LithiumTitanateBasedBatteriesfor HighRateandHighCycleLifeApplications

Dr.MuMu Moorthi
VPBusinessDevelopment

Introduction
Ingeneral,thedemandforsmallerand lighterbatterieshasbeengrowingdrastically duringthelastdecade.Conventionallead acidbatterieshavebeeninusesince1860in stationaryapplications.Leadacidbatteries arestillwidelyusedduetotheirlowcost, maturedstateofdevelopmentand ruggednesscomparedtootherbattery technologies.However,leadacidbatteries (bothfloodedandVRLA)areheavierand bulkier.Theyalsodonotcyclewelltomeet someofthedemandingnewapplication needs. Nickelcadmiumbatterieshavebeenused indeepcycleapplications.Theyaresmaller andlightercomparedtoleadacidbatteries. Largebatterieshavetohavelargeamounts offreeelectrolytewithinthebattery.Like floodedleadacidbatteries,NiCadbatteries havetobemaintainedperiodically.NiCad batteriesalsohavememoryeffect,which resultsinlowerusablecapacityoveraperiod oftime. Theywerealsothechoiceof batteriesforportableapplicationslike camerasandotherportabledevices. However,theuseofthesebatterieshasbeen reducedsignificantlyduetoenvironmental concernsrelatedtotheuseofcadmium. Manycountries,includingtheUnitedStates, havebannedcadmiumrecycling. Toaddresstheseissues,NickelMetal Hydride(NiMH)batteriesbecamean alternativesolutionforportableapplications. NiMH batterytechnologywasnotsuccessful inlargestationaryapplicationsduetothe highcostofnickelandpatentlimitations relatedtothistechnology.Another disadvantagewithNiMH batteriesisthehigh selfdischargerate.ThoughNiMH batteries arelighterandsmallercomparedtoleadacid batteries,lithiumionbatteriesappeartobe muchmorepromising.Also,therecharge timesforallthesebatterytechnologiesare severalhours.Thiscanbeveryinconvenient inapplicationsthatrequirequickcharge, suchasinelectricvehicles.Forspecific applicationswheretheavailabilityofgrid powerislimited,theneedforhighcyclelife batterieswithquickchargecapabilityis becomingmoreandmorecritical.Ifabattery doesnotcyclewellinanapplicationwhere cyclingperformanceisimportant,the customerisleftwithtwochoices:either replacethebatteriesoftenorusealternate

LithiumTitanateBasedBatteriesforHighRateandHighCycleLifeApplications

sourcesofpower,suchasdieselengines. However,bothoftheseoptionsareexpensive. Lithiumbatterieswerefirstproposedin1976 [1]andhavebeenwidelyusedinportable applicationssincetheearly1990s.Inrecentyears, thehighpriceofoilhasprovidedtheincentivefor researcherstolookintonewbatterytechnologies foruseinelectricvehicleapplications.Among lithiumbatteriestherearethreedifferent categories,namely:lithiummetal,lithiumpolymer andlithiumion. Lithiumiondoesnothaveadefinedunique chemistrylikeleadacid,nickelmetalhydrideor NickelCadmiumbatteries.Ithasanumberof differentpossiblecombinations,providinga numberofpossibilitiestoavarietyofapplication requirements.Alithiumioncellhasthreemain components:positiveelectrode(cathode), negativeelectrode(anode)andseparator.This hasbothadvantagesanddisadvantages.Onthe onehand,variouscathodeandanodematerials provideflexibilitytodesignbatteriesforspecific applicationneeds,butontheotherhandthelarge numberofpossiblechemistriescreatesconfusion tothecustomersuntilaparticularchemistryis fullydevelopedandsuccessfullytestedinthefield. Thedifferentoptionsavailableforeachofthese components(andtheirbenefitsand disadvantages)aredescribedindetailbelow.The batteryselectricalandperformance characteristicslikevoltage,capacity,energy density,ratecapability,cyclelife,andcalendarlife willchangeasonechoosesdifferentmaterialsfor anode,cathode,electrolyteandseparator.Aswill beshownlater,thereisnooneparticular combinationofthesecellcomponentsthatcan

meeteveryrequirementinallapplications.Onehas tochooseandmodifythecellcomponentstomeet theapplicationneeds.Inaddition,onecanalso changethecathodeandanodematerial composition,particlesizeandmorphologyto achieveaspecificbatteryperformance. Figure1showstherangeofdifferentbattery technologiescomparedintermsofvolumetric energydensity(Wh/l)andgravimetricenergy density(Wh/kg).AscanbeobservedinFigure1, lithiumbatteriesaremuchsmallerandlighter comparedtoallothertechnologies.Theredbox showstherangeofnewlithiumbatterytechnologies withuniquebatteryperformance.Insharpcontrast tolithiumbatteries,flowbatteriesarethemost bulkyamongalltheenergystoragetechnologies.
Figure1

Principleofoperation
Figure2showsthebasicprincipleofoperationofa lithiumioncell.Also,thefollowingtwoequations

showthechargeanddischargereactionsina lithiumionbattery.Thereareanumberof materialchoicesavailableforbothcathodeand anodematerials,whichwillbediscussedlater. Whenthebatteryischarged,thelithiumionsin thecathodematerial(lithiumcompound)migrate viaaseparatorinbetweenthelayersofcarbon materialthatformtheanodeandchargecurrent flows.Similarly,whenthebatteryisdischarged, thelithiumionsinthecarbonmaterialthatform theanodemigrateviaaseparatortothecathode materialanddischargecurrentflows.

CathodeMaterials
Anumberofdifferentcathodematerialshave beenevaluatedsince1990.Theavailable materialsincludeLithiumcobaltoxide(LC), LithiumNickelCobaltAluminumOxide(NCA), LithiumManganeseSpinel(LiMn2O4),Lithium NickelCobaltManganeseoxide(NCM)andOlivine basedmaterials,suchasLithiumIronPhosphate (LFP). Thefirstcommerciallithiumbatteriesused lithiumastheanode.However,thepoorcyclelife andsafetyissuesassociatedwiththeuseof metalliclithiumforcedscientiststolookfor alternativeanodematerials.LiCoO2cathode,in conjunctionwithcarbonasnegativeelectrode, wasintroducedintheearly1990s[1,2].Until recently,LiCoO2waspredominantlyusedin portablelithiumbatterieslikelaptopsandcellular phones.ThecyclelifeofthebatterieswithLiCoO2 wasbetween500 700,dependinguponthe manufacturerandthecelldesign.Overtheyears, batterieswithLiCoO2cathodealsohadsafety relatedincidentsandthecostofLiCoO2has increasedovertime.Duetothesereasons,it becamenecessarytoidentifynewcathode materials.Lithiated manganeseoxide,alsoknown asspinel duetoitsspinelcrystalstructure, yieldedasimilarenergydensityasLiCoO2,but withamuchlowercyclelife. Othermixedmetaloxidesbaseduponnickel oxide(LiNiO2)werealsoexplored.Twosuch materialswerelithiumnickelcobaltaluminum oxide(NCA)andlithiumnickelmanganesecobalt oxide(NMC).NCAhasslightlylowervoltageand hencebettersafetycharacteristics,comparedto LiCoO2basedcells.Ontheotherhand, NCAhas muchbettercyclelife.NMChasslightlylower

Figure2
Cobalttype:Charging LiCoO2+Cn>Li1XCoO2+CnLix Manganesetype:Charging LiMn2O4+Cn>Li1XMn2O4+CnLix Cobalttype:Discharging Li1XCoO2+CnLix>LiCoO2+Cn Manganesetype:Discharging Li1XMn2O4+CnLix>LiMn2O4+Cn

Chargee
Positive Separator Negative

Li

Dischargee

LithiumTitanateBasedBatteriesforHighRateandHighCycleLifeApplications

cyclelifecomparedtoNCAandhassimilarsafety characteristics.Evenwithinthesemixedmetal oxides,variationsintheratiosofthecationshave alsobeenstudied. Althoughtherewassomeimprovementinthe safetyduetotheuseofmixedmetaloxides,itwas stillnecessarytofurtherimprovethesafety featuresofthepositiveelectrode.Lithiated iron phosphate(LiFePO4)wasthesolutionforthe safetyissuesassociatedwiththepositive electrode.Lithiumironphosphateisalsoknown asLFPforshortinthebatteryindustry.LFPgave reasonablecalendarlifeandexcellentcycling characteristicswhenoperatedatmoderate temperatures.TheenergydensityofLFPbased materialswasmuchlowerthanLiCoO2ormixed metaloxides,butthehighratecapabilityofLFP basedbatteriesmadethemattractivefor applicationsinpowertools.Table1showsthelist

ofcathodematerialsusedinlithiumionbatteries alongwiththeiradvantagesandlimitationswhen usedwithcarbonastheanodematerial.

AnodeMaterials
Todate,carbonhasbeenthemostcommonly usedanodematerialinalithiumioncell.Oneof thesyntheticmaterialsusedisMeso Carbon MicroBeads (MCMB).MCMBhasahighenergy density:350plusmAh/g.Thismaterialhasgood performance,butisexpensive.Modifiednatural graphite,ontheotherhand,islessexpensivethan MCMBandmanyvarietiesareavailable. Amorphouscarbongivesgoodpower,buthasa lowerenergydensitythangraphite.Although hardcarbonsaregoodforhighratecapability, theygivelowercapacity:~200mAh/g.Much researchisstillongoingwithsingleandmulti wallednanotubes andgraphemes;howeverthey seemexpensiveatthistimeforcommercialuse.

Table1 Material
LithiumCobalt LithiumNickelCobalt AluminumOxide(NCA) LithiumNickel ManganeseCobalt Oxide(NMC) Lithium ManganeseOxide

Chemicalformula
LiCoO2

Advantages
Highenergydensity, Reasonablygoodcyclelife HighCapacity180mAh/g,Reasonably goodcyclelife,Slightlybettersafety thanlithiumcobaltoxide HighCapacity,200mAh/g,Reasonably goodcalendarlife.Cyclelifeisless thanNCA.Safetyslightlybetterthan lithiumcobalt. Highpower,highvoltage,lowercost andimprovedabusetolerance

Disadvantages
Safetyandcost

LiNi0.8Co0.15Al0.05O2

Safety

LiNi0.33Mn0.33Co0.33O2

Energydensity

LiMn2O4

Calendarlifewhenusedwith graphite,lowcapacity,125 mAh/g. Poorenergydensity,Low operatingvoltage,3.4V,low capacity,134mAh/g

LithiumIron Phosphate(LFP)

LiFePO4

Bettersafety,highratecapability,good cyclelifeatnormaltemperatures

Lithiumtitanate(Li4Ti5O12,referredtoasLTO inthebatteryindustry)isapromisinganode materialforcertainnicheapplicationsthatrequire highratecapabilityandlongcyclelife.LTOoffers advantagesintermsofpowerandchemical stability,butLTObasedbatterieshavelower voltage:2.5Vvs.LiCoO2and1.9Vvs.LFP. Nevertheless,theloweroperatingvoltagebrings significantadvantagesintermsofsafety.Further, thesebatteriescanbechargedfast.Datashows thatthesebatteriescanbesafelychargedatrates higherthan10C.Thismeansthebatterycanbe chargedinlessthan10minutes.TheLTObased batteriesalsohaveawideroperatingtemperature rangeandarechargeefficiencyexceeding98%. AlthoughtheenergydensityofLTObased batteriesislowcomparedtootherlithiumion batteries,itisstillhigherthanleadacidandNiCad batteries.Therearenumerousapplicationswhere leadacidbatteriesandNiCadbatteriesareusedin conjunctionwithgenerators.Thevolumetric changeduringchargeanddischargeisverysmall comparedtocarbonandresultsprovidemuch longercyclelife.LTObasedbatteriesprovide muchbetterlowtemperatureperformance comparedtocarbonbasedbatteries.Thelarge cyclelifeandhighratecapabilityofLTObased batteriesalsobringsuniqueadvantagesin applicationswherethereliabilityofthegridis poor.Whenthegridpowerisavailable,the batteriescanbechargedquicklyanddischarged slowly.Thiswillsaveasignificantamountofcost intermsofdieselandfrequentreplacementsof VRLAbatteries.Forelectricvehicles,thefast rechargecapabilitymakesahugedifferencein rechargetimecomparedtootherchemistries:10 minutesforLTObasedbatteriescomparedto8 hoursforcertainchemistries.

ToshibahasalreadyintroducedLTObased batteriesforelectricbikeapplications.Utilities oftenhavepeakproblemsassociatedwithdemand andproduction.Often,theydonotproduce sufficientpowertomeetthepeakdemand,while theycanproducemuchmorethanwhatisneeded duringoffpeakhours.Buildingpowerplantsjust tomeetthepeakdemandscanbeexpensive. Batteriesinthisapplication,however,oftendonot requirehighenergydensity.LTObasedlithium batterieswillbeasuitabletechnologyforthis application.Also,thelowerchargevoltage providesanoptionfornewaqueousbased electrolytes,whichbringsuniqueadvantagesin floatchargeapplications. Tinandsiliconbasedalloysandintermetallic materialsarealsobeingexploredbyanumberof researchers;however,thereareanumberof challengesthatneedtobeovercomebefore implementingtheseintermetallics incommercial applications.

Electrolytes
Sincethecellvoltageoflithiumcellsishigherthan thepotentialatwhichaqueoussolutions electrolyze,onehastousenonaqueous electrolytesinlithiumionbatteries.Therearea numberofliquidorganicsolventoptionsavailable foruseaslithiumionbatteryelectrolytes. Mixturesofdimethyl carbonate(DMC)[4], ethylenecarbonate(EC),diethylcarbonate(DEC), andethylmethyl carbonate(EMC)withdissolved lithiumhexafluorophosphate (LiPF6)areamong themostcommonlyusedelectrolytes.Theratioof eachcomponentinthemixtureisoftenoptimized byeachcellmanufacturer.Theabovedescribed electrolytenormallyworkswellatroom

LithiumTitanateBasedBatteriesforHighRateandHighCycleLifeApplications

temperatures.However,underabuseconditions, suchasoverchargeorhigheroperating temperatures,decompositionreactionscanoccur. Conductingsolidpolymerelectrolytescan replacesolventbasedelectrolytes.Theyoffer greateradvantagewhenusedwithalithiummetal anode.Someofthechallengesrelatetothe degreeofconductivityatlowtemperatures.Ionic liquidsofferadvantagesinstabilityathigher voltagesandhavebetterabusetolerance,butthey arestillintheearlystagesofdevelopment.

challengesexistinwindinglargeelectrodesfor largeformatcells.Also,thechallengerelatingto attachingtabsforhighpowercelldesignstill remains.Largercylindricalcellshaveissueswith uniformheatdissipation.Duringhighrate discharge,thecoreofthecellsbecomeshotter thantheoutside.Thehighertemperaturemakes theinnerpartofthebatteryagefaster,which resultsintheprematurelossofcapacityforthe entirecell. Theflat/prismaticstackdesignismost commonlyusedinlithiumpolymercells.This designoffersadvantagesinbuildinglarge,high powercellsandprovidesameanstodissipateheat efficientlysothecellsageuniformly.Also,whena largenumberofcellsarepackedforaspecific applicationthenthisdesignprovidesmuchbetter safetycharacteristics.Thisdesign,however,has itsownchallenges:anexternalsupportstructureis neededfortheelectrodestack.Further,single sidedtabdesigncellshaveissueswithuniform currentdensityandimpedance.

Container/CellDesign
Lithiumbatteriescomeinbothcylindricalandflat pack(prismatic)designs.Ametalcan(spiralwind) isoneofthemostcommondesignsandhasa limitednumberofparts(oneanode,onecathode andoneseparator).Thestrengthprovidedbythe metalcylinderisanaddedadvantage.18650 cylindricalcellsarethemostwidelyusedlithium ioncells.Thesearebeingusedinlaptopsand manyotherportabledevices.However,
Figure3

Courtesy:JimMcDowall [5]

CellCharacteristics
Theactivematerialsdiscussedaboveforcathode andanodematerialscaneachbecombinedto formanelectrochemicalcell.Eachcellwillyield differentcharacteristics,dependinguponthe combinationoftheparticularcathodeandanode. Figure3showsthevoltagerangeforsomepopular cathodeandanodematerialcombinations.For example,thehighestvoltageofthelithiumcellis obtainedfromacellmadefromLiCoO2and carbonanode(3.8V).Similarly,forthelithiumcell withLFPascathodeandLTOasanode,thevoltage wasonly1.9V,whichisevenlowerthanthatofa leadacidcell.Thelargervoltagecellsbringhigher energyandpowerdensities,whilethelower voltagecellshavebettersafetyfeatures.The lowervoltagecellswillofcoursehavelower energyandpowerdensities. GiventhattheLTOanodematerialoperatesat ahighervoltage(lessnegative),theoverallcell voltageislowerandhencetheoverheating problemwithrespecttosolidelectrolyteinterface (SEI)iseliminated.Also,thehighernegative voltageofLTOallowsthemtoberechargedata higherrate,sometimesaslittleasfiveminutes. Duetothishighernegativevoltage,theoverallcell voltageislowerandhencetheenergyandpower densitiesarealsolower.Thecyclelifeforthese batterieshasbeenreportedtobemorethan 10,000at80%depthofdischarge.Duetothelow energyandpowerdensity,thesebatteriesarenot attractivefortraditionalportableapplications. However,thelongcyclelife,safety,andfast chargeanddischargecapabilitiesofLTOcellsbring uniquevaluestoapplicationswherethese attributesarecritical.Theseapplicationsinclude: telecom,datacenterUPS,aerospace,sensors, renewableenergy,andtheSmartGrid.

Chargebalancerequirements
AqueoussystemslikeVRLAandNiCadarecharged about100mVabovetheopencircuitvoltageof thecell.Theelectrochemistryinthesesystemsis largelyregulatedbysidereactionsinvolvingwater. Thesesystemscantypicallytoleratemoderate levelsofovercharging.Theexcesschargecurrent isconsumedbytheabovementionedside reactions.Lithiumsystemsarenotaqueousand thesidereactionsareabsent.Alloftheapplied chargeisgoingtochargethebatteries,therefore thechargingisefficient.However,itlacksthe regulatingmechanismsuppliedbytheside reactions,andmustbeprovidedelectronically. Thevariationofstateofchargeamongthecellsin abatterypackcanaffectthebatterydischarge capacity.Itisessentialtokeepthecellvoltages closetoeachother.Also,oneneedstoavoidover chargingthecell.Theexternalcellbalancing functionwillbringthevoltageofthecellscloseto eachother. Likeanyotherenergystoragesystem,thereare issuesrelatedtosafetythatneedtobeaddressed. Thetwomainsafetyissuesrelatedtolithiumion batteriesareoverchargingandoverheating.Also, allthesituationsrelatingtotheapplicationlike temperature,operatingvoltagewindow,andheat dissipationshouldbeconsideredintothebattery packdesign.Sincelithiumionbatterieshaveto haveelectronicbatterymanagementsystem,it providestheopportunitytoaddsmartness into thebatterysystem.Thefunctionsincludestateof charge,dischargehistory,batterydiagnostic capability,reservetimeprediction,remotebattery monitoringandalarmcapability.Duetoitslow voltageofoperationthelithiumtitanatebased batteriesoffermuchsaferoperatingparameters.

LithiumTitanateBasedBatteriesforHighRateandHighCycleLifeApplications

Summary
Lithiumbatteriesprovideavarietyofdesign choicestomeetavarietyofapplicationneeds. Nosinglechemistrywillmeetalltheapplication needs.Anumberofdifferentcathode,anode, andelectrolytematerialsofferbothadvantages anddisadvantages.UsingLithiumTitanateasan anodematerialoffersexcellentrecharge capability,safety,andexceptionallylargecycle life.Inspiteofitslowerenergydensity,itoffers exceptionaladvantagesoverotherchemistriesin numerousapplications.

References
1. ElectricalEnergyStorageandIntercalation Chemistry, Whittingham,M.S.,Science 11June 1976:Vol.192.no.4244,pp.1126 1127 2. Phosphoolivines asPositiveElectrode MaterialsforRechargeableLithiumBatteries, A.K.Padhi,K.S.Nanjundaswamy,andJ.B. Goodenough,J.Electrochem.Soc.,Volume144, Issue4,pp.11881194(1997) 3. "LithiuminsertionintoFe2(SO4)3frameworks," A.ManthiramandJ.B.Goodenough, Corresponding(16May1989),JournalofPower Sources (ElsevierB.V.)26(34):403408. 4. Mixedsolventelectrolyteforhighvoltage lithiummetalsecondarycells, Katsuya Hayashi*,YasueNemoto,Shinichi Tobishima andJunichi Yamaki,Electrochimica Acta, Volume44,Issue14,1March1999,Pages 23372343. 5. UnderstandingLithiumiontechnology, Jim McDowall,Batcon 2008ConferenceProceedings

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