A Computational and Spectroscopic Study of the - Roginskii et al. - Unknown - Unknown

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SupportingInformationAComputationalandSpectroscopicStudyoftheElectronicStructureofV2O5-BasedCathodeMaterialsEvgeniiM.Roginskii,,yMikhailB.Smirnov,zKonstantinS.Smirnov,,{RitaBaddour-Hadjean,xJean-PierrePereira-Ramos,xAlexanderN.Smirnov,yandValeryYu.DavydovyyIoffeInstitute,Polytekhnicheskaya26,194021St.Petersburg,RussiazFacultyofPhysics,St.PetersburgStateUniversity,Petrodvoretz,194508St.Petersburg,Russia{Univ.Lille,CNRS,UMR8516–LASIRe–LaboratoireAvancédeSpectroscopiepourlesInteractionslaRéactivitéetl’Environnement,F-59000Lille,FrancexInstitutdeChimieetdesMatériauxParis-Est(ICMPE),UMR7182CNRSetUniversitéParis-EstCréteil,2rueHenriDunant,94320Thiais,FranceE-mail:e.roginskii@mail.ioffe.ru;konstantin.smirnov@univ-lille.frS1

1TableS1:Structuralparametersof-VO,0-VO,-LiVOand-NaVO.25252525PhaseSpaceGroupExperimentalLDA+Ua(Å)b(Å)c(Å)a(Å)b(Å)c(Å)-V2O5Pmmn11.5054(3)3.5563(1)4.3765(2)11.7413.5823.8570-VOPnma9.6885(2)3.6039(1)10.6731(2)9.7913.5829.53425-LiV2O5Pnma9.9483(2)3.5863(1)10.0458(3)9.5793.56410.453-NaV2O5Pnma9.7805(3)3.6299(1)11.8871(5)9.5543.55111.844TableS2:Experimentalandcalculatedunitcellparametersandbondlengths(inÅ)of-MeV2O5,(Me=Li,Na).-LiV2O5-NaV2O5ParameterExp.bPBE-D2+UcLDA+UExp.bPBE-D2+UaLDA+Ua9.6959.7919.5799.7819.9059.554b3.6063.6013.5643.6303.6263.551c10.67810.78110.45311.88712.13811.844Va-O1a1.5951.6461.6271.5481.6431.616Va-O2a21.8921.9021.8701.9091.9111.865(Va-O2a)LS1.9752.0261.9771.9702.0351.977Va-O31.7371.7461.7211.7941.7471.720Vb-O1b1.5761.6591.6371.5871.6521.621Vb-O2b21.9371.9701.9331.9531.9701.930(Vb-O2b)LS1.9672.0071.9621.9491.9961.943Vb-O31.9612.0101.9451.8822.0171.941bRef.1;cGGA(PBE)+UlevelwithD2dispersioncorrections,ref.2.S2

2TableS3:Directandindirect(inparentheses)bandgapvalues(ineV)calculatedbyGW@LDA+Umethodfor-VO,0-VO,-LiVOand-NaVO.0025252525PhaseU=4eVUaeffLR-V2O52.89(2.42)2.89(2.42)0-VO3.17(3.09)3.12(3.04)25-LiV2O51.21(1.21)1.30(1.30)-NaV2O51.18(1.18)1.32(1.32)aULRdenotesUobtainedbythelinearresponsemethod:U=4:5eV,4.9eVand5.2eVforthe-V2O5and-V2O5and-MeV2O5,respectively.InthecalculationsusingULR,J=0:1ULR.a)c)145124272329987737965171462Intensity(arb.units)100253Intensity(arb.units)53328599436954964620510370119530440548252720040060080010002004006008001000Ramanshit,cm-1-1Ramanshit,cmb)d)138717100532329754695985Intensity(arb.units)470655153Intensity(arb.units)1552821004110103893126172267695250349388190239299392501534604723753102319120040060080010002004006008001000Ramanshit,cm-1-1Ramanshit,cmFigureS1:Ramanspectraof-V2O5(a),-V2O5(b),-LiV2O5(c),and-NaV2O5(d)recordedwiththewavelengthofincidentradiation0=633nm.S3

31.00a)EF1.00b)EF0.750.750.500.500.250.250.000.000.250.25DOS(arb.unit)DOS(arb.unit)0.500.50LDA+U,spinupLDA+U,spinup0.75LDA+U,spindown0.75LDA+U,spindownPBE+U+D2,spinupPBE+U+D2,spinupPBE+U+D2,spindownPBE+U+D2,spindown1.001.004321012343210123Energy(eV)Energy(eV)FigureS2:Electronicdensityofstates(DOS)of-LiV2O5obtainedintheLDA+Ucalcula-tionswith(a)Ueff=4eVand(b)Ueff=4:7eV(valuecomputedwiththelinearresponsemethod),comparedwithDOSobtainedatthePBE+U+D2levelinref2.6543210Energy,eV-1-2-3-4-5ΓZTYSXURFigureS3:Electronicbandstructureof-NaV2O5calculatedinG0W0@LDA+Uapproxima-tion.Redandblacklinesstandforthespinupandspindownstates,respectively;dashedlinesindicatethepositionsoftheFermilevel(E=0)andthebottomoftheconductionband.S4

43.0a2.52.01.5b1.0Intensity(arb.units)0.5c0.020040060080010001200Ramanshift,cm1FigureS4:ExperimentalRamanspectraof-NaV2O5recordedwiththewavelengthsofexcitingradiation0=785nm(a),0=633nm(b),andexperimentalRamanspectrumof-LiV2O5obtainedwith0=785nm(c).S5

5References(1)Emery,N.;Baddour-Hadjean,R.;Batyrbekuly,D.;Laïk,B.;Bakenov,Z.;Pereira-Ramos,J.-P.-Na0:96V2O5:ANewCompetitiveCathodeMaterialforSodium-IonBat-teriesSynthesizedbyaSoftChemistryRoute.Chem.Mater.2018,30,5305–5314,DOI:10.1021/acs.chemmater.8b02066.(2)Smirnov,M.B.;Roginskii,E.;Kazimirov,V.Y.;Smirnov,K.S.;Baddour-Hadjean,R.;Pereira-Ramos,J.-P.;Zhandun,V.SpectroscopicandComputationalStudyofStructuralChangesin-LiV2O5CathodicMaterialInducedbyLithiumIntercalation.J.Phys.Chem.C2015,119,20801–20809,DOI:10.1021/acs.jpcc.5b05540.S6