全固态薄膜锂电池研究进展和产业化展望_陈牧

20143461－20JOUＲNALOFAEＲONAUTICALMATEＲIALS2014Vol.34No.6pp．1－20100095、、。、、。、、。、、。LiPONdoi10.11868/j.issn.1005-5053.2014.6.001TM911TQ152O646．21A1005-5053201406-0001-202014-09-032014-09-201966—[e-mail]1985—、[e-mail]。、、。。20、、1。、。、、、、。。“”7872013132。。TeslaModelS。201343。、———4。———5～7、、、。1、、8。/34、、、、、、、、。“”9、“”10、“”11。LiLiLiLi。“”。。1、、、10μm。LiCoO2、LiLiCoO2幑幐xLi++Li1－xCoO2+xe－0．5＜x＜111ab7Fig．1Anall-solid-statethinfilmlithiumbatteryaworkingprinciplesandlayeredstructurecomparedwithlithiumionbatterybcross-sectionalfield-emissionscanningelectronmicroscopeimage7Ｒeprintedfrom7withpermissionfromtheAmericanChemicalSocietyCopyright2012．LiCoO2Co3+Co4+Li+Li+Li。。//Li+。Li+“”rockingchair12。。Co4+、。1a、。1、、、2345、、。14500095%100080%2－40～150℃263、4、、、。。2“”。1972LiLiI13。1983Kanehori14Li/Li3．6Si0．6P0．4O4/TiS2。TiS2CVDLi3．6Si0．6P0．4O4LiWO3WO3-V2O52．5V3～16μA/cm245～150μAh/cm2200。2090。Bates1992Li-PONLi3PO1－xNx415。LiPON。1016。LiPON20。、、、、2。。、、。2、Fig．2Adevelopmenthistoryofelectrodeandelectrolytethinfilms2．1。/。。、LiCoO217、LiNiO218、LiMn2O419、LiFePO420LiNiMn2O214、LiNiCoMnO2221。Li//。LiCoO2/。LT-334LiCoO2HT-LiCoO2。HT-LiCoO2Li+Li+。101104Li+3．9V3．5～4．2Vx0．5～1．0。HT-LiCoO2137mAh/g700mAh/cm369μAh/cm2·μm。LiCoO2TiFeNiZr。LiNiO2LiCoO2Li+。1Table1MainelectrochemicalpropertiesoftypicalcathodethinfilmsCrystallinestructureCathodefilmsSpecificcapacity/mAh/gVolumetriccapacity/mAh/cm3LicontentvariationxPotentialplateauvsLi/Li+/VLayeredhexagonalLixCoO21377000．5－13．9LixNiO2150－2006500．35－0．853．8SpinelcubicLixMn2O41206500－14．11－23．0OlivineorthorhombicLixFePO4140－1706100．1－13．4LixMnPO41715900－14．1LixCoPO41676200－14．9LayeredV2O51184000－0．83．0LiMn2O4Li+LiCoO2LiCoO2。LixMn2O43．5～4．5V0＜x＜1。1＜x＜2LixMn2O43VJahn-TellerLixMn2O419。LiMn2O44．1V。LiMn2O412V。LiFePO4--Li+。3．4V20。。LiMn-PO4LiCoPO4。V2O5、、、、。3．2V3．4VLixV2O5x0～0．82．3Vx2。2．2、、、。。。2080Li2O-P2O5-Nb2O5Li2O-V2O5-SiO2Li2O-B2O3-SiO23242Li2O-P2O5-TiO252Li2O-SiO2-P2O2627528、。LiPON。NLi3PO47×10－8S/cm。Bates1992Ar/N2Li3PO4LiPON26。LiPONLi5．5V3×10－6S/cm8×10－13S/cm0．55eV46、。22930、MOCVD。Kim31MOCVDLiC11H19O2C2H53PO4LiPON2．96×10－7S/cm。Li-PONNLi3PO4—O—ONN——N＜LiPON。NLi-PON32。LiPONSiLiSiPON8．8×10－6S/cm33。LLTOLi3xLa2/3－xTiO310－5S/cmLLTOLiCoO234。1000℃LLTOO2Li2O。LLTO10－8～10－9S/cm35。LiNbO3LiTaO3LiNbO32．2×10－9～8．4×10－7S/cm3610－5S/cm37LiTaO38×10－8S/cm3810－11S/cm3。Li+。2．3Li+。、3860mAh/g180℃250℃。。Li、、。。TiO2、TiO2Li+1．8VLixTiO20＜x＜0．5168mAh/g660mAh/cm339。LixTi5O124＜x＜70．2%。Li+LixTi5O121．5～1．6V175mAh/g610mAh/cm340。IVSiGeSnPb4Li。Si3579mAh/gLi15Si4300%41GeLi21Ge51600mAh/gLi+GeSi100SnLiLi21Sn5963mAh/g359%Li21Sn5PbLi21Pb5556mAh/g42。Li2OLi3N4344MOx+2xLi++2xe－幑幐M+xLi2ONaClMnOFeOCoONiOCu2OCu3N45Sn3N464Zn3N472Ge3N484。Li。MOxMM+xLi++xe－幑幐LixMLi+。SnOSnOSnLiLi21Sn5。Li2O49。、Ge、SnSi、、、、SnSi。“”Li11。2．4、2。、、、。534。3“”。1、、1～1000mm2。。。。2＜2Ω/□。3～1μm300～700℃。4～1μm。5～1μmSn3N4V2O5。62。7。2Table2SummaryofmainfabricationmethodsofactivethinfilmsPreparationmethodsCathodematerialsElectrolytematerialsAnodematerialsPreparationmethoddescriptionCharacteristicsofthemethodMagnetronsputteringPhysicalLiCoO1750～522LiNiO532LiMn2O19544LiFePO2055564LiCoPO574V2O585LiPON15LiNbO593LiTaO603SnO2Sn3N464V2O5TiO61622Li4Ti5O6312Targetsurfacesaresputteredbyionsinvacuumandproducetargetionsontosubstrates．Prosuniformfilmcompositionandthicknesshighpurityandstrongadhesiontosubstrates．Conslowdepositionratebyr．f．sputteringhighcost．E-beamevaporationPhysical—LLTO64LiPON65Li9Materialsareevaporatedlocallybyhigh-powerelectronbeamsandaretransformedintogaseousphasesandprecipitateontosub-strates．Prosfastdepositionratefilmsofhighpurity．Consevaporationofhighmeltingpointmaterialshighcost．PulsedlaserdepositionPhysicalLiCoO662LiNiO672LiMn2O684LiFePO69704V2O71725LiPON3273LLTO3474LiNbO753LiTaO763TiO772Li4Ti5O7812Pulsedlaserisfocusedontargetsurfacerapidlyevaporatestar-getmaterialofhighenergiestosubstrates．Pulsedlaserisfocusedontar-getsurfacerapidlyevaporatestargetmaterialofhighenergiestosubstrates．ElectrostaticsprayingPhysicalLiNiO792LiCoPO804LiMnPO814——Highvoltagesareappliedonsurfaceofsolutionscontainingprecursorstoproduceaerosols．Aerosolsarecoatedontosub-stratesviaelectrostaticcoating．Proshighefficiencysimpleequipmenteasytooperate．Consrequirementofconduc-tivefilmsandpostannealingtreatments．Sol-geldepositionChemicalLiCoO5182～842LiNiO852LiMn2O86874LiFePO88～914V2O92935LLTO94LiNbO953LiTaO963TiO972Li4Ti5O9812Afterhydrolysisandpolyconden-sationreactionsoforganicsol-ventsolutionswithcompoundssolisspin-coatedontosubstratesandannealedintogel．Proseasytodopingmodifica-tionsimpleprocesslowcostlargefilmareasuitableformassproduction．ChemicalvapordepositionChemicalLiCoO991002LiMn2O1014V2O1025LiPON83LiNbO1033LiTaO1043AmorphousSi105106TiO1072Mixedgasesareintroducedintovacuumchambersheatedcrackedreactedandcondensedintofilms．Prosfilmsofhighqualityanduniformthicknesshighcoat-ingrateeasytomassproduc-tion．Conscontrollingfilmcompo-sitionsbytuninggasespartialpressures．663Fig．3AprocessflowdiagramofmanufacturingsinglethinfilmlithiumbatterybyPVD4。1、。LiCoO2LiMn2O4LiFePO4400～700℃Li+。。、、、。2LiPON1×10－6S/cm。3、、。。4、、、。Li/LiP