LLZO固態(tài)鋰電池關(guān)鍵界面問題

XiangxinGuoQingdaoUniversityEmail：xxguo@123BackgroundandmotivationHigh-energy-densityandhigh-safebatterContinuousdemandingforincreasingenergydensity→500Wh/kg→400Wh/kg300Wh/kg《中國制造2025》4CriticalInterfacialissuesHigh-mass-loadingcathodes(NMCorLFP)withsolid-electrolytecoatingormixingReducedthicknessofsolidelectrolytesHigh-capacityanodeswithstablesolidelectrolyteinterphaselayerMulti-scalephysical,chemicalandelectrochemicalinterfacesZ.J.Bi,X.X.Guo*,EnergyMater.2(2022)200011CriticalInterfacialissuesSummaryofinterfacesN.Zhao,X.X.Guo*,L.-Z.Fan*,C.-W.Nan*etal.,Joule,3(2019)1-10.SurfacepropertiesofLLZOelectrolytesHanyuHuo,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)252-262.6SurfacepropertiesofLLZOelectrolytesMorphologyandamountofLi2CO3onsurfacesZ.Bi,J.Gao,X.F.WangandX.X.Guoetal.,ComparativeStudyofStabilityagainstMoistureforSolidGarnetElectrolyteswithDifferentDopants.Energies2022,15,3206./10.3390/en150932067SolutionforsurfaceLi2CO3contaminationACSAMI12（2020）PPC/PPC/LLZOwithandwithoutcoating賈夢洋8SurfacecoatingbyPDAreducespHto8-9,suppressreactionbetweenPPC/LLZO,aswellasagglomerationofsub-micro-sizedparticles;whileincreasestheconductivity賈夢洋8SolutionforsurfaceLi2CO3contaminationH.Y.Huo,N.Zhao,X.X.Guo*,X.L.Sun*etal.,In-situformedLi2CO3-freegarnet/Liinterfacebyrapidacidtreatmentfordendrite-freesolid-statebatteries,NanoEnergy61(2019)119-125.completelyremovesurfaceLi2CO3withoutdestroyingphasestructure趙寧9霍瀚宇趙寧9EffectsofLi2CO3LLZOwithandwithoutLi2CO3(a)Li+mobilityandconductivityincrease(b)Electrochemicalwindowincreasedto5VHanyuHuo,X.XGuo*,X.L.Sun*etal.,Li2CO3effects:Newinsightsintopolymer/garnetelectrolytesfordendrite-freesolidlithiumbatteries,NanoEnergy73(2020)104836.(c)Transfernumberincreasedto0.5anddendritedepressedElectrolytelayers:polymer/electrolyteInterfacesMultifunction：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.Li/LLZOinterfaces表面無碳酸鋰陶瓷和Li界面去除Li2CO3的LLZTO界面電阻由940降低至26Ωcm2H.Y.Huo,N.Zhao,X.X.Guo*,X.L.Sun*etal.,In-situformedLi2CO3-freegarnet/Liinterfacebyrapidacidtreatmentfordendrite-freesolid-statebatteries,NanoEnergy61(2019)119-125.Li/LLZOinterfaces:introductionofILLi金屬負極貫穿LLZO的解決方案：引入中間層(IL)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/LLZOinterfaces:3Dionic-electronicnetworkILLi金屬貫通LLZO陶瓷片電解質(zhì)解決方案：構(gòu)建三維離子電子混合導(dǎo)電中間層mixedconductivegarnet/Liinterfacefordendrite-freesolidlithiummetalbatteries,EnergyEnviron.Sci.13(2020)127.霍瀚宇趙寧Li/LLZOinterfaces:3Dionic-electronicnetworkILLi金屬貫通LLZO陶瓷片電解質(zhì)解決方案：構(gòu)建三維離子電子混合導(dǎo)電中間層原始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,EnergyEnviron.13(2020)127.Li/LLZOinterfaces:thinflexibleelectronicblockingIL鋰金屬貫穿LLZO陶瓷解決方案：構(gòu)建柔性電子絕緣高離子導(dǎo)通中間層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atureCommunicationsLi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：過電勢電子注入JianGao,JianxunZhu,XiaoleiLi,Zhou,RationalDesignofMixedLi7La3Zr2O12forLithiuCompositecathodes:coatingbytheelectrolytes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Compositecathodes:coatingbyLi+/e正極表面包覆離子電子雙導(dǎo)電聚合物LCO包覆離子電子雙導(dǎo)電聚合物(PANI-PEG)之后倍率性能和循環(huán)穩(wěn)定性顯著提高M.Y.Jia&X.X.Guoetal.ACSAMI(2022）,inpressSolidificationstrategiesZ.J.Bi,X.XGuo*,EnergyMater.,2(2022)200011畢志杰Electrolyte/electrodeinterfaces原位反應(yīng)界面:InsitusolidifiedinterfacesLi/LLZTO界面：醚類電解液,ether-based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，抑制鋰枝晶的有機柔性層--維持穩(wěn)定的界面接觸穩(wěn)定性高陰離子基團原位分解為子傳輸W.L.Huang,Z.J.Bi*,黃瑋麟XiangxinGuo*etal.,Chem.黃瑋麟Eng.J.,424(2021)13042321Electrolyte/electrodeinterfaces原位聚合界面:in-situsolidifiedinterfaces