ORIGINALPAPER
High-performancethin-filmLi4Ti5O12electrodesfabricatedbyusingink-jetprintingtechniqueandtheirelectrochemicalproperties
YaominZhao&GuoqunLiu&LingLiu&ZhiyuJiang
Received:14February2008/Accepted:28April2008/Publishedonline:20June2008#Springer-Verlag2008
AbstractLi4Ti5O12thin-filmanodewithhighdischargecapacityandexcellentcyclestabilityforrechargeablelithiumionbatterieswaspreparedsuccessfullybyusingink-jetprintingtechnique.ThepreparedLi4Ti5O12thinfilmwerecharacterizedbyscanningelectronmicroscopy,transmissionelectronmicroscopy,X-raydiffraction,X-rayphotoelectronspectroscopy,cyclicvoltammograms,andgalvanostaticcharge–dischargemeasurements.Itwasfoundthattheaveragethicknessof10-layerLi4Ti5O12filmwasabout1.7~1.8μmandtheactivematerialLi4Ti5O12inthethinfilmwasnano-sizedabout50–300nm.ItwasalsofoundthatthepreparedLi4Ti5O12thinfilmexhibitedahighdischargecapacityofabout174mAh/gandthedischargecapacityinthe300thcycleretained88%ofthelargestdischargecapacityatacurrentdensityof10.4μA/cm2inthepotentialrangeof1.0–2.0V.
KeywordsInk-jetprinting.Thinfilm.Li4Ti5O12.Lithium-ionbattery
Introduction
SpinelLi4Ti5O12iswell-knownforitsexcellentelectro-chemicalpropertiesandhasfounditsversatilepotentialapplicationsinmanyfieldstillnow.Firstly,spinelLi4Ti5O12hasbeendemonstratedasapromisinganodematerialforlithium-ionbatteriesbecauseithasgoodLi-ionintercalationandde-intercalationreversibilityandexhibitsnostructuralchangeduringcharge-dischargecycling[1].Itexhibitsaworkingpotentialof1.55Vvs.Li+/Lianditstheoreticaldischargecapacityis175mAh/g[2–3].Thisanode,whencoupledwiththe4VavailablecathodessuchasLiCoO2[4–7]orLiMn2O4[8–11],canprovideacellwithanoperatingvoltageof2.5VwhichistwicethatofNi/MHorNi/Cd.Secondly,theimprovedsafetyandreliabilityofthespinelcomparedwiththatofcarbonelectrodesmakethelithium-ionbatteriesusingLi4Ti5O12materialasanodesuitableforelectricvehicleandpowerstoragebatteries.Thirdly,itcanalsobeusedinhybridsupercapacitorsbycombinationwithactivecarbonorsomeconductivepolymersjustbecauseofitssuperiorcycle-abilityandsafety[12–16].
Meanwhile,manystudieshavebeencarriedoutonrechargeablelithiummicrobatteriesbecausethemicroscalebatterieswillbeutilizedinvariousapplicationfieldsrelatedtomicrosystems,suchasmicrosensors,micromechanics,microelectronics,andsoon[17].Li4Ti5O12intheformofthinfilmisalsofindingitspotentialapplicationasanodeinallsolid-statelithiumionmicrobatteries.Manytechniquessuchasspraypyrolysis,magnetronsputtering,electrostaticspraypyrolysis,pulsedlaserdeposition,softsolutionprocessing,hydrothermalmethod,sol-gelmethodandsoonhavebeenappliedtostudytheLiCoO2thinfilmcathode.Bycomparison,fewertechniqueshavebeenreportedtoinvestigateLi4Ti5O12thinfilmanode.Upto
Y.Zhao(*):G.Liu
SchoolofMaterialandChemicalEngineering,ZhongyuanUniversityofTechnology,Zhengzhou450007,China
e-mail:zhaoyaomin@zzti.edu.cn
L.Liu:Z.Jiang
DepartmentofChemistry,andShanghaiKeyLaboratoryofMolecularCatalysisandInnovativeMaterials,FudanUniversity,
Shanghai200433,ChinaZ.Jiang
e-mail:zyjiang@fudan.ac.cn
706JSolidStateElectrochem(2009)13:705–711
now,thinfilmLi4Ti5O12hasbeenfabricatedforanodeinlithiumionbatteriesbythefollowingthreetechniques[17–21]accordingtosomerelatedreportsasfarasweknow.Firstly,magnetronsputtering[18]isatypicalmethodsforthinfilmpreparation.C.-L.Wangetalfabricatedspinel-phaseLi4Ti5O12thinfilmsbyradiofrequencymagnetronsputteringonanAu/Ti/SiO2/Sisub-stratefollowedbyanannealingprocessat500~700°C[18].Besides,electrostaticspraydeposition[19]andspin-coatingmethod[17,20–21]havebeenalsoemployedtoobtainLi4Ti5O12thinfilms.Y.YuetalreportedporousthinfilmsofLi4Ti5O12preparedbyelectrostaticspraydepositiontechniquewithlithiumacetateandtitaniumbutoxideastheprecursors.Theyfoundthatthecapacityretained150mAh/gafter70cycleswhentheheatingprocesswascarriedoutat700°C[19].ThinfilmsofLi4Ti5O12withathicknessof1μmwerepreparedbyY.H.Rhoetal.fromprecursorsobtainedbyasol–gelprocessusingpoly(vinylpyrrolidone)followedbyaheattreatmentat600–800°Cfor1h[20].
Atthesametime,theapplicationofink-jetprintingtechnologyhasbeensuccessfullyextendedfromitstraditionalareasintomoreextensivefieldssuchasfabricationoffield-
effecttransistors[22–23],protein[24],high-densitybacterialcolony[25],evencellandorgans[26]inrecentyears.Thin-filmelectrets[27]andpolymerfilms[28]arealsoreportedbyink-jetprintingmethod.MnO2thinfilmelectrodeforprimarybatteryandSnO2thinfilmelectrodeforrecharge-ablelithiumionbatterieshavebeenintroducedinourpreviouspapers[29–30].Sinceink-jetprintingtechniquehasmanyadvantagessuchassimpledevice,low-cost,andfacilefabricationprocess,easeofmassfabricationandsoon,itisfindingincreasingapplicationfieldsandamorepromisingfutureisonitsway.Here,wereportedLi4Ti5O12thinfilmelectrodesuccessfullyfabricatedbyasimpleink-jetprintingtechnique.ThepreparedLi4Ti5O12thinfilmelectrodedisplayedhighdischargecapacityandexcellentcyclestability.
Experimental
PreparationofLi4Ti5O12ink
ThespecificpreparationprocessofLi4Ti5O12inkisverysimilartoourpreviouswork,asshowninFig.1[30].Prior
Fig.1Flowchartshowingprep-arationofLi4Ti5O12inkforsub-sequentink-jetprintingprocess
JSolidStateElectrochem(2009)13:705–711totheLi4Ti5O12inkpreparation,theelectrochemicallyactiveLi4Ti5O12washome-madebysolid-statereactionprocessaidedwithawet-ballmillingprocess(powderLi4Ti5O12forshorthereafter).Thentheinksolutionwaspre-paredasfollows:firstly,Li4Ti5O12suspensionwaspreparedbyadding50mgpolymerichyperdispersantCH10B(Shang-haiSanzhengPolymerMaterialCo.Ltd)in10mlmixturesolvent(distilledwater/absoluteethanol/diethyleneglycol/triethanolamine/isopropylalcohol=56:18:5:1:1bymassratio)andthenfollowedbyadditionof400mgLi4Ti5O12powder.Theobtainedmixturewasball-milledat450rpmfor6handthenthestableLi4Ti5O12suspensionwasachieved.TheotherkindofpolymerichyperdispersantCH12B(ShanghaiSanzhengPolymerMaterialCo.Ltd)wasemployedtodispersetheconductiveagentacetyleneblack(AB).Follow-ingthesameprocedure,CH12B100mgwasdissolvedin
Fig.2SEMimagesforLi4Ti5O12thinfilmsonAusubstrateannealedat550°Cfor90min.asurfaceviewwithlowmagnification(×1000);bacross-sectionalview;csurfaceviewwithhighmagnification(×10,000),InsetisTEMimagefornano-sizedLi4Ti5O12inthethinfilm
707
Fig.3X-raydiffractionpatternsofapowderLi4Ti5O12andbtheas-preparedLi4Ti5O12thinfilmannealedat550°Cfor90min
10-mlmixturesolventandthenfollowedbyadditionof40mgAB.Theas-preparedmixturewasball-milledat450rpmfor6handthenthestableABsuspensionwasattained.Finally,thestablesuspensionLi4Ti5O12andthestablesuspensionABweremixedbyacertainvolumeratioandthenabout5%water-solublesodiumofcarboxymethylcellulose(CMCS)wasaddedasbinder,whichdidnotdestroythestabilityofthedispersionsystem.ThenthemixturesuspensioncontainingLi4Ti5O12,AB,andCMCSwasultrasonicallydispersedfor20min,keptalonefor3~5h,discardedsmallamountofsedimentatthebottomandfinallytheupperstablepartformedtheprintsuspensionnamedasLi4Ti5O12ink.
PreparationofthinfilmLi4Ti5O12electrodes
TheLi4Ti5O12ink10~15mlwastransferredintoawell-cleanedblackCanonBC-03cartridgeandthenink-jetprintedthroughCanon1000SPprinterontoAusubstratefollowedbyanannealingprocessat550°Cfor90minaccordingtothepre-designedelectrodesizeandshape.Inourexperiment,werepeatedtheprintingprocesstentimesinordertoachieveenoughcapacityforsubsequentelectrochemicalmeasurements.Theas-printedLi4Ti5O12filmsweredriedunderinfraredlightat80°Cfor2h,compressedat5MPa,annealedat550°Cfor90min(as-preparedLi4Ti5O12thinfilmforshorthereafter)andfinallyusedforthesubsequentcharacterizationandmeasurements.Characterizations
ThemorphologyandthicknessofLi4Ti5O12filmwereexaminedbymeansofscanningelectronmicroscopy(SEM,PhilipsXL30)andtransmissionelectronmicrosco-py(TEM,JoelJEM2010).X-raydiffraction(XRD)andX-rayphotoelectronspectroscopy(XPS))wereemployedto
708JSolidStateElectrochem(2009)13:705–711
Fig.4XPSsurveyspectra(A)andtheTi2pregion(B);aLi4Ti5O12thinfilmonAusubstrateannealedat550°Cfor90min;bpowderLi4Ti5O12home-madebysolidstatereactionprocess
investigatethestructureandcompositionofas-preparedLi4Ti5O12thinfilm.XRDpatternswererecordedonaBrukerD8advanceddiffractometerwithCuKαradiation,operatedat40mAand40kV.Cyclicvoltammograms(CV)andgalvanostaticcharge–dischargemeasurementswereperformedonaCHI660electrochemicalworkstation(CHI,USA)withconventionalthree-electrodecell.Twolithiumplateswereusedasboththereferenceandcounterelectrode.Alltheelectrodesweredriedundervacuumat90°Cfor12hbeforetheywereconstructedinadry-airfilledbox.OnemolarLiPF6inethylcarbonate(EC)anddimethylcarbonate(DMC)(EC,DMC=1:1byvolume)wasusedastheelectrolyte.CVmeasurementswereconductedatdifferentsweepratesoverthepotentialrangeof1.0–2.0V.Galvanostaticcharge–dischargemeasure-mentswereperformedoverthepotentialrangeof1.0–2.0V.TheexactmassofLi4Ti5O12inthethinfilmswasobtainedasfollows:firstly,theas-preparedthin-filmwasassembledintothree-electrodeglasscellforcharge–dischargemeasurements.Whenthemeasurementswerefinished,thecellsweredisassembled.TheLi4Ti5O12contentinthethinfilmwasdeterminedbyinductivelycoupledargonplasma(ICP)method(IRISIntrepid,ThermoElementalCompany)afterthesamplewassolubizedinconcentratedHNO3–HClsolution.ThemassofLi4Ti5O12wascalculatedonthebasisofthemassoftitaniumachievedbyICPresult.
imageofLi4Ti5O12particlesinthethinfilm(insetinFig.2b)showsthattheparticlesizeofnano-sizedLi4Ti5O12rangesfrom30~300nm.Thecross-sectionalviewoftheas-preparedLi4Ti5O12thinfilmsonAusubstraterevealsthattheaveragethicknessof10-layerfilmisabout1.7~1.8μm,whichwasusedforsubsequentelectrochem-icalmeasurements.
TheX-raydiffractionofas-preparedLi4Ti5O12thinfilm(b)issimilartothatofpowderLi4Ti5O12(a)areshowninFig.3.ThemaindiffractionpeaksofLi4Ti5O12(111,311.400)areindexedbasedonaface-centeredcubicspinelstructurewithanFd3mspacegroup,whichisingoodagreementwiththeJCPDSreference(26–1198)andcorrespondstotypicalpure-phasedspinelstructure[31–32].Inaddition,thepeaksattributedtothesubstrateAuforas-preparedLi4Ti5O12thinfilmsarealsoclearlyobservedandindexed.
ThesurveyXPSspectracorrespondingtoLi4Ti5O12thinfilmonAusubstrateannealedat550°Cfor90min(a)and
Resultsanddiscussion
Electronmicrographsofas-preparedLi4Ti5O12thinfilmsonAusubstratearepresentedinFig.2.ItcanbeseenthatthedistributionofLi4Ti5O12thinfilmisveryuniform(Fig.2a)andtheparticlesarenano-sized(Fig.2b).TEM
Fig.5Comparisonofcyclicvoltammogramsatascanrateof0.1mV/sinamixedsolventofethylenecarbonateanddimethylcarbonatecontaining1.0mol/dm3LiPF6betweenas-preparedLi4Ti5O12thinfilmelectrodeandpowderLi4Ti5O12electrode
JSolidStateElectrochem(2009)13:705–711Fig.6aCyclicvoltammogramsofas-preparedLi4Ti5O12thinfilmelectrodeatdifferentscanratesof(1)0.1,(2)0.2,(3)0.3,(4)0.4,(5)0.5,(6)0.6,(7)0.7,(8)0.8,(9)0.9,(10)1.0mV/sinamixedsolvent
powderLi4Ti5O12(b)arepresentedinFig.4a.TheTi2p,O1s,andLi1sphotoelectronpeaksareclearlyobserved.CarbonpeakspresentinthespectraofpowderLi4Ti5O12areattributedtoathincontaminationlayerwhereasthatintheas-preparedLi4Ti5O12thinfilmcomesfromconductiveagentAB,thepolymericdispersantsCH10B,CH12BandthebinderCMCS.ThehighresolutionspectraoftheTi2pcorrespondingtoboththeas-preparedLi4Ti5O12thinfilm(a)andpowderLi4Ti5O12(b)areshowninFig.4b.ThespectrumcorrespondingtoLi4Ti5O12thinfilminFig.4b(a)ischaracterizedbyamaindoubletcomposedoftwosymmetricpeakssituatedatEb(Ti2p3/2)=459.0eVandEb(Ti2p1/2)=464.8eV.ThismaindoubletisassignedtotitaniumintheIVoxidationstate.Inaddition,itisnecessarytotakeintoaccountthedifferencebetweenthetwosamples.ThebindingenergyforLi4Ti5O12thinfilmincreasedabout0.5eVcomparedwithpowderLi4Ti5O12.Fig.7DischargeandchargecurvesofLi4Ti5O12filmpreparedonAusubstrateannealedat550°Cfor90minatacurrentdensityof10.4µA/cm2inamixedsolventofethylenecarbonateanddimethylcarbonatecontaining1.0mol/dm3LiPF6709
ofethylenecarbonateanddimethylcarbonatecontaining1.0mol/dm3LiPF6;banodicandcathodicpeakcurrentasafunctionofscanrate
Themainreasonforthisphenomenonistheparticlesizedifference.PowderLi4Ti5O12waspreparedbysolidstatereactionprocessandcomposedofbothnano-sizedandmicro-sizedparticleswhereasLi4Ti5O12thinfilmwascomposedofonlynano-sizedparticlesrangedfrom30–300nmshowninFig.3.TheLi4Ti5O12particleswithlargersizethan300nmarenoteffectivelydispersedduringtheinkpreparationandthereforedonotexistintheas-preparedthinfilm.
Figure5showsCVcurvesofas-preparedLi4Ti5O12thinfilmelectrodecomparedwithLi4Ti5O12powderatascanrateof0.1mV/sinamixedsolventofethylenecarbonateanddimethylcarbonatecontaining1.0mol/dm3LiPF6.TwosharpredoxpeaksforLi4Ti5O12thinfilmwereobservedat1.55and1.60Vvs.Li+/Liforcathodicandanodicscansrespectively,whichindicatesthatas-preparedLi4Ti5O12thinfilmexhibitsatypicalbehaviorfortwo-phasereaction
Fig.8Dischargecapacityandcoulumbicefficiencyofas-printedthinfilmLi4Ti5O12electrodeasafunctionofcyclenumberduringthefirst300cyclesataconstantdischargecurrentdensityof10.4µA/cm2inpotentialrangeof1.0–2.0V
710duringLi+ionextractionandinsertionprocesses[11,22–23].Itcanbealsoclearlyfoundthattheredoxpeaksweresharperandthepeakseparationwassmallerforas-preparedLi4Ti5O12thinfilmcomparedwiththoseforpowderLi4Ti5O12electrode.
CVcurvesofLi4Ti5O12thinfilmonAusubstrateannealedat550°Cfor90minatdifferentscanratesfrom0.1to1.0mV/sareshowninFig.6a.Accordingly,theanodicandcathodicpeakcurrentasafunctionofscanratearepresentedinFig.6b.ItcanbeseenfromFig.6thattheanodicandcathodicpeakseparationwas74mVwhenthescanratewas0.1mV/sforas-preparedLi4Ti5O12thinfilm.Thepeakseparationincreasesslightlywiththeincreaseofscanrate.Theanodicpeaksshowapositiveshiftfrom1.625to1.676V(64mVshifted)versusLi+/Liwiththeincreaseofscanratefrom0.1to1.0mV/s.Itiseasytounderstandthatthepeakshiftwiththeincreasingscanratewascausedbythepolarizationofchargetransferreaction.Thepeakcurrentislinearlydependentonthesweeprate,whichindicatesthatthediffusionoflithiumioninsidetheelectrodeisnotthedominatingfactorforas-preparedLi4Ti5O12electrode.Thechargetransferprocessistherate-determiningstep.Thisphenomenonischaracteristicofthinfilmelectrode.
Figure7showsdischarge–chargecurvesinthesecond,tenth,20th,30th,40th,and50thcycleofLi4Ti5O12filmpreparedonAusubstrateannealedat550°Cfor90minatacurrentdensityof10.4μA/cm2inamixedsolventofethylenecarbonateanddimethylcarbonatecontaining1.0moldm−3LiPF6.Ononehand,theshapeofcharge-dischargecurvesoftheas-preparedLi4Ti5O12filmissimilartothatofpowderLi4Ti5O12,whichindicatestheas-preparedLi4Ti5O12filmhasthesamecharge-dischargemechanismaspowderLi4Ti5O12electrode.Ontheotherhand,thecharge-dischargebehaviorforas-preparedLi4Ti5O12thinfilmisverydifferentfrompowderLi4Ti5O12electrode.Anelectrochemicalactivationprocessexistedinas-preparedLi4Ti5O12filmsannealedat550°Cfor90min.Thedischargecapacityissmallduringthefirstseveralcyclesandincreaseswiththecycleprocessarecarriedthrough.Thedischargecapacityinthesecond,tenth,20th,30th,40th,and50thcycleofas-preparedLi4Ti5O12filmis117,157,166,170,172and174mAh/grespectively.Thereasonforthisphenomenonisnotclearyetandfurtherinvestigationisrequired.
Figure8displaysthespecificdischargecapacityandcoulumbicefficiencyofas-preparedLi4Ti5O12thinfilmannealedat500°Cfor90minasafunctionofcyclenumberduringthefirst300cyclesataconstantcurrentdensityof10.4µA/cm2inpotentialrangeof1.0–2.0VversusLi+/Li.Theinitialdischargecapacityis97mAh/g,butthedischargecapacityincreaseswiththeprocessofcyclingandthedischargecapacityinthe42ndcycle
JSolidStateElectrochem(2009)13:705–711
reaches174mAh/g,whichisalmostnearthetheoreticalvalueofspinelLi4Ti5O12material(175mAh/g).Thedischargecapacityinthe300thcycle(153mAh.g−1)is88%ofthelargestdischargecapacity,whichshowstheexcellentcyclestabilityofas-preparedLi4Ti5O12thinfilms.Theinitialcoulumbicefficiencyis16.8%andtheefficiencyalsoincreaseswiththeincreaseofcyclenumber.Thecoulumbicefficiencymaintains98%orsoafterthe30thcycle.WithregardtotheirreversiblecapacityofLi4Ti5O12thinfilmduringthefirstseveralcycles,itcanbemainlyattributedtoparasiticcathodicreactionsduetoenhancedadsorptionofreducibleimpuritiessuchashumidityandthequalityofthespinelcrystallinelatticeitself[2].
Conclusion
Inthiswork,Li4Ti5O12thinfilmsonAusubstratefabricatedbyusingink-jetprintingtechniquefollowedbyanannealingprocessat550°Cfor90minasananodeforrechargeablelithiumionbatterieswereinvestigatedindetail.Theas-preparedLi4Ti5O12thinfilmsannealedat550°Cfor90mindisplayeditslargestdischargecapacityabout174mAh/g.Thedischargecapacityinthe300thcycle(153mAhg−1)is88%ofthelargestdischargecapacity.Theexcellentelectrochemicalpropertiesoftheas-preparedLi4Ti5O12thinfilmssuggestthepromisingapplicationofink-jetprintingtechniquetothinfilmelec-trodesforlithiumionbatteries.
AcknowledgementsThisworkwassupportedbytheNationalNatureScienceFoundationofChina;KeyYouthTeacherFoundationofZhongyuanUniversityofTechnology.
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