Toward Understanding the Lithium Transport Mechanism in Garnet-type Solid Electrolytes Li+ Ion Exchanges and Their Mobility at OctahedralTetrahedral Sites

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1、Articlepubs.acs.org/cmTowardUnderstandingtheLithiumTransportMechanisminGarnet-+typeSolidElectrolytes:LiIonExchangesandTheirMobilityatOctahedral/TetrahedralSites††‡,§§††DaweiWang,GuimingZhong,WeiKongPang,ZaipingGuo,YixiaoLi,MatthewJ.McDonald,,∥⊥,†RiqiangFu,*Jin-XiaoMi,andYongYang*†CollaborativeI

2、nnovationCenterofChemistryforEnergyMaterials,StateKeyLabofPhysicalChemistryofSolidSurfaceand⊥DepartmentofChemistry,CollegeofChemistryandChemicalEngineeringandDepartmentofMaterialScienceandEngineering,XiamenUniversity,Xiamen361005,China‡TheBraggInstitute,AustralianNuclearScienceandTechnologyOrga

3、nisation,LockedBag2001,KirraweeDC,NewSouthWales2232,Australia§InstituteforSuperconductingandElectronicMaterials,UniversityofWollongong,Wollongong,NewSouthWales2522,Australia∥NationalHighMagneticFieldLaboratory,1800E.PaulDiracDrive,Tallahassee,Florida32310,UnitedStates*SSupportingInformationABST

4、RACT:Thecubicgarnet-typesolidelectrolyteLi7La3Zr2O12withaliovalentdopingexhibitsahighionicconductivity,reachingupto∼10−3S/cmatroomtemperature.FullyunderstandingtheLi+transportmechanismincludingLi+mobilityatdifferentsitesisakeytopicinthisfield,andLi7−2x−3yAlyLa3Zr2−xWxO12(0≤x≤1)areselectedastarget

5、electrolytes.X-rayandneutrondiffractionaswellasacimpedanceresultsshowthatalowamountofaliovalentsubstitutionofZrwithWdoesnotobviouslyaffectthecrystalstructureandtheactivationenergyofLi+ionjumping,butitdoesnoticeablyvarythedistributionofLi+ions,electrostaticattraction/repulsion,andcrystaldefects,wh

6、ichincreasethelithiumjumprateandthecreationenergyofmobileLi+ions.Forthefirsttime,high-resolutionNMRresultsshowevidencethatthe24d,96h,and48gsitescanbewell-resolved.Inaddition,ionicexchangebetweenthe24dand96hsitesisclearlyobserved,demonstratingalithiumtransportrouteof24d−96h−48g−96h−24d.Thelithium

7、mobilityatthe24dsitesisfoundtodominatethetotalionicconductivityofthesamples,withdiffusioncoefficientsof10−9m2s−1and10−12m2s−1attheoctahedralandtetrahedralsites,respectively.conductivityofthecubicphase,usingelementssuchasAl3+,1.INTROD