全固态锂电池界面的研究进展-张强

5520169EnergyStorageScienceandTechnologyVol.5No.5Sep.20161,21,2331,2131520121000493300384doi:10.12028/j.issn.2095-4239.2016.0036TM911A2095-4239201605-659-09ResearchprogressoninterfacesofallsolidstatelithiumbatteriesZHANGQiang1,2,YAOXiayin1,2,ZHANGHongzhou3,ZHANGLianqi3,XUXiaoxiong1,2(1NingboInstituteofMaterialsTechnologyandEngineering,ChineseAcademyofSciences,Ningbo315201,Zhejiang,China;2UniversityofChineseAcademyofScience,Beijing100049,China,3SchoolofMaterialsScienceandEngineering,TianjinUniversityofTechnology,Tianjin300384,China)Abstract:Comparedwithconventionallithiumionbatteries,allsolidstatelithiumbatteriesbasedonsolidelectrolytesarenewresearchhotspots,inviewofsuchpotentialmeritsashighsafety,longcyclelifeandhighenergydensity.Furthermore,allsolidstatelithiumbatteriescouldbewildlyusedonelectricvehiclesandsmartgridinthenearfuture.Thesolid-solidcontactresistanceofinterfacesbetweenelectrodesandsolidelectrolytesislargerthansolid-liquidcontactresistance.Meanwhile,interfacecompatibilityandstabilityhavesignificantinfluenceoncycleperformanceandratecapability.Moreover,grainboundariesinelectrolytesdetermineoverallconductivity.Thus,interfaceissueshavegreateffectonelectrochemicalperformancesofallsolidstatelithiumbatteries.Thispaperpresentsabriefreviewonallkindsofinterfacesinallsolidstatelithiumbatteries,coveringinterfaceoptimizingmechanismandmodificationmethods.Thechallengesoninterfaceinallsolidstatelithiumbatteriesaresuggestedaswell.Keywords:allsolidstatelithiumbatteries;solidelectrolytes;interfacemodification2016-07-042016-07-19ADA09010201515023171992—[e-mail][e-mail][e-mail]1[1-2]660201651[2]Fig.1Developmentdirectionofenergystoragebatteries[2][3]fastionconductorssuperionconductors10−110−4S/cm10−6S/cm≤0.30eVtion1[4][5][6-7]ZHU[8]ZHU31231/2[9]WOO[10]HRTEMEDSLiCoO2S66152[3]Fig.2Thediagramofpotentialchangeintheheterojunctionbetweenaionicconductorandsemiconductor[3]OCo30nmCoS33/[10]Fig.3Reactionatelectrode/solidelectrolytesinterface[10][11]OKUMURA[12]LiCoO2NbO2CoO4OHTA[13-14]LiCoO2Li4Ti5O12LiNbO3Li4Ti5O12LiNbO310−510−6S/cm5nmOHTALi3.25Ge0.25P0.75S4thio-LISICONLi-InSAKUDA[15-17]PLDLiCoO2Li2SiO380Li2S·20P2S580Li2S·20P2S5SAKUDAArrhenius4Fig.4Schematicillustrationsofoxidebufferlayerreducingspacechargelayer66220165XU[18]LiAlxCo1−xO2LiAlxCo1−xO2x=0.08AlCoc/aXU[19]1nmTaO3LiCoO2TaO35.3eV0.11nm0.11nmLi+Li+Li3.25Ge0.25P0.75S43105Ω·cm24103Ω·cm2XU[18,20]LiNi0.8Co0.15Al0.05O2LiNi0.8Co0.15Al0.05O2LiNi0.8Co0.15Al0.05O2Li10GeP2S12/Li-In652Ω·cm2480Ω·cm2198Ω·cm246.7mA·h/g89mA·h/g146mA·h/g40.9%56%76%OHTA[21]Li6.75La3Zr1.75Nb0.25O12500nmLiCoO2Li3BO3210−6S/cmLiCoO2Li6.75La3Zr1.75Nb0.25O12PVD[22]HOSHINA[23-25]PVPLi1+xAlxTi2−x(PO4)3LiMn2O4LiNi0.5Mn1.5O41μmAl2O3[10]SiO2[26]TiO2[27]ZrO2[28]CoSNiS[29]Li2CO3[30]Li2SiO3[31]Li2ZrO3[32]Li4SiO4-Li3PO4Li4GeO4-Li3PO4[33]2/−3.04Vvs.NHE3862mA·h/gsolid-electrolyteinterphaseSEI[34][35]WENZEL[36]366355/abc[36]Fig.5Typesofinterfacesbetweenlithiummetalandsolidelectrolytes:(a)Non-reactiveandthermodynamicallystableinterface;(b)Reactiveandmixedconductinginterphase(MCI);(c)ReactiveandmetastableSEI[36]SEISEISEI5WENZEL[37-38]Li7P3S11Li10GeP2S12XXPSSEILi2SLi3PLi-GeWENZEL30hLi7P3S11Li10GeP2S12SEI2.3nm20nm1SEI23nm370nmSEI0.28kΩ·cm24.3kΩ·cm23Li10GeP2S1212mS/cm1[35]Li10GeP2S12Ge4+Ge4+ONG[39]Li10±1MP2X12M=Ge,Si,Sn,AlPX=O,SSeONGSEISEISHIN[40]Li10GeP2S12Li3PS4Li10GeP2S12Li3PS4SHINLi10GeP2S12Li0.5InLi3PS4SAKUMA[41]Li4−xGe1−xPxS4Liy-MM=Sn,SiSEIGeSEILi-MM=Sn,SiMLiOGAWA[42]Li20nmSiLiCoO2Li2S-P2S5SiSi10076%Si1000100%OGAWAAlSnSiSi66420165AlSnLi0.35La0.55TiO310−310−4S/cmTi4+WENZEL[36]Li0.35La0.55TiO3XPSLa3+Ti4+Ti3+Ti2+TiOAl2O3Li7La3Zr2O12Li7La3Zr2O12WOLFENSTINE[43]Li7La3Zr2O12DU[44]Li7−xLaxZr2−xTaxO12LiCoO260NASICONLi1+xAlxTi2−x(PO4)3Li1+xAlxGe2−x(PO4)3HASEGAWA[45]1μmLiPONLi1.3Al0.3Ti1.7(PO4)3KOTOBUKI[46]Li1+xAlxGe2−x(PO4)3300μm10−3S/cmPMMA[47][48]33PerovskiteNASICONLISICONthio-LISICONGarnetAl2O3-LiILiPON[49]Li2S-P2S5Li2S-MS2-P2S5M=Ge,Si,Sn,AlPITO[50]3hLi7P3S11300Li4P2S6Li7P3S11Li4P2S6MINAMI[51-52]70Li2S·30P2S5MINAMI7506655Li7P3S112.110−3S/cmLi4P2S721030min2801h5.210−3S/cmMIZUNO[53]420Li7P3S11β-Li3PS4Li4P2S7MURUGAN[54]Li7La3Zr2O12310−4S/cmKOTOBUKI[55]Al2O3Li7La3Zr2O12Al2O3Li7La3Zr2O12BUSCHMANN[56]AlTaWOLFENSTINE[57]KOTOBUKI[58-59]NASICONXU[60-61]SPSXULi2O0.05molLi1.5Al0.5Ge1.5(PO4)37.2510−4S/cmZHU[62]Li1.5Al0.5Ge1.5(PO4)34100Ω·cm2200Ω·cm2[1]TARASCONJMARMANDM.Issuesandchallengesfacingrechargeablelithiumbatteries[J].Nature20014146861359-367.[2][3].[J].201324331-341.XUXiaoxiongQIUZhijunGUANYibiaoetal.All-solid-statelithium-ionbatteriesState-of-the-artdevelopmentandperspective[J].EnergyStorageScienceandTechnology201324331-341.[4]AGRAWALRCGUPTARK.SuperionicsolidCompositeelectrolytephase–Anoverview[J].JournalofMaterialsScience19993461131-1162.[5]MAIERJ.NanoionicsIontransportandelectrochemicalstorageinconfinedsystems[J].Nat.Mater.2005411805-815.[6]AONOHSUGIMOTOESADAOKAYetal.TheelectricalpropertiesofceramicelectrolytesforLiMxT