钛酸锂电池应用介绍

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.23,2016EVbatteries1UnderstandtheLTO23Applications(EV&ESS)4Who’swhoinLTOContentsSafetyConsistency(orReliability)Longcyclelife(10-15yrs?)Highpowerdensity(HEV)Highenergydensity(BEV)Lowcost(5-10%lower/year?)High&lowtemperatureperformance(-40to65oC)RequirementofLi-ioncellsforxEVAluminumcasedprismaticcellsforxEVAluminumcasedLi-ioncellforxEVPouchprismaticcellsforxEVPouchprismaticcellsforxEVHowthecellfails(thenightmareforLIBengineers)?Abnormalamountofheatgeneratedinternallyinthecellmostlyfromgraphiteanodecouldleadtofireorexplosion!起始状态Initialstate经长期循环

AfterextensivecyclingTheinternalmechanicalstressofelectrodescausedbycharging/discharginggraphiteleadstoelectrodedisconnectioninthecell!Theexpansion/contractionoftheLIBBriefhistoryofLTOIn1971,spineltypeLi4Ti5O12

orLTO

wasfirstreportedbyDeschanvres

etal.

DeschanvresA,RaveauB,SekkalZ.Miseenevidencecristallographiqued'une

nouvellesolutionsolidedetypespinelleLi1Ti2,O4(0≤x≤0.33)[J].Mat.Res.Bull.,

1971,6(8):699-704.In1989,Colbowetal.hadstudiedmorethanitsstructuralpropertiesbutalsothepossibilityofusingLTOasanelectrochemicalmaterial.ColbowKM,DahnJR,HaeringRR.StructureandElectrochemistryoftheSpinel

OxidesLiTi2O4andLi4/3Ti5/3O4[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.……..

HowtheLTOchemistryworks?Li4Ti5O12Chemicalformula:Li3(Li1Ti5)O12

Chargebalanced:Li+3(Li+1Ti4+5)O2-12

Spinel=AM2O4or(AM2O4)x3=A3M6O12

[Li+3]8a[Li+Ti4+5]16d[O2-12]32e

[Li+6]16c[Li+Ti3+3Ti4+2]16d[O2-12]32e

Dischargestate:Chargestate:Theoreticalcapacity:175mAh/gadisch=0.836nm;aCh=0.837nm“Zerostrained”crystallatticeSpacegroup:Fd3ma=0.836nm5Ti4+/1Li+in16dsiteorOhLi+in8asiteorTd(Disch)Li+in16csiteorOh(Ch)6Li+movefrom8ato16cIsgraphitetheangel/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)Al3+/Ga3+Mg2+Al/Galowered0.045VinLTOvoltageEfforttolowertheE.P.ofLTOLTOturnedmetallicunderareducingatm.0min30minObservation:

AlongresidencetimeofLTOinareducingatmosphereof5%H2S+95%H2seemsenabledthemetallicnatureofthematerial.120min.Control300min.300min.120min.AnoxygendeficiencyintheLTOcouldbethereasonforanexpansionofcrystallatticecausedbythereducingatmosphere.Thisoxygendeficiencyseemsrelevanttotheincreasingmetallicnatureofthecompoundwhichisdesiredasananodematerial.XRDshowedalatticeexpansionduetoH2!Acontinuousshiftof2Ɵpeakaround18.4degreeindicateanexpansionincrystallatticecausedbyreductionof5%H2S+95%H2.

16TGAresultconfirmedanO-deficiencyintheLTOLTO-CcompositeLTO(pristine)LTO’sElectroniccond.(S/cm)ValenceofTi-ionsLi4Ti5O1210-9+4Li7Ti5O1210-2+3&+4Li4Ti5O12-x-C10-7Little+3&Lotof+4CarboncoatedLTOThetableshows2importantresults:-Inachargedstate,LTOisveryconductive;-TheoxygendeficiencyinLTOenhancestheconductivity&lowersvoltageofLTO.TGAresultfurtherconfirmedthatanoxygendeficientexistsintheLTO.Thelithiumintercalationvoltageisfoundtodecreaseby0.06V(fromtheoriginal1.55Vto1.49V),whichgivesrisetoatleast5%increaseinenergydensityonthefullcelllevel.A0.06VvoltagereductioninducedbyO-vacancyinLTOSafestAnodeTargetedmarket&IPLongestcyclelifeHighratecapabilityLow/highTperformanceCosteffectivePro’s&Con’sofLTOLTOCon’sofLTO

LowenergydensityHighmaterialcost?Cellgassing(know-how)?Marketisnotobvious?(educatetheconsumers)PriceofvariousanodematerialsIsLTOmaterialexpensive?Rawmaterial:73%TiO2+27%Li2CO3Forevery100kgLTOmaterial,

(100*73%*30RMB/kg+100*27%*48RMB/kg)/84%=3486RMBrawmaterialcostis~35RMB/kgmanufacturingcostis~15RMB/kgtotalcostis~50RMB/kg Markupforoverheadcost+profit:80RMB/kgsourceBTRClariantOurCalc.Price(RMB/kg)22078880LTOcouldbesoldcheaper!IsLTOmaterialexpensive?Totalownershipcost(TOC)MaterialCost1(RMB/kg)EnergyDensity2(Wh/kg)Efficiency(%)Cyclelife3(100%DepthofDischarge,0.2Crate)TOC(relativetographite)Graphite705269920001LTO10038399250000.16

211calculatedbasedonrawmaterialcost,manufacturecostincludingutilitycostandlabor,andayieldof70%2uselithiumcobaltoxide(LCO)asthecathode3usereporteddatafromindustrialvendorsSupply/demandworldofanodematerials国内钛酸锂相关产业

II.

Domestic（国内）河北银隆材料(3000吨/年)电池(20,

60Ah软包、30,

55Ah圆柱)应用(EB

、ES/张北&宝清)湖州微宏材料(自供)电池(10Ah、8万/天)应用(重庆公交、英国、荷兰等约3000多辆、

LpTOTM储能系统销往美国、重庆等地)四川兴能材料(3000吨/年)电池(20AhLTO/NCM软包)应用(电动大巴销往欧洲)天津捷威电池(美国奥钛技术转让,60Ah已出货2000万Ah)应用(快充大巴、调频储能电站) 深圳贝特瑞材料(碳包覆LTO、无碳包覆LT O)锦州朋太钛白粉材料(LTO、钛白粉）安徽天康材料(自产)电池应用河北强能材料(低价LTO)合肥国轩电池应用湖南杉杉材料天津大学电池（400Ah

LTO/LFP）2010/09/20市场快讯.珠海银通控股的香港佳能公司将投资4,890万美元购买美国奥钛公司51%的股份。并在中国珠海打造世界最大钛酸锂生产基地。CanonInvestmentHoldingsLimitedPlanstoInvest$48.9MillioninAltairNanotechnologies,Inc.ComprehensiveAgreementIncludesEquityInvestment,thePurchaseofProductsandServicesandPrivilegedAccesstotheChinaMarketRENO,NV--(Marketwire-09/20/10)-AltairNanotechnologies,Inc.(Altair)(NASDAQ:ALTI-News)todayannouncedthatitreachedadefinitiveagreementwherebyCanonInvestmentHoldingsLimitedwouldpurchasenewlyissuedcommonsharesofAltairNanotechnologies,Inc.resultingin51%ofAltair'sfullydilutedcommonsharesimmediatelyfollowingclosing.Canonhasagreedtopurchaseapproximately125,917,996sharesat$0.3882pershare,providing$48.9millioninproceedstofundthecontemplatedestablishmentofalithium-titanatemanufacturingfacilityinChinaandAltair'sworkingcapitalrequirementsandoperationsintheUnitedStates.………….…钛酸锂电池的四大市场：军用交通电网工业Theenergystoragesystem(ESS)

builtbyAltairnanoTechnology2

ESSinoperationatAES

for8years2ESSinoperationatPJM&ILP80ProterraelectricbusesinCaliforniaforover7years.河北银隆/北方奥钛的钛酸锂电池钛酸锂储能系统国家电网张北风光储输示范站

-

2MW

LTO-ESS深圳宝清电池储能站

-

1MWhLTO-ESS混合动力与纯电动大巴

-珠海350辆

-石家庄220辆

-邯郸600辆

-湛江50辆

-北京50辆仿古游览车银隆第四代高密度钛酸锂快充电池河北银隆/北方奥钛的钛酸锂电池IssuesintheLTOcellmanufacturingCCTplanofMVMVwillstarttwodemocitybuslineinJanuary2011.5km湖州微宏在重庆运行的钛酸锂电动大巴四川兴能具有3K吨的钛酸锂年产能序号

30Ah钛酸锂电芯产品参数

项目

参数1电芯型号ITP74/212/2692标称电压(V)2.233标称容量(Ah)304电芯内阻（1kHz)/mΩ≤0.65重量能量密度(Wh/kg)85@1C6体积能量密度(Wh/L)174.6@1C7标准充放电电流/A30(1C)8最大持续充电倍率10C9最大持续放电倍率10C10最大脉冲充电倍率（50%SOC，10S）26C11最大脉冲放电倍率（50%SOC，10S）28C12工作温度范围/℃

-40~6013

-20℃容量保持率≥70%（1C）14

-40℃容量保持率≥55%（1C）15常温循环寿命（4C/4C,100%DOD）20000周16安全性满足GBT31485-2015测试标准捷威动力的30Ah钛酸锂电池捷威6分钟快充“高安全、长寿命、宽温度窗口”30Ah钛酸锂电池开发成功International(国际）AltairnanoTechnology（美国奥钛）LTOmaterials-goodmaterialsbuttooexpensive!Cells&packs-largestcapacity(65Ah)

withgoodperformanceApplications–AES/FR,CA/Proterra,HI/windfarms,PJM&ILP/grid,…Toshiba（日本东芝）SCiBcells-3.2,10&20AhAl-casedcellsApplications–e-motors,HEV’s,SLIcells,ESincludingFES.IshiharaSangyo(日本石原）LTOmaterials

withseveralgradesTitanKogyo（日本钛工业）LTOmaterialssupplyingToshibaJohnsonMathew（英国庄信万丰）LFP

asmainproduct,LTOmaterialsinsmallsupplies.国外钛酸锂相关产业日本东通工推出的Style-D超小型Piana双座车采用新日本电池的7.2kWhNCM/LTO电池.-5分钟充满电-无需BMS-2017年上市-时尚（stylish)城市代步车-安全的电动车（finally）！-大功率充电-长寿命，低维护（廉价）-冬天可打起火来！Non-mainstreamEV’s?EV’s

builtbySuzuki,Mitsubishi&HondaEV,EB&ISSusingLTOcellsHowtoachieveahighenergycell?A3.5VLTOcellcanbebuiltbyusing5Vcathode(LiNi0.5Mn1.5O4,LCP,LCMP,…etc.)stableelectrolytesystems(PC?newLisalt?)anti-oxidationseparators(ceramic?)……Roadtoglory?Finally,somethingelseabouttheLTOtechnologyLTOmaterials&CellsAlcurrentcollectorusedforbothanode&cathodeintheLTOcells($,wt.).PCbasedelectrolyteprovidebetterhigh/