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ConfidentialResearchandDevelopmentLFP–OlivinetypeLithiumIronPhosphateCathodeFamily

橄欖石結(jié)構(gòu)鋰化合物陰極LFPUniqueSolution—LFP-NCONextGenerationofLFP-NCOTheCapacityoftheProductionProcessandEquipmentConfidential＊PreviousShortcomings:Slowkinetics（kainetiks動力）oflithiumiondiffusion(擴散傳播)throughtheLiFePO4/FePO4interfaces.（N-Typesemiconductors）

Improvement

MinimizeparticlesizeSol-gel濕法-凝膠法Co-precipitations沉淀Hydrothermal熱

Solvothermal溶劑法Spraypyrolysis噴霧熱分解etc.*Lowelectronicconductivity.導電度

ImprovementSupervalentcationdoping(LiMXFe1-xPO4,M=Zr4+、Nb5+)EnhanceelectronicconductivityAddedconductiveagentMetals(Ag、Cu)CarboncoatingImprovementstoLFP

A.S.Andersson,J.O.Thomas,JournalofPowerSource.,2001,97-98,498-502.ConfidentialLFPA123Li1-xM’FePO4LiFe1-xM’xPO4(M’=IIA,IIIA,IVA,VA,VIA,IIIB)LiFeNbxPO4LiMPO4(M=Fe,Mn,Ni,Ti)C-LixM1-yM’yPO4

LiCoPO4、LiFeCoPO4(Japan)PhostechLiMPO4?zM’OxNano-Cocrystalline-OlivineLiMPO4coatedwithMandM’OAleeesLiFePO4XLiFeM’PO4X(M’=atleastoneelements≧+2;

X=Halide)ValenceThePatentLandscapeofLFPCathodeMaterialsConfidentialResearchandDevelopmentLFP–OlivinetypeLithiumIronPhosphateCathodeFamily.

LFPUniqueSolution—LFP-NCO LithiumIronPhosphate–NanoCocrystallineOlivineNextGenerationofLFP-NCOTheCapacityoftheProductionProcessandEquipmentConfidentialLFPUniqueSolution—LFP-NCO1.PatentBarrier2.LowConductivity3.LowCapacity4.Feionprecipitation

(LifeCycleProblem)5.InconsistencyinproductqualityNewTypeOlivineCathodeLFP-NCO(LithiumIronPhosphate-NanoCo-crystallineOlivine)LiFePO4CathodemainchallengesDoping-TypeOlivinecathodeExpensivenanotechnologiesAleeesSolutionOtherSolutionConfidentialFePO4Mn+LiLiFePO4?zM’OFirstreactionMillSprayDryerAnnealLiFePO4?zM’O(M’O=Metaloxide)AleeesNCOisanon-dividablesinglecompoundsynthesizedthroughthesimultaneouscrystallizationprocesswithcompoundsoflithium,iron,phosphateandothermetalsasprecursorstoformnon-dopedandnon-coatedmaterials.ProcessofLFP-NCOFePO4andMetalOxidearecombinedtogethertightlybyelectricattractionforceByannealingprocess，themetaloxidecauseslatticeeffectinLiFePO4structuretobecomenewP-TypesemiconductorwithelectronholesConfidentiala(?)b(?)c(?)V(?3)FesiteLiFePO4

110.3346.0084.693291.3921LiFe0.99Ti0.01PO4

210.3236.0034.696291.0770.984LiFePO4·zTiO210.3676.0324.713294.7241LiFePO4·zV2O310.2955.9894.685288.8581LiFePO4·zCr2O310.2995.9884.677288.4881(1)J.Electrochem.Soc

144,(1997)1188-1194.

(2)

J.ElectrochemSoc153,(2006)A25-A31.XRDRefinementofLFP-NCODatasource：NationalSynchrotronRadiationResearchCenter(NSRRC).NonDopingTypeMaterialConfidentialEXAFSSpectrumofLFP-NCOmaterial

LiFePO4·zCr2O3LiFePO4·zTiO2LiFePO4LiFePO4·zCr2O3EnvironmentsofFeandCraredifferentEnvironmentsofFeandCraredifferentCrK-edgeFeK-edgeDatasource：NationalSynchrotronRadiationResearchCenter(NSRRC).NonDopingTypeMaterialConfidential．MetalOxideisco-crystallizedwithLiFePO4insolidsolution,soitcancreateanelectron-deficientstateandisevenlydispersedoverthematerial.．TheresearchofY.M.Chiang[1]in2002indicatedthatpureLiFePO4seemstobeanN-typesemiconductor.．MetaloxideinLFP-NCOcancreateanelectron-deficientenvironmentandreduceLiFePO4energybandtoincreaseelectronicconductivity.LiFePO4MetalOxide[1]S.Y.Chung,J.T.Bloking,andY.M.Chiang,Nat.Mater.,1,1232002.LFP-NCOconceptualmodelConfidentialE(eV)WhatIpeIMFPCrossSection1080V2p3/2197414.70.3225900

153911.30.5223LiFePO4:V2O5E(eV)WhatIpeIMFPCrossSection1080V2p3/2123914.70.3225900

925

11.30.5223LiFePO4:V2O5+SnO2CarbonV2O5LiFePO4V2O5CarbonFailed!!d~7.3?,determinefromP2pLiFePO4·zV2O3/CusingXPSV2pAmorphousCarbonLiFePO4V2O3Datasource：NationalSynchrotronRadiationResearchCenter(NSRRC).ConfidentialAmorphousCarbonLiFePO4V2O3thedensityofLiFePO4·zV2O3is3.595g/cm3.2.theradiusofaLiFePO4·zV2O3particleis235?.3.Amorphouscarbonwithathicknessof7.3?onthesurfaceofLiFePO4·zV2O3particle.4.Vanadiumisestimatedtobe2.2mol%.LiFePO4·zV2O3/CusingXPSV2pDatasource：NationalSynchrotronRadiationResearchCenter(NSRRC).ConfidentialFeMapOMapPMapCrMapDatasource：NationalSynchrotronRadiationResearchCenter(NSRRC).TEM&EELSAnalysisonLFP-NCOConfidentialSampleElectroconducticityσ(S/cm)LiFePO410-9~10-10[1]LiFePO4(/C)4.75*10-4LiFePO4．zV2O3(/C)1.9*10-2LiFePO4．zTiO2(/C)4.5*10-2LiFePO4．zCr2O3(/C)3.3*10-21.Chung,S.Y.,BlokingJ.T.,Chiang,Y.M.NatureMater.1,123–128(2002).IncreaseElectro-conductivityLFP-NCOincreases1MtimesofconductivityoverLiFePO4.Datasource：NationalSynchrotronRadiationResearchCenter(NSRRC).ConfidentialNCOIncreasedElectro-conductivityLFP-NCOsuccessfullyincreasesN-TypeLiFePO4136mAh/gto158mAh/g.(Increasingcapacity16％

)LiFePO4LFP-NCOMaterialConfidentialFe2+Feionprecipitationcausesamicroshortinsidethebatteryandaffectsthelifecycleofthebattery.

PreventionofFeionprecipitationAfterdissemblingthebatteryundertestconditions,theEDSonthebatteryseparatorhadnoFeionprecipitation.Fe2+SeparatorofanodesideDatasource：NationalSynchrotronRadiationResearchCenter(NSRRC).ConfidentialLFP-NCOtechnologycansuppressthegraingrowthintheannealingprocessinordertominimizeparticlesize.Withasmallerparticlesize,theinterfacebetweenLiFePO4/FePO4isshortened,so

thattheoverallcharging/dischargingperformanceisimproved.MinimizedparticlesizeLiFePO4LFP-NCOMaterialDatasource：NationalSynchrotronRadiationResearchCenter(NSRRC).ConfidentialByco-crystallingmetaloxide,LFP-NCOtechnologycansuppressthegraingrowthintheannealingprocessinordertominimizeparticlesize.Withasmallerparticlesize,theinterfacebetweenLiFePO4/FePO4isshortened,sothatthehighCratecharging/dischargingcapacityandcyclelifeperformanceisimproved.MinimizedparticlesizeThelifecycleperformanceofLFP-NCOunder5CdischargerateConfidential※SolidStateProcessRawMaterialsHowtocontroltheFe2+?Howtomakesurethesematerialsinsolidstatecanmixthoroughly?Howtocontrolthefinalproductquality?ChemicalReactionMechanism:Fe(3+)PO4+Li2CO3+reducingagent→LiFePO4AnnealMixingMicroMixingSolidStateSynthesisMethodConfidentialLFP-NCOFirstreactionMillSprayDryerAnneal※Topreventtheironoveroxidingto3valence,weuseironpowderasthestarting

material.

※Alltherawmaterialiswelldispersedbyliquidreaction.※Themetaloxideprecursorwilltotallydissolveinthesolutionandavoidtheby-products(Li3PO4)affectingthepropertyoftheproduct.NanoMixingAdvantagesofLFP-NCOProcessConfidentialComparisonofLFP-NCOProcessSolidStateProcessNCO&Sol-GelProcessLiFePO4/Li3PO4LiFePO4·zM’OConfidentialItemsEquipment/MethodUnitSpecificationAppearanceSurfaceareaMountechMacsorb-1201/BETm2/g11±2TappeddensityQuantachromeAT-2g/mL1.0±0.2Particlesize(D10)HORIBALA-950μm<3Particlesize(D50)HORIBALA-950μm4±2Particlesize(D95)HORIBALA-950μm<10MoistureKEMMKC-520ADP511Sppm<700ElementanalysisElectrochemicalCharacterizationArbinBT2000Discharge@C/10mAh/g155±31stcoulombefficiency%>90PressedDensity--

g/cm3

1.8~2.2AleeesM12specificationConfidentialItemsEquipment/MethodUnitSpecificationAppearanceSurfaceareaMountechMacsorb-1201/BETm2/g12±2TappeddensityQuantachromeAT-2g/mL1.0±0.2Particlesize(D10)HORIBALA-950μm<3Particlesize(D50)HORIBALA-950μm4±2Particlesize(D95)HORIBALA-950μm<10MoistureKEMMKC-520ADP511Sppm<700ElectrochemicalCharacterizationArbinBT2000Discharge@C/10mAh/g153±31stcoulombefficiency

%>90PressedDensity--

g/cm3

1.8~2.2AleeesM121specificationConfidentialCustomer:JFEJFEistheleadinghigh-qualityanodematerialcompanyinJapanandNo.2steelprovider.70％anodematerialsalesgoestoSony、SanyoandToyotaConfidentialCustomer:BYD18650typecellConfidentialCustomer:BYD18650typecellThecapacityis1.6Ahunder2CdischargerateThecapacityis1.6Ahunder0.2Cdischargerateat60℃ConfidentialThecapacitystillobtainedmorethan90%after2000timescycleunder1Cchargeand2Cdischargerate.Customer:Enertech18.5AhCellConfidentialResearchandDevelopmentLFP–OlivinetypeLithiumIronPhosphateCathodeFamily.

LFPUniqueSolution—LFP-NCONextGenerationofLFP-NCOTheCapacityoftheProductionProcessandEquipmentConfidentialNextGenerationofLFP-NCOThewetprocessandSol-Gelcanproducebothpowertypeandenergytypecathodematerial.NextgenerationofLFP-NCOcanproducebatterycellswithbetterenergyandpowerdensity.UsingtheHIBSalliance,cellsindifferentformatscanservedifferentdemandsfrompackcompanies.ConfidentialGoal：Increase2Cdischargingcapacity(2C>150mAh/g)MetalOxidenano-fiberandnano-tubeaddition：

AnextensiontoLFP-NCO,wherelayer-structuremetaloxidenano-fiberornano-tubeisusedasconductingwirebetweenparticlestoenhancetheconductivityrateonelectronsandionsforbetterperformance.e-Li+AleeesFutureR&DProject(1)ConfidentialGoal：Increase2Cdischargingcapacity(2C>150mAh/g)FutureR&DProject(2)(B)AddedPolymercarbonsource:

LiFePO4itselfhasalowconductivityproblem.Tosolvethisproblem,mostresearchfocusesonreducingthesizeoftheprimaryparticlestoreduceaggregation.LoweraggregationcanreduceionmovementdistancetoincreasethedischargingcapacityathigherC-rate.Wewillchooseapolymeradditivewhichdecomposesatatemperaturegreaterthan400℃asaprecursorforcarbon.DuringtheLFPtransitionphase,thesimultaneouspolymeradditivedecompositioncaneffectivelyhelptoreducetheprimaryparticlesize.ConfidentialGoal:Increasethepressdensitytogreaterthan2.7g/cm2Solution:usingnewpowderdesignPressdensitydirectlyaffectstheenergydensityinbatterydesign.Withhigherpressdensity,thereismoreactivecathodematerialinthesameareaononesideoftheelectrode.Hence,thevolumetriccapacityishigher.

Forasetofsamesizespheres,theoreticallyhexagonal-close-packed,HCP,

isthebestpackingchoice.However,therearestilldeadspaces.Researchonproperdistributiondesignonsmallerparticlesforfillingupthegapmightbringabouttheoptimaldensityforbatterypowder.FutureR&DProject(PowderDesign)ConfidentialE861(Powertype)TargetSpec

E862(Energytype)TargetSpecTapDensity0.7~0.91.2~1.8PressDensity2.2~2.42.7~2.9D10<1.5<3D504±26±2D95<10<12Moisture<700<700SurfaceArea14~1812