROCO2LiROLiPEO-Li[5,30-31]Li+SEISEISEISEI[32]SEISEISEISEISEI4.11Table1ThebasicphysicalpropertiesofsomeorganicsolventsinlithiumionbatteriesTm/Tb/ε(25)η(25)/cPEC36.424889.781.90(40)PC48.824264.922.53BC53240533.2DMC4.6913.1070.59(20)DEC74.31262.8050.75EMC531102.9580.65γγBL43.5204391.73EA84776.020.45MF99328.50.33THF109667.40.4622-Me-THF137806.20.47DMM105412.70.331,2DME58847.20.46AN48.881.635.950.341266201434.9Vvs.Li+/Li1985Thomas[34]LiCoO2PCTarascon[35-36]LiMn2O4Aurbach[37]LiCoO2LiMn2O4LiNiO2FTIRSEMXPSSEILi2CO3[38-39]SEI[33]Li2CO3ROCO2LiSEILi2CO3ROCO2LiLi2CO3ROCO2LiCO2CO32SEISEISEITEMSEI[40]LiCoO2DMCLiCoO2DMC25nmROCO2LiROLiLi2CO3LiCoO2Co3O4LiCoO2LiCoO2SEISEISEI[33][33,41]Li+LiLiCoO2Li1+x(NiCoMn)O2CO2CO4.4DSCTG-MSARCLiPF6[42-47]LiPF6PF5CO2[48-49]DMDOHCLiPF6(s)LiF(s)+PF5(g)12673H3COCOOCH3+PF5H3CFH3COCH3CO22OOOPF5/HFCH3CH2n+n OC(OCH2CH2)n+nCO2O3OOOH3C+nOCOOCH3 OOOOOODMDOHC485[46]ARC123167[44]3[41][33,41,50]εLi+2.04.0Vvs.Li+/Li[51]C==OC≡≡NS==OO[41]1[52] [41] 3.1.1PC[53]Sony[54]PCSEIPC[55-57]PCLi[55,58]LiLiLiPCLiPC[59]PCLi+[56,60]PC3.1.2PCEC[61]ECElliot[62]1964EC2070Scrosati[63]PCEC26820143[64-66]ECPCSEIEC3.1.3ECECPC[67-68][8,65-66,69]PC1994TarasconGuyomardDMC[6-7]DMCEC[41][69]DMCDECEMC[70-71]DMCEC3.1.42080PCLi[10]THF[10]2-Me-THF[11]DME[12][13][65]PtTHF4.0Vvs.Li+/Li5.0V[72]4.0V4.0V[73-74]150[41][33,41]LiFLiClLi2O[75-76]BrIS2LiAlX4X[77]AlX3AlX4LiClO4LiMFnMBAsPSbn46[LiCF3SO3LiN(SO2CF3)2]23.2.1LiPF6LiPF6[78-79]5.1Vvs.Li+/Li[80-82]2693 2Table2Thephysicalandchemicalpropertiesofsomecommonlyusedlithiumsaltsinlithiumionbatteries/g·mol1(1mol/LinEC/DMC,20)/mS·cm1LiPF6151.9110.00LiBF493.7414.50LiClO4106.4019.00LiAsF6195.8511.10(25)LiCF3SO3156.0111.70(inPC25)()LiTFSI287.0816.18()LiBETI387.1115.45LiFSI187.0710.40(25)()()LiTNFSI437.1111.55()()LiFNFSI387.1114.70LiBOB193.7917.50(25) LiPF6LiPF6[12,46]LiPF6(s) LiF(s)+PF5(g)PF5PF5LiPF6LiPF6LiPF6HFLiFLiF[83]2011LiPF6LiPF6LiPF6LiPF6LiPF6SUTERAKEMIFA3.2.2LiPF6LiPF6LiBF4LiPF6LiBF4[84][85-86]LiPF65.0Vvs.Li+/Li[87-88]LiClO4LiBF4[78]LiBF4Li[89]3.2.3LiClO45.1Vvs.Li+/LiLiPF6LiBF4LiClO4SEI[70,90]HFLiFLiClO4[60,90]LiClO43.2.4LiAsF6LiPF61.15Vvs.Li+/LiSEILiFAsF[91][7,92]LiAsF6LiAsF6AsAsF6+2eAsF3+3F[13]LiAsF63.2.5[29]LiPF6LiBF427020143[41]LiCF3SO3LiPF6[93][78][80]3.2.6()()LiTFSIF3CSOONLiSOOCF3[94]Armand[95]3M2090SEILiTFSI5.0Vvs.Li+/Li[93]LiTFSI[80,96]LiBF4[97][98]3.2.7LiFSILiTFSIArmand[99]1999Zaghib[100-101]LiPF6[102]ClLiClO4R1SOONLiSOOR2R1=CnF2n+1R2=CmF2m+1nm0LiFNFSIn=0m=4[103]3.2.8LiBOBLischka[104]1999PnmaOBOOOOOOOBOBLi+[105]LiBOB[18,106-108]LiBOB1.6Vvs.Li+/LiPCECLiPF6ECLiPF6205020602713410SEISEI3.1SEICovalent1997SO2[109]PCVC[110]PCSEIPS[111]ES[112][113]1996NH3[114]12--4[115-116][117-118][119-122]TMP[123-124]TEP[123-124]MFA[125]EFA[126]1003.3[127-131][132][133][134]HFLiPF6HF[135]HFHMDS[136-137]MEC[138]FEC[139-143]LiBOBLiODFB[144-145][146][147]2,2,2-TTFP[148]LiPF65[33,149-151]27220143300[33]1914Walden[152-153]2070[27