拉曼光谱在锂离子电池研究中的应用

171Vol．17No．120112ELECTROCHEMISTRYFeb．20111006-3471201101-0012-12*1001902010-09-212010-11-05*[e-mail]8632009AA033101、50972164、KJCX2-YW-W26“”Ramanspectroscopy、LiMn2O4LiFePO4、/．-SERSO646A1928ChandrasekharaVenkataRaman1930．．Raman、、、、、、、．、、、、、、．、、、．、、、、-．．、、、X、、、、、、、X、X1．．11．1R-3m166290～350mAh/g、500～100090%～93%．1000～2000cm－11582cm－1E2g2G-band1330cm－1A1gD-band．Gsp2．D、、、．D．GDLa2．MCMB5～20μm．MCMB．MCMB3．1MCMB．1580cm－11360cm－1．MCMBDG4．1MCMB4Fig．1RamanspectraoftheMCMBsheat-treatedatdiffer-enttemperaturesreprintedwithpermissionfromref4copyright1996TheElectrochemicalSociety1．2LiMxMn2-xO4LiMn2O4Fd-3m2253．9～4．1Vvs．Li/Li+、95～120mAh/g、、．5625cm－1A1g426～432cm－1Eg365～380cm－1、480～485cm－1、580～590cm－1Fg．A1gMnO6Mn—O．LiMn2O4Mn．JulienLiMn2O4A1gMn—OMn4+O6Mn3+O6．580cm－1Mn4+—OLiMn2O4Mn4+5．Hwang580cm－1625cm－1A1gMn4+O6Mn3+O66．LiMn2O4Mn4+Mn3+7-8．LiMxMn2-xO4M=Ni、Co．A1gLiMxMn2-xO4MnMO6M—OA1g．Ni2aLiNixMn2-xO4x=0．2A1gLiNi0．2Mn1．8O4MnNiO69．LiNi0．5Mn1．5O4．Amdouni10LiNi0．5Mn1．5O4Fd-3mNi2+Mn3+P4332Ni2+Mn4+．LiNi0．5Mn1．5O4NiMnXXRD．、2b．1．1．3FTIR．．Li-ClO4-EC、PC、DMSO、DMF-PAN16-21．LiClO4/ECEC713cm－1LiClO416．EC·31·11Tab．1WavenumbersofRaman-activemodesofsomeimportantcathodeandanodematerialsofthelithiumionbatteryMaterialsAssignmentsofmainRamanbands/cm－1Graphite21580E2g21330A1gHardcarbon261590E2g21355A1gLiCoO211595A1g485EgLiMn2O45625A1g580F2g483F2g426Eg382F2gLiFePO4301071999953292226Si12520crystalline480amorphousLi4Ti5O1213671A1g430Eg347F2g271F2g232F2gTiO2anatase14639Eg518A1gB1g398B1g198Eg144EgV2O515994Ag700B1gB3g526Ag282B1gB3g144B1gB3g2NiLiNixMn2-xO4a9Fd-3m、P4332LiNi0．5Mn1．5O4LiMn2O4b10Fig．2RamanspectraoftheLiNixMn2-xO4aandtheLiNi0．5Mn1．5O4powdersFd-3mandP4332comparedwiththatofLiMn2O4breprintedwithpermissionfromref9copyright2006Elsevierareprintedwithpermissionfromref10copyright2007ElsevierbCO893cm－1Li+17．713cm－1Li+--ClO4-Li+ClO4-n．EC/LiClO4/PANPAN帒帒CN2000cm－1Li+PAN帒帒CNN18．PC19DMSODMF20Li+．3PC/LiClO4/PANPAN帒帒CN．PCaPAN2240cm－1PCb19．Li+PAN．·41·20113PC/LiClO4/PANPCab帒帒CN19帒帒Fig．3RamanspectraoftheCNstretchingmodeofPANinPC/LiClO4/PANaandinplasticizer-freeLiClO4/PANbreprintedwithpermissionfromref19copyright1997TheElectrochemicalSocietyLi+Li+--ClO4-．PAN、、．4LiCF3SO3-SO3abFig．4RamanspectraoftheSO3symmetricstretchingbandaandtherelativeamountofdifferentionicspeciesbinLiCF3SO3∶acetamidecomplexwithdifferentmolarratios、、、、．、、22-24．LiCF3SO3/CH3CONH2COLi+LiCF3SO3．CF3SO3-SO3NH2、．-、--、“”．CF3SO3-SO3CF3Li+“”、．4LiCF3SO3LiCF3SO3SO3ab．．31032cm－1、1040cm－1、1050cm－1、．．·51·15Hab1000℃cd27LaFig．5RamanspectraofthehardcarbonsphereswithhighHcontentabandthehardcarbonspheresheat-treatedat1000℃cdafterdifferentcyclesanditscalculatedLavaluesreprintedwithpermissionfromref27copyright2007Elsevier．2/-/-．2．1、．25-26．．1000℃H．27．1590cm－11355cm－1GD．LaGD．5H1000℃La．HLa5．HLa．HLiLiHLiHHC．H—C—C—27．2．2LiFePO4LiFePO4、、170mAh/g．LiFePO4．LiFePO4/LiFePO4/FePO4GibotXRDLiFePO428．LiFe-PO429．PO43-900～1100cm－13P—O400cm－1PO43-Fe2+·61·2011．LiFePO4LiFePO4LiFePO4．BurbaFTIRLiFePO430．LixFePO4LiFePO4FePO4LiFePO4FePO4LiFePO4．FePO4LiFePO4FePO4x=0．38FePO4．LiFePO4．FePO4LiFePO4．2．3Li-AgSEI1．0V-SolidElectrolyteInterphaseSEI．SEI31-34．SEI．70SERS35-37．AgSEI38-39．AgSERS．0．8V0．4V0V715cm－1744cm－11090cm－11460cm－1Li2CO31009cm－11146cm－11380cm－1SEIROCO2Li．SERSAuAgSERSSEI．、SERS3640．“”41．SERSSEI．STMTERS42．SNOM．-．3/Ra-man．．/．Raman．XRD．1143-52．XRDRaman．3．148-50．LiClO4/EC∶PCSFG60．2VG．Li+G1578cm－1E2g2i1602cm－1E2g2b．LiD．HardwickL．J．LiD50．．SFG44Li+-PC0．8V．G0．8V1597cm－1G．E2g2bLi+-·71·1E-band．SFG6SFG44LiClO4/EC∶DMCELi+50．Li+-．3．2LiMxMn2-xO4LiMn2O4LiMn2O4LiXMnXRD．Ni、CoLiMxMn2-xO4．7LiNi0．5Mn1．5O451．bc500cm－1Ni2+—O53-544．68V488cm－1Delichere53Cordba-Torresi54Ni3+—O488cm－1540cm－1Ni4+—O7LiNi0．5Mn1．5O4abc647．1nm51Fig．7CyclicvoltammogramsoftheLiNi0．5Mn1．5O4thinfilmsin1mol/LLiBF4-EC-DMCaanditsin-situRamanspectra647．1nmlaserexcitationforpotentialscanningfrom3．40Vto5．00Vbandfrom5．00Vto3．40Vcreprintedwithpermissionfromref51copyright2002TheRoyalSocietyofChemistry6SFG6aSFG44b1mol/LLiClO4-EC-PC50Fig．6Firstlithiationcurveanditsin-situRamanspectraseriesoftheSFG6graphiteaandtheSFG44graphitebin1mol·L－1LiClO4-EC-PCsolutionreprintedwithpermissionfromref50copyright2007Elsevier·81·20118LiCoMnO4abc647．1nm52Fig．8CyclicvoltammogramoftheLiCoMnO4thinfilmsin1mol·L－1LiBF4-EC-DMCanditsin-situRamanspectra647．1nmlaserexcitationforpotentialscanningfrom3．50Vto5．50Vbandfrom5．50Vto3．50Vcreprintedwithpermissionfromref52copyright2004Elsevier9MoO3a．1．5V～3．0Vb．10mV～3．0Vc．Fig．9Firstdischarge/chargecurvesoftheMoO3nano-beltsvoltageranges/Va．1．5～3．0b．0．01～3．0c．in-situRa-manspectrameasuredatdifferentstatesofcharge632．8nmlaserexcitation55-56．a4．72V4．78VC/C'Ni2+Ni3+D/D'Ni3+Ni4+．LiCoMnO4852．aDbc550cm－1Co4+—O．LiNi0．5Mn1．5O4540cm－1Ni4+—OLiMn2O4．．·91·1///．LiNi0．5Mn1．5O4．．1/2．Li4Ti5O12LiCoO211．．．9MoO3．2．75VMoO3．0．5VMoO3MoLi2O．MoOLi2OLixMoO3．、X、．．．57．4．、、．Raman．References1Baddour-HadjeanRPereira-RamosJP．Ramanmi-crospectrometryappliedtothestudyofelectrodemate-rialsforlithiumbatteriesJ．ChemRev201011031278-1319．2TuinstraFKoenigJL．RamanspectrumofgraphiteJ．JChemPhys1970