固体电解质材料应用于固态电池体系中的关键问题与应对方案

固体电解质材料应用于固态电池体系中的关键问题和应对方案郭向欣单位：青岛大学联系方法：演讲提纲SolidLithiumBatteries(SLB)FeaturesandadvantagesHigh-V&large-capacitycathodesLi-richanodesSolidLithiumBatteries：developmentroadmapReductionReductionofliquidcontentbyintroductionofsolidelectrolytes液态凝胶液态凝胶半固态准固态全固态25%10%5%0%ReducedReducedthicknessofsolidelectrolytes5050Ωcm230Ωcm220Ωcm2<10Ωcm2HighHigh-capacityanodeswithstablesolidelectrolyteinterphaselayer石墨石墨预锂化石墨/硅碳锂金属0%30%50%100%6mAh/cm2400Wh/kg4mAh/cm2300Wh/kg>7mAh/cm2500Wh6mAh/cm2400Wh/kg4mAh/cm2300Wh/kg>7mAh/cm2500Wh/kg2mhA/cm2270Wh/kgResearchesinSolidGuogroupinQingdao氧化物卤化物硫化物陶瓷片有机无机复合膜微型纽扣大容量软包风光储新能源汽车赵宁毕志杰贾梦洋翟朋博固体电解质材料：各有所长、各有所短关键问题：在固态电池体系中考察固体电解质材料的构型、表面特性设计和优化Keymaterials：solidstateelectrolytesHigh-mass-loadingcathodes(NMCorLFP)withsolid-electrolytecoatingormixingReducedthicknessofsolidelectrolytesHigh-capacityanodeswithstablesolidelectrolyteinterphaselayerMulti-scalephysical,chemicalandelectrochemicalinterfaces毕志杰Z.J.Bi,X.X.Guo*,Solidificationforsolid-statelithiumbatterieswithhighenergydensityandlongcyclelife.EnergyMater.2(2022)200011毕志杰CriticalInterfacialissuesSummaryofinterfacesN.Zhao,X.X.Guo*,L.-Z.Fan*,C.-W.Nan*etal.,Joule,3(2019)1-10.赵宁翟朋博翟朋博，郭向欣等，锂镧锆氧（LLZO）基固态锂电池界面关键问题研究进展，储能科学与技术11(9):284（2022）锂镧锆氧固体电解质粉体的关键问题和解决方案KeypointI:SurfaceLi2CO3ofLLZOHanyuHuo,X.XGuo*,X.L.Sun*etal.,Li2CO3effects:Newinsightsintopolymer/garnetelectrolytesfordendrite-freesolidlithiumbatteries,NanoEnergy73(2020)104836.H.Y.Huo,V.T.,X.X.Guo*,C.-W.Nan*,X.L.Sun*etal.,Li2CO3:ACriticalIssuefor霍翰宇DevelopingSolidGarnetBatteries,ACSEnergyLett.5(2020)252-262.SurfacepropertiesofLLZOelectrolytesMorphologyandamountofLi2CO3onsurfacesX.F.WangandX.X.Guoetal.,ComparativeStudyofStabilityagainstMoistureforSolidGarnetElectrolyteswithDifferentDopants.Energies2022,15,3206./10.3390/en15093206SolutionforsurfaceLi2CO3contaminationM.Y.Jia,X.X.Guo*,Air-stabledopamine-treatedgarnetceramicparticlesforhigh-performancecompositeelectrolytes,J.PowerSources,486(2021)229363贾梦洋SolutionforsurfaceLi2CO3contaminationH.Y.Huo,N.Zhao,X.X.Guo*,X.L.Sun*etal.,In-situformedLi2CO3-freegarnet/Liinterfacebyrapidacidtreatmentfordendrite-freesolid-statebatteries,NanoEnergy61(2019)119-125.completelyremovesurfaceLi2CO3withoutdestroyingphasestructure霍瀚宇赵宁SolutionforsurfaceLi2CO3contaminationZJBi&XXGuoetal.,MoltenSaltDrivenConversionReactionEnablingLithiophilicandAir-StableGarnetSurfaceforSolid-StateLithiumBatteries,Adv.Funct.Mater.2022,2208751毕志杰锂镧锆氧基电解质层与锂金属负极、正极在电池体系中的界面设计制备与性能优化LLZO陶瓷片电解质和电池LCONCMLFPLCONCMLFPLCOLFP622LCOLFP622Joule2(2018)1J.PowerSourcesJoule2(2018)1NanoEnergyCEJ387(2020)124089J.Inorg.Mater.(2018)CEJ424(2021)130423LLZTOagainstLiLi金属负极的贯穿室温最大临界电流密度大部分小于1mA/cm2(体相材料致密度、测试温度和锂剥离和沉积的量不一致)W.L.Huang,N.Zhao*,X.X.Guo*,L.-Z.Fan,C.-W.Nan*etal.,CanwefindsolutiontoeliminateLipenetrationthroughsolidgarnetelectrolytes?MaterialsTodayNano10(2020)100075黄炜麟赵宁Li金属贯通LLZO陶瓷片电解质的理论研究Li金属成核和生长的理论研究锂金属贯穿陶瓷电解质的两要素：电场：局部过电势JianGao,JianxunZhu,XiaoleiLi,Zhou,RationalDesignofMixedLi7La3Zr2O12forLithiuLi/LLZOinterfaces构建三维离子电子混合导电中间层解决Li金属在LLZO陶瓷电解质中的生成mixedconductivegarnet/Liinterfacefordendrite-freesolidlithiummetalbatteries,EnergyEnviron.Sci.13(2020)127.霍瀚宇赵宁构建三维离子电子混合导电界面原始LLZTO可观察到沿陶瓷晶界贯通的锂金属，而具有混合电导界面的LLZTO在0.5mA/cm2电流密度下稳定循环400hSun*etal.,Designofamixedclithiummetalbatteries,EnergyEn13(2020)127.Li/LLZOinterfaces:insulatingthinpolymerIL构建柔性电子绝缘高离子导通中间层解决锂金属在LLZO陶瓷电解质中的生长界面润湿性合金或转化反应界面基于取代反应的柔基于取代反应的柔性聚合物界面优异的柔韧性聚合物界面聚合物界面(PEO(LiTFSI))+界面传输困难缓解界面应力离子/电子界面传输模型NatureCommunicationsElectrolytesagainstcathodes:garnetcoated正极表面包覆garnet纳米颗粒Z.J.Bi,C.S.Wang*,X.X.Guo*etal.,Chem.Eng.J.,387(2020)124089;Z.J.Bi,XiangxinGuo*etal.,J.Mater.Chem.A,8(2020)4252-4256.双管齐下：正极表面包覆LLZO纳米颗粒和构筑类LiPON正极电解质界面LCOorLMO/LLZTO/Li电池循定循环100圈以上，容量保持率80%以上毕志杰Electrolytesagainstcathodes:polymercoated正极表面包覆离子电子双导电聚合物:PANI-PEG实现正极内部离子电子导电网络的构建促进CEI层的稳定形成M.Y.Jia,X.X.Guo*etal.,Ionic-electronicDual-conductivePolymerModifiedLiCoO2CathodesforSolidLithiumBatteries,Chem.Commun.,2022,AcceptedLCO电池循定循环200圈以上，容量保持率91.8%.贾梦洋Li/LLZOinterfaces:in-situreactedIL原位反应界面减小界面电阻醚类电解质原位分解为梯度中间相：匀电场，抑制锂枝晶的有机柔性层--维持稳定的界面接触稳定性高阴离子基团原位分解为子传输W.L.Huang,Z.J.Bi*,黄玮麟XiangxinGuo*etal.,Chem.Eng.J.,424(2021)130423黄玮麟PEO/nano-LLZTOmembranes1.借助渗流效应提高电解质膜离子电导率：improvementofconductivitythroughpe粉体粒度逐渐减小粉体粒度逐渐减小J.Zhang,N.Zhao,P.K.Chu,X.X.Guo*,Z.F.Di*,X.Wang,H.Lietal.,FlexibleandIon-张静娴张静娴赵宁Electrolytes…,NanoEnergy28(2016)447–454.赵宁PEO/LLZTO(Li2CO3-free)membranesLLZOwithandwithoutLi2CO3(a)Li+mobilityandconductivityincrease(b)Electrochemicalwindowincreasedto5VHanyuHuo,X.XGuo*,X.L.Sun*etal.,Li2CO3effects:Newinsightsintopolymer/garnetelectrolytesfordendrite-freesolidlithiumbatteries,NanoEnergy73(2020)104836.(c)Transfernumberincreasedto0.5anddendritedepressedConstructionofcompositemembraneswithvaried-sizeparticles2.借助固体粉体尺度的调控实现柔性膜兼顾抑制锂枝晶和界面相容性Multifunction：dendritedepression,improveinterfacecompatibilityH.Y.Huo,X.X.Guo*,X.L.Sun*etal,RationalDesignofHierarchical"Ceramic-in-Polymer"and"Polymer-in-Ceramic"ElectrolytesforDendrite-FreeSolid-StateBatteries,AdvancedEnergyMaterials9(2019)1804004.霍瀚宇Constructionofcompositemembraneswithvaried-compositionparticles借助单层膜成分的调控实现柔性膜兼顾耐高电压和对金属锂稳定Doublelayers：standhighvoltageanddendritedepressionS.Mu,Z.J.Bi*,X.X.Guo*etal.,Heterogeneouselectrolytemembranesenablingdouble-sidestableinterfacesforsolidlithiumbatteries,JournalofEnergyChemistry60(2021)162-168.穆爽毕志杰PPC:LLZTOmembranes填料表面修饰实现化学稳定、电化学性能优异的柔性膜Surfacecoating：chemicalstableandgreatchemicalpropertiesM.Y.Jia,N.Zhao,Z.J.Bi,Z.Q.Fu,F.F.Xu,C.Shi*,X.X.Guo*,Polydopaminecoatedgarnetparticleshomogeneouslydistributinginpoly(propylenecarbonate)sforconductiveandstablemembraneelectrolytesofsolidlithiumbatteries.ACSAppl.Mater.Interfaces,2020,12(41):46162–46169.贾梦洋ModificationofSPEmembraneswith2Dmaterials借助氟化石墨烯构筑稳定SEI和CEI，使柔性膜兼顾对金属锂和高压正极稳定2Dfluorinatedgraphene：LiF-richSEI,dendritedepression,electrochemicallystableCEI,standhighvoltageP.BZhai,X.X.Guo*,Y.J.Gong*etal.,Two-dimensionalFluorinatedGrapheneReinforcedSolidPolymerElectr