固體電解質(zhì)材料應(yīng)用于固態(tài)電池體系中的關(guān)鍵問題與應(yīng)對方案

固體電解質(zhì)材料應(yīng)用于固態(tài)電池體系中的關(guān)鍵問題和應(yīng)對方案郭向欣單位：青島大學(xué)聯(lián)系方法：演講提綱SolidLithiumBatteries(SLB)FeaturesandadvantagesHigh-V&large-capacitycathodesLi-richanodesSolidLithiumBatteries：developmentroadmapReductionReductionofliquidcontentbyintroductionofsolidelectrolytes液態(tài)凝膠液態(tài)凝膠半固態(tài)準(zhǔn)固態(tài)全固態(tài)25%10%5%0%ReducedReducedthicknessofsolidelectrolytes5050Ωcm230Ωcm220Ωcm2<10Ωcm2HighHigh-capacityanodeswithstablesolidelectrolyteinterphaselayer石墨石墨預(yù)鋰化石墨/硅碳鋰金屬0%30%50%100%6mAh/cm2400Wh/kg4mAh/cm2300Wh/kg>7mAh/cm2500Wh6mAh/cm2400Wh/kg4mAh/cm2300Wh/kg>7mAh/cm2500Wh/kg2mhA/cm2270Wh/kgResearchesinSolidGuogroupinQingdao氧化物鹵化物硫化物陶瓷片有機(jī)無機(jī)復(fù)合膜微型紐扣大容量軟包風(fēng)光儲新能源汽車趙寧畢志杰賈夢洋翟朋博固體電解質(zhì)材料：各有所長、各有所短關(guān)鍵問題：在固態(tài)電池體系中考察固體電解質(zhì)材料的構(gòu)型、表面特性設(shè)計和優(yōu)化Keymaterials：solidstateelectrolytesHigh-mass-loadingcathodes(NMCorLFP)withsolid-electrolytecoatingormixingReducedthicknessofsolidelectrolytesHigh-capacityanodeswithstablesolidelectrolyteinterphaselayerMulti-scalephysical,chemicalandelectrochemicalinterfaces畢志杰Z.J.Bi,X.X.Guo*,Solidificationforsolid-statelithiumbatterieswithhighenergydensityandlongcyclelife.EnergyMater.2(2022)200011畢志杰CriticalInterfacialissuesSummaryofinterfacesN.Zhao,X.X.Guo*,L.-Z.Fan*,C.-W.Nan*etal.,Joule,3(2019)1-10.趙寧翟朋博翟朋博，郭向欣等，鋰鑭鋯氧（LLZO）基固態(tài)鋰電池界面關(guān)鍵問題研究進(jìn)展，儲能科學(xué)與技術(shù)11(9):284（2022）鋰鑭鋯氧固體電解質(zhì)粉體的關(guān)鍵問題和解決方案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賈夢洋SolutionforsurfaceLi2CO3contaminationH.Y.Huo,N.Zhao,X.X.Guo*,X.L.Sun*etal.,In-situformedLi2CO3-freegarnet/Liinterfacebyrapidacidtreatmentfordendrite-freesolid-statebatteries,NanoEnergy61(2019)119-125.completelyremovesurfaceLi2CO3withoutdestroyingphasestructure霍瀚宇趙寧SolutionforsurfaceLi2CO3contaminationZJBi&XXGuoetal.,MoltenSaltDrivenConversionReactionEnablingLithiophilicandAir-StableGarnetSurfaceforSolid-StateLithiumBatteries,Adv.Funct.Mater.2022,2208751畢志杰鋰鑭鋯氧基電解質(zhì)層與鋰金屬負(fù)極、正極在電池體系中的界面設(shè)計制備與性能優(yōu)化LLZO陶瓷片電解質(zhì)和電池LCONCMLFPLCONCMLFPLCOLFP622LCOLFP622Joule2(2018)1J.PowerSourcesJoule2(2018)1NanoEnergyCEJ387(2020)124089J.Inorg.Mater.(2018)CEJ424(2021)130423LLZTOagainstLiLi金屬負(fù)極的貫穿室溫最大臨界電流密度大部分小于1mA/cm2(體相材料致密度、測試溫度和鋰剝離和沉積的量不一致)W.L.Huang,N.Zhao*,X.X.Guo*,L.-Z.Fan,C.-W.Nan*etal.,CanwefindsolutiontoeliminateLipenetrationthroughsolidgarnetelectrolytes?MaterialsTodayNano10(2020)100075黃煒麟趙寧Li金屬貫通LLZO陶瓷片電解質(zhì)的理論研究Li金屬成核和生長的理論研究鋰金屬貫穿陶瓷電解質(zhì)的兩要素：電場：局部過電勢JianGao,JianxunZhu,XiaoleiLi,Zhou,RationalDesignofMixedLi7La3Zr2O12forLithiuLi/LLZOinterfaces構(gòu)建三維離子電子混合導(dǎo)電中間層解決Li金屬在LLZO陶瓷電解質(zhì)中的生成mixedconductivegarnet/Liinterfacefordendrite-freesolidlithiummetalbatteries,EnergyEnviron.Sci.13(2020)127.霍瀚宇趙寧構(gòu)建三維離子電子混合導(dǎo)電界面原始LLZTO可觀察到沿陶瓷晶界貫通的鋰金屬，而具有混合電導(dǎo)界面的LLZTO在0.5mA/cm2電流密度下穩(wěn)定循環(huán)400hSun*etal.,Designofamixedclithiummetalbatteries,EnergyEn13(2020)127.Li/LLZOinterfaces:insulatingthinpolymerIL構(gòu)建柔性電子絕緣高離子導(dǎo)通中間層解決鋰金屬在LLZO陶瓷電解質(zhì)中的生長界面潤濕性合金或轉(zhuǎn)化反應(yīng)界面基于取代反應(yīng)的柔基于取代反應(yīng)的柔性聚合物界面優(yōu)異的柔韌性聚合物界面聚合物界面(PEO(LiTFSI))+界面?zhèn)鬏斃щy緩解界面應(yīng)力離子/電子界面?zhèn)鬏斈Ｐ蚇atureCommunicationsElectrolytesagainstcathodes:garnetcoated正極表面包覆garnet納米顆粒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.雙管齊下：正極表面包覆LLZO納米顆粒和構(gòu)筑類LiPON正極電解質(zhì)界面LCOorLMO/LLZTO/Li電池循定循環(huán)100圈以上，容量保持率80%以上畢志杰Electrolytesagainstcathodes:polymercoated正極表面包覆離子電子雙導(dǎo)電聚合物:PANI-PEG實現(xiàn)正極內(nèi)部離子電子導(dǎo)電網(wǎng)絡(luò)的構(gòu)建促進(jìn)CEI層的穩(wěn)定形成M.Y.Jia,X.X.Guo*etal.,Ionic-electronicDual-conductivePolymerModifiedLiCoO2CathodesforSolidLithiumBatteries,Chem.Commun.,2022,AcceptedLCO電池循定循環(huán)200圈以上，容量保持率91.8%.賈夢洋Li/LLZOinterfaces:in-situreactedIL原位反應(yīng)界面減小界面電阻醚類電解質(zhì)原位分解為梯度中間相：勻電場，抑制鋰枝晶的有機(jī)柔性層--維持穩(wěn)定的界面接觸穩(wěn)定性高陰離子基團(tuán)原位分解為子傳輸W.L.Huang,Z.J.Bi*,黃瑋麟XiangxinGuo*etal.,Chem.Eng.J.,424(2021)130423黃瑋麟PEO/nano-LLZTOmembranes1.借助滲流效應(yīng)提高電解質(zhì)膜離子電導(dǎo)率：improvementofconductivitythroughpe粉體粒度逐漸減小粉體粒度逐漸減小J.Zhang,N.Zhao,P.K.Chu,X.X.Guo*,Z.F.Di*,X.Wang,H.Lietal.,FlexibleandIon-張靜嫻張靜嫻趙寧Electrolytes…,NanoEnergy28(2016)447–454.趙寧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.借助固體粉體尺度的調(diào)控實現(xiàn)柔性膜兼顧抑制鋰枝晶和界面相容性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借助單層膜成分的調(diào)控實現(xiàn)柔性膜兼顧耐高電壓和對金屬鋰穩(wěn)定Doublelayers：standhighvoltageanddendritedepressionS.Mu,Z.J.Bi*,X.X.Guo*etal.,Heterogeneouselectrolytemembranesenablingdouble-sidestableinterfacesforsolidlithiumbatteries,JournalofEnergyChemistry60(2021)162-168.穆爽畢志杰PPC:LLZTOmembranes填料表面修飾實現(xiàn)化學(xué)穩(wěn)定、電化學(xué)性能優(yōu)異的柔性膜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.賈夢洋ModificationofSPEmembraneswith2Dmaterials借助氟化石墨烯構(gòu)筑穩(wěn)定SEI和CEI，使柔性膜兼顧對金屬鋰和高壓正極穩(wěn)定2Dfluorinatedgraphene：LiF-richSEI,dendritedepression,electrochemicallystableCEI,standhighvoltageP.BZhai,X.X.Guo*,Y.J.Gong*etal.,Two-dimensionalFluorinatedGrapheneReinforcedSolidPolymerElectr