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20143461-20JOURNALOFAERONAUTICALMATERIALS2014Vol.34No.6pp.1-20100095、、。、、。、、。、、。LiPONdoi10.11868/j.issn.1005-5053.2014.6.001TM911TQ152O646.21A1005-5053201406-0001-202014-09-032014-09-201966—E-mailyue.yan@biam.ac.cn1985—、E-mailchenmu2013@tsinghua.org.cn。、、。。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—ONN——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
本文标题:全固态薄膜锂电池研究进展和产业化展望_陈牧
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