钛酸锂电池应用介绍

ShandongYuhuangNewEnergyTechnologyCo.,Ltd.(YHNETC)非主流锂电技术–钛酸锂Non-mainstreamLi-ionbatterytechnology-LTO薛嘉渔首席科学家山东玉皇新能源科技有限公司Sept.23,2016ShandongYuhuangNewEnergyTechnologyCo.,Ltd.(YHNETC)EVbatteries1UnderstandtheLTO23Applications(EV&ESS)4Who’swhoinLTOContentsShandongYuhuangNewEnergyTechnologyCo.,Ltd.(YHNETC)1.Safety2.Consistency(orReliability)3.Longcyclelife(10-15yrs?)4.Highpowerdensity(HEV)5.Highenergydensity(BEV)6.Lowcost(5-10%lower/year?)7.High&lowtemperatureperformance(-40to65oC)RequirementofLi-ioncellsforxEVShandongYuhuangNewEnergyTechnologyCo.,Ltd.(YHNETC)AluminumcasedprismaticcellsforxEVShandongYuhuangNewEnergyTechnologyCo.,Ltd.(YHNETC)AluminumcasedLi-ioncellforxEVShandongYuhuangNewEnergyTechnologyCo.,Ltd.(YHNETC)PouchprismaticcellsforxEVShandongYuhuangNewEnergyTechnologyCo.,Ltd.(YHNETC)PouchprismaticcellsforxEVShandongYuhuangNewEnergyTechnologyCo.,Ltd.(YHNETC)Howthecellfails(thenightmareforLIBengineers)?Abnormalamountofheatgeneratedinternallyinthecellmostlyfromgraphiteanodecouldleadtofireorexplosion!ShandongYuhuangNewEnergyTechnologyCo.,Ltd.(YHNETC)起始状态Initialstate经长期循环AfterextensivecyclingTheinternalmechanicalstressofelectrodescausedbycharging/discharginggraphiteleadstoelectrodedisconnectioninthecell!Theexpansion/contractionoftheLIBShandongYuhuangNewEnergyTechnologyCo.,Ltd.(YHNETC)BriefhistoryofLTOIn1971,spineltypeLi4Ti5O12orLTOwasfirstreportedbyDeschanvresetal.DeschanvresA,RaveauB,SekkalZ.Miseenevidencecristallographiqued'unenouvellesolutionsolidedetypespinelleLi1Ti2,O4(0≤x≤0.33)[J].Mat.Res.Bull.,1971,6(8):699-704.In1989,Colbowetal.hadstudiedmorethanitsstructuralpropertiesbutalsothepossibilityofusingLTOasanelectrochemicalmaterial.ColbowKM,DahnJR,HaeringRR.StructureandElectrochemistryoftheSpinelOxidesLiTi2O4andLi4/3Ti5/3O4[J].J.PowerSources,1989,26(3-4):397-402.In1995,Ohzukuetal.referredtheLTOasa“zerostrainedmaterial”.OzukuT,UedaA,YamamotoN.Zero-StrainInsertionMaterialofLi[Li1/3Ti5/3]O4forRechargeableLithiumCells[J].J.Electrochem.Soc.,1995,142(5):1431-1435.……..ShandongYuhuangNewEnergyTechnologyCo.,Ltd.(YHNETC)HowtheLTOchemistryworks?Li4Ti5O12Chemicalformula:Li3(Li1Ti5)O12Chargebalanced:Li+3(Li+1Ti4+5)O2-12Spinel=AM2O4or(AM2O4)x3=A3M6O12[Li+3]8a[Li+Ti4+5]16d[O2-12]32e[Li+6]16c[Li+Ti3+3Ti4+2]16d[O2-12]32eDischargestate:Chargestate:Theoreticalcapacity:175mAh/gadisch=0.836nm;aCh=0.837nm“Zerostrained”crystallatticeSpacegroup:Fd3ma=0.836nm5Ti4+/1Li+in16dsiteorOhLi+in8asiteorTd(Disch)Li+in16csiteorOh(Ch)6Li+movefrom8ato16cShandongYuhuangNewEnergyTechnologyCo.,Ltd.(YHNETC)Isgraphitetheangel/devilintheLi-ioncells?Graphiteistheangel!1.OKlowTperformance2.OKcyclelife3.OKcharge/dischargerate4.Cellexpansion5.Highenergydensity(E.D.)LTOshowsjusttheoppositeofgraphite:-noSEI(1-3)-“Zerostress”crystallattice(4)-E.P.=1.55V,safebutlessE.D.!Graphiteisthedevil!-DuetoSEI(1-3)-Intrinsiclayerexpansion(4)-IntrinsicE.P.≈Li0(5)ShandongYuhuangNewEnergyTechnologyCo.,Ltd.(YHNETC)Al3+/Ga3+Mg2+Al/Galowered0.045VinLTOvoltageEfforttolowertheE.P.ofLTOShandongYuhuangNewEnergyTechnologyCo.,Ltd.(YHNETC)LTOturnedmetallicunderareducingatm.0min30minObservation:AlongresidencetimeofLTOinareducingatmosphereof5%H2S+95%H2seemsenabledthemetallicnatureofthematerial.ShandongYuhuangNewEnergyTechnologyCo.,Ltd.(YHNETC)120min.Control300min.10203040506070800200040006000IntensityA-B2LTO-00-026-119810203040506070800200040006000IntensityAB3LTO-00-026-1198300min.120min.-AnoxygendeficiencyintheLTOcouldbethereasonforanexpansionofcrystallatticecausedbythereducingatmosphere.-Thisoxygendeficiencyseemsrelevanttotheincreasingmetallicnatureofthecompoundwhichisdesiredasananodematerial.XRDshowedalatticeexpansionduetoH2!17.518.018.519.019.50200040006000800010000IntensityAB2LTO-00-026-1198Rutile-01-071-6411BTRAB3Acontinuousshiftof2Ɵpeakaround18.4degreeindicateanexpansionincrystallatticecausedbyreductionof5%H2S+95%H2.ShandongYuhuangNewEnergyTechnologyCo.,Ltd.(YHNETC)99.599.699.799.899.9100100.1100.2100.3020040060080010001200Weight(%Temperature(C)16TGAresultconfirmedanO-deficiencyintheLTO99.599.699.799.899.9100100.1100.2100.302004006008001000Weight%Temperature(C)TGLTO-CcompositeLTO(pristine)LTO’sElectroniccond.(S/cm)ValenceofTi-ionsLi4Ti5O1210-9+4Li7Ti5O1210-2+3&+4Li4Ti5O12-x-C10-7Little+3&Lotof+4CarboncoatedLTOThetableshows2importantresults:-Inachargedstate,LTOisveryconductive;-TheoxygendeficiencyinLTOenhancestheconductivity&lowersvoltageofLTO.TGAresultfurtherconfirmedthatanoxygendeficientexistsintheLTO.ShandongYuhuangNewEnergyTechnologyCo.,Ltd.(YHNETC)Thelithiumintercalationvoltageisfoundtodecreaseby0.06V(fromtheoriginal1.55Vto1.49V),whichgivesrisetoatleast5%increaseinenergydensityonthefullcelllevel.A0.06VvoltagereductioninducedbyO-vacancyinLTOShandongYuhuangNewEnergyTechnologyCo.,Ltd.(YHNETC)SafestAnodeTargetedmarket&IPLongestcyclelifeHighratecapabilityLow/highTperformanceCosteffectivePro’s&Con’sofLTOLTOCon’sofLTO-Lowenergydensity-Highmaterialcost?-Cellgassing(know-how)?-Marketisnotobvious?(educatetheconsumers)ShandongYuhuangNewEnergyTechnologyCo.,Ltd.(YHNETC)P