东方理工大学孙学良：卤化物固态电解质

宁波东方理工大学OxideOxideNaHHalide>低电子导(针对隔膜层)批量合成ChallengesChallengesNarrowelectrochemicalwindowimpedance3.Mechanicalstrain3.ChemicalcompatibilityOxideOxideHalideNHalideMaterialChallenges(Solid-StateElectrolyte)NarrowelectrochemicalwindowChallengesChallengesofAlI-Solid-State>>EngineeringChallengesEngineeringChallengesimpedance3.Mechanicalstrain3.ChemicalcompatibilityChemicalReviowsi2016116(1).140-162LISICON-likeAIgY7ositGrzie?NASICONUZr,(PDJnicConductivityofSolidStateElectroyyteoverLiquid:Organicelectrolyte:10mScm¹,Na2.sgSbosaWo.12S:32SchoydeI□FrekledefecVacancyLtesitial-Vacaacy-Ssbstitutimaluallee2016LI2016LI9.54Si1.74P1.44S11.7CI0.3(2.5×10-2)OxidationThermalAirstabilityReviewPapers:2000Thio-LISICONLG-PS(10-3)Liang,Sun*,etal.,Acc.Chem.Res.54,1023-1033.(2021Liang,Sun*,etal.,Acc.Chem.Res.54,1023-1033.(2021)WangWang,Sunetal.,ScienceAdvance(2022).Jung2023LI9.54[SIO.6Ge0.4]1.74P1.44S11.1Bro.300.6(3.2×10-2)2011LGPS(1.2×10-2)2011LGPS(1.2×10-2)2008Argyrodite2023LiMOCI4(M=Nb,Ta)(1.24×10-22023gtassyLiTaCI6(1.1×10-22021Li3YBr3CS(0.72×10-3)Li₂TICl₄(400°C)LI₁52Mn124Cl₄LIsInBr,CL,LIsInBr,CL,2006.KojiYamadehigh-temperaturehigh-temperaturehigh-temperature1981,H.D.LutUpto10-4ScmUpto10-4Scm-1syntheslzedInwater,2019.YangShao-Hom201820192020SynthesisofLIYBr2020,Xueliang2020,XueliangA.Sun2020,XueliangA.SunIn-sltuSynthesis2020,XuellangA.SunAIr-Stablllty2020.XueliangA.SunSynthesisofLIYCL202SynthesisofLIYCLZrdopedLI₃YCIandZrdopedLI₃YCIandctrolytefor0162Percolatlonthres'!valueTargetPercolatlonthres'!valueK.Kang,etal.Scicncc2023,382,573.·. 05ULD:~11一1111na,-a,-万5ODigH.Yao,etal.Nature2023,616,77Low-costsynthesisLow-costsynthesisLi2.25Zro.7sFeo.25Cl₆:~1*10-3Scm-1bTol 山山44yifm.2023AEM.2021,11,200330yifm.2023AEM.2021,11,200330bl.Nat.Commun.2Chem.Int.Ed.2019..........·.....Scl.,2019EApplicatioeywordsintitlChem.Nat.Commun.Scl.Adv.2023eywordsintitlChem.Nat.Commun.Scl.Adv.2023xLi₂O-TaCl₅FmōmFmōm023ProProspect描描t1320142015201620172018201920202021202220232024Yeart AgnvironAgnviron.Scl.20ZJ,220TAnionAnionSublatticeStructureControlLi₂MCloM=Ho,Dy,Y,Er,Tm>1mS.cm¹),OrthorombiceznooeeoroherroopaLlang,Li,InCl₆FLi,InCl₆FMonoclinicororconcenvaJACS,2020MonoclinlcZhang,JACS,2020MonoclinlcZhang,Sun*etLYC,LEC,trigonalg含需含。unetal.,Ady.,2021。unetPremixing十3.Water-AssistedLiquidPhaseSynthesis十Wel-chemistrysynthesis.·Na(124)Na(124)Sm(113.2)Sm(113.2)Tb¹(109.5)Y(107.5)Y(90),Er²·(89)9-foldCoordinationOctahedralvoid9-foldCoordinationOctahedralvoidLi(76),ScLi(76),Sc¹(74.5)Zr(72)Tetrahedralvoid;OctahedralvoidTe11Oct3-Te12tructuralpatternof[MCl]x-tricappedtrigonalmClmCl,LaCl₃,CeCl₃,etc.LIStackingStacking4.52'A4.52'AFu,X.Fu,X.Sun*StructuredeterminationStructuredeterminationsmd,r⁰29Smd,(0231Smd,(0231withProf.YifeiMoExperimentExperiment10101010,CMCM-Sm.·0LICIDM-LCionicdiffusionbehaviorin(SmCl₃@LZC:103ationicdiffusionbehaviorin(SmCl₃@LZC:103atRT)XRDframework—lonicconductvnty-HalidesHabdeswthSmCI,wthoutSmCI,-HalidesHabdeswthSmCI,wthoutSmCI,会BM-SmCl₃·05LICIExponmentalplotCa!culatedpattemDfforonceRDfforonceBelowBelowthedetecbonfim1SmClohost650000)A)A(6PDF5LI'atomCIatomVacancyDM-Smc,.051londingca.6mg/cm²Areal85%rotontion85%rotontion400.5LI₂ZrCle0.5LI₂ZrClebofo%%。orthorhombic/HighEntropyAnionNa-Ta-O-CI蜜orthorhombicmonoclinic嗨蜜、癣步Li.Sun,et.al.Nat.Commun.2023Wang.Sun.et.al.Scl.Adv.2021Liang.Sun",et.al.J.AmLI,Sun",et.al.Angew.Chem.2019.K.Kang.etal.Sclence2023L.Nazar,etalNat.Enorgy2022Jung.etalAEM2021Jung.etalAEM2021Li.Sun,etFu,Sun",etal.J.AmLi.Sun,etFu.Sun”,etal.Adv.Mater.2023H.Yao,etal.Nature2023H.Xiangetal.Nat.Commun.2024304222(-ganksIruiuslstre0.302Ls₃PSC,Arorodile)00.302Ls₃PSC,Arorodile)0021CatbodCatbod2m1o10.2712m1o10.2717514₂S-P,inxLi₂O-TaCI₅COCPrpitLI·IvdrareLono-CVclinanumber0504205042theionicconductivityandactivationenergyrk0396rk03960.2710.2710一0一5LIxvalueinxLi₂O-TaCl,OOC十ALi-5LIxvalueinxLi₂O-TaCl,OOC十ALi-inxLi₂O-TaCl₅Liresultingintheformationofcorner-sharingZr-O/Clpolyhedrons.TheuniquestructurereducestheenergytheenergybarriersforLi-iontranspoTTRTa0a0GoocechanicalpropertyandelectrochemicalGoocechanicalpropertyandelectrochemicalperformanceofLi-Zr-O-ClanditsinvobedASSBs.aSun.J.AmaSun.J.Am.Chem.Soc.s.Zhang,xCretenumberuDuDZhangmun.mun.FromFromMaterialDesigntoPracticalApplicationsaREVIEWELECTROCHEMISTRYfinFrommaterialdesigntopracticalapplicationScIENCEADVANCES·SeD2022·vc2Tngonal0o-00BCBCCao=≤Y.inULo)x=F.QBr.DCBromuoesloddesmSouoVReaoocnldosopacn)CubicReaoocnldosopacn)Eccpccp020002LionmgrabonpatnggratcnpanyinhoanonLamoPmScratcnpanyinhoanonLamouonmgratonpaeaynccp~1~1mS/cm低低场氏Y.Hu,etal.NotMinEncrg2023,8,2221自自AIOCI/LiCI相界2Li₂O₂+2A1Cl₃2LiAlOCl₂+2LiCl+O₂↑9LiCl+8AICl₃+6H₂O△6Al15OCl₄+12HCl1NPDF27AINMRTOF-AL2AL1LiAIOCIAL2LIAIOCI-681AICI,6HOAs(ppn)30A₂O₂CI,云LIAIOCI-981AL1[AI,O.CI]ZD+-3ao32LiAIOCI-ab1:AICLAlOCl₂Al₄O₄Cl₃Al₂OCl₅Al₂O₂ClAl₂Al₂OCl₅Al₃O₃ClAl₃O₃ClAl₃O₇Cl₂Al₆O₇Cl₃J.Liang*,X.Sunl.dv.Moted.3009265%capadtyrotertion75Discharoe2040200eS0I3008486%capocyCoulombicefciencyChargeDischarge200reterdion9s400B5OAI₃O₂CL₆OAl₃O₂CleAl₂O₂Cl₆OLAIOC651LL1L123-50-50X.Li'血er.,accepted.0.10.10.01OCrust55432B4r4rLi₂CO₃price:>$10OOO/tAbundanceandwide800000YearBIERGYEBIERGYEConfiguration:fromliquidTheBottleneck:Smoothandtoall-solid-stateAO*AOotAdvantagesomeos通es482(2021):228872.JournalofWeldingjontsforeviewsournal1TraditionalNa+electβ-AluBin且wmSediamCoaductrityZectrohenialSablllyWladowlonisCondortivityClhalcogcnideDxfroakDxfroakMecLaekcetSreagrolytesNASICONCoedectltyElectrocbemkaMectaakaISragdywMechnnkcalStraderialsToday41(2020):200-218.ctivitysibilitybilisHzH₂HzH₂+Na(BH)₆NaBH₄B+B₉H1Na(B+B₉H1NaFAlF₃+FzNaAlF₃+FzNasAl₃F14AICl₃+AICl₃+Cl₂A+NaCINa₂O₂Na₂O₂NaIO₃+NalNa₂Oz+NaBrNa₂Oz+NaBrHighmechanicalNa₂Oz+Na14AlaO13NaAl,Oa+Na2O2Na3OBrNasAIO4NaAIOz+Na₂OzNaAIO₂+NaAIOz+Na₂OzNaAIO₂+Na₂O₂strengthAzO+ONa¹7AlsO16Al₂O₃+O₂NazZrSiAl₂O₃+O₂NazZrSi₄O21+O2+ZrSIO₄ZrSIOaZrSIOa+O₂+NaZrz(POa)+SiO2Na₃P+ZrOz+NaNa₃P+ZrOz+Na₃PO4NaTIOn+NaPOu+NaPOz+Zr₂P₂O₂+ZrP₂O₇Oz+Na₂Oz+Na₂SiO₃NaB₂Os+NaO₂Na4SiO4Na³BO3NaNbO+ONaSbONaNbO+ONaSbO₃+O₂O₂+CO₂Na3NbO4Na₃SbO4Na₂S+Na₂S+Na₂0Oz+SO₃O₂+Nb₂O₃P₂OO₂+Nb₂O₃P₂O₃+OzNa₃POs+Na₃PNa;Sb+Na₂SNa₂SNaSbSz+NaS₂NaSbSz+NaS₂NaSi+NaSi+Na₂SNa₂SI₂SNa3PS4Na₂SI₂SNa₂Se55CederZ.,Wolfgang,eral.ACSApplledEnergyMaterialsNaAIClACSEnergyLettersJ.Mater.Chem.A,2022一1.3mScm1Na-A-OCIglasSNatureEnergy,2023uu~2.7mScm-1NaSmClxandNaTaCl,compositeX.Sun,etal.Adv.Mater.20233see4%0.0031mScm-1;NaTaCLS.Ohno,etACSMaterialsLett.2024AmorphousNaTaClX.Sun,etal.Matter,20242020202120222D234品4-46-46Ur01wcmrSpinelNa₂Y₂BClSpinelNa₂Y₂BClZrOzNa₂ZrCl₆EnergyStorageMaterialsal.ACSMaterialsLett.Z,WolfgangACSMaterialsLett.Z,Wolfgang,etCommun.2023ACSAppl.EneroVater.Nature0.29mScm1Na₁-ZrLa₁-Cl₄H.Xiang,etal.NatCommun,202428303Na-Ta-0-ClglasSX.Sun,etal.Angew.Chem.IntEd.2024trigonaltrigonal温ooo障亶Li,Sun.et.al.Nat.Commun.2023jo[jo[orthorhombicorthorhombicWang,Wang,Sun*,et.al.EES,2023Wang,Sun*,et.al.Sci.AdWang,Sun*,et.al.Sci.AdLiang,Sun*.et.al.J.Am.Chem.Soc.2020Li,Sun*,et.al.Angew.Chem.2019.K.Kang,etal.Sclence20234.52ALi,Sun*,etal.Angew.Chem.2023Fu,Sun*,etal.J.Am.Chem.Soc.2023Li,Sun*,etal.Angew.Chem.2023ZHighEntropyX.Sun,×.Lietal.,Angew.Chem.2024X.Sun,×.Lietal.,Angew.Chem.2024S.S.Zhang,×.Sun*,et.al.J.Am.Chem.Soc.2024S.Zhang,×.Sun*,et.al20242024Y.Hu,etY.Hu,etddUCl₂-typeNaozM.z₅Cl₆(M=La,Sm),P6y/m[MCle]⁶-(1-×)[HCF-Sm]·×[LCF-Ta]amorphousNa₂HfCl₆NaTaCl₆x=0.38-30004000D1809*CAmorphizodiwithProf.YifeiMa62[HCF-Snp.62[HCF-Sm1-038ncF-Ta]a62[HCF-Snp.62[HCF-Sm1-038ncF-Ta]aNaPs4PCa32Ns1eameop可5己o°32movato0005714C210Crystnlizod大O4.00.62NSCVoltage0.2C88.3%B0Voltage0.2C88.3%B060DischargodNao.85Mno.5Nio32282.4091.0%Fe07O₂91.0%Fe07O₂OutstandinOutstandin9Adv.Md9Asuperionicconductorsforall-solid-stateXlaotingLno⁰,ShuminXlaotingLno⁰,ShuminZhang².MenghaoYang.BiwelXiao,WolhanU',FolpengYeng.HuiDuen',JianwonLieng',BoUnFuOHamidrezaAbdolvandO',JinghuaGuo0.GrahamKing'&XuellangSunuRacaivad:22Fobruary2023Accepted:29August2024PublisheJonline01October2024一一·一一OxychlorideSSEs:2-MclyC),M=Hf,Zr,Ta20msonSo5id-szeeectoye⁵Elecrochemicalwindow(Yv.Na"/N:SnEDistinctiveE1)AmorphousNMOCfeaturehighionicconductelectrochemicalwindow.2)AmorphousNMOCarecharacterizedbyhighlydisorderedMCl₆octahedrons,M-O-Clunits,andM-centeredconnectedviaedge-orcorner-sharingO/Cl.3)ThedifferentconnectionsbetweenM-centeredpolyhedronsinNMQCSSEsleadtovariationsirioniccondudV,ationenergy,andthermaCNMNFO/CNT/NHOCNHOCAI-solid-statesodium-ionbatteryRT.02cRT.02cAnode:Na15SnDeDergergeocathode,thefavthefavAImostaemicalproSS.3emicalproSS.3OutlineofThisTalkSputterArDetectorsampleholdersample-sample5mpleholderominBindingenergy/eyLi-stable(thermodynamically)SSEsstabilitystabilityO00000opO0oooo0o6AuVoltage²&s.Li2-52-5thDischargeDischarge0₃nC₃nC20406080100120140160180stabilitystabilitystabilitystabilityStabilityagainstcathode40恋主三面望怎8空89高负高UMgCIL₂MgBr.U.TI₃O1Li₀PS,CILISns.em.Mate28,1,266-2730s.Limetal)1GeP₂S₁2]Li₃PS3L₂OCI□i StrategiestostabilizeStrategiestostabilizeLiPN2,6.9×10-7S/cm(400Li₇PN4,1.7×10-5S/cm(400LiPN2,6.9×10-7S/cm(400Li₇PN4,1.7×10-5S/cm(400Vacancy-richL₉N₂Cl₃,4.3×10-5S/cm(25℃)2000~nowLiLiandXiaandWangetXiaandWangetetal.,Li₇N₂I-0.5LiOH,5.2×10⁴S/cm(25℃)AseriesoflithiumnitridophosphatesAseriesoflithiumnitridophosphates i~P3O3N×h0ifilmS/Sc(5C)NCINCI4.5(5)%inVacancy0%in4.3×10-5S/cmA1ObservedCalculaled2wR=15.1%24rIA6-50AwR=10.5%rIALi,N;CIImprovedioniccondty:A40-foldincreaseinroom-temperatureionicconductivity(4.3×10-5S/cm)Lithium-compatibSolid-stateAFM(2019)ACSr个2019EnergyLett.AEM(2020)7.1×10-4S/cm2020AEM(2021)Adv.Mater.8/sno1.8×10-3S/cm1.21×10-3S/cm2021Angew.Chem0.42×103S/cnSci.Adv.(2023)j94.3×10-5S/cm4.3×10-5S/cm20222023AEM(2024)Nat.Commun.(2024)JACS(2024)Li2.5No.5So.2.14×10-3S/cr2.14×10-3S/cr2024chemistryInterfaceAlucone-coatedchemistryInterfaceAlucone-coated个点LixSiSy-coatedLixSiSy-coated司platingplatingAFMAFMauceneloytEnergyAcC.Mater.ResauceneloytEnergyAcC.Mater.Res.Prog.Mater.Sci.EES(2020)AEM(2019)Nat.Commun.(2021)4.5(5)%inNClVacancy-triggeredfastlithium-ioncondfction4.3×10-S/cmA1(411A1A1(411A1A6wR=10.5%CalculatedOifferenceCalculated04-6mprovedionicconductivity:A40-fomprovedionicconductivity:A40-foeaseinroom-temperatureconductivity(4.3×10-5S4077000NCM83:4.460.5COChargeefficlency90.35%capacity4040cycles.90.35%capacityretentionretentionover1500NCM83cathodeLNCSSEcyclesat0.5C202efficiency Discharge40o0Y.LimAh/crCAntifluoriteAntifluorite2.1×104LiSLi₂.5No.5S0.5TOF-NPDRwp=2.51%Difference6A12.1281inLi-SSE-LisymmetriccellsSymmetricbatteriesLi₃InCl₆Li₃InCl₆LI10GoP₂S12metalinanAr-filledgloveboxLi₂₅NoSoLi₃InCl₆Ll10GeP₂0.5000LrHHHHHMLi₆PS₅CILLNoSc4n4n00bleemiclencynm.-...2..NewsuperioniclithiumnitridehaliLi₃xMCIyN×(M=TaorLa,1≤3x≤1.4,y=5or3)IncorporationLiLaCl₃No.333:σ(30℃)=0.01mS/cmTaCl₅/LaCl₃AmorphouslatticeLTCN/LLCNofLi-CIbondsacrossthe-naceamongtheTaClNypolyhedrabystretchingTa-Cl.14DoEctx30四20CaeDsve2CaeDsvecoc高