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Volume8,Issue21
November9,2015
Pages35393555

Review

AdvancesandFutureChallengesinPrintedBatteries
RicardoE.Sousa, Dr.CarlosM.Costa, Prof.SenentxuLancerosMndez

Firstpublished:
25September2015

Fullpublicationhistory

DOI:
10.1002/cssc.201500657
Citedby:
4articles

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FundingInformation

Abstract
Thereisanincreasinginterestinthinandflexibleenergystoragedevicestomeetmodernsocietysneeds
forapplicationssuchasradiofrequencysensing,interactivepackaging,andotherconsumerproducts.
Printedbatteriescomplywiththeserequirementsandareanexcellentalternativetoconventionalbatteries
formanyapplications.Flexibleandmicrobatteriesarealsoincludedintheareaofprintedbatterieswhen
fabricatedusingprintingtechnologies.Themaincharacteristics,advantages,disadvantages,
developments,andprintingtechniquesofprintedbatteriesarepresentedanddiscussedinthisReview.
Thestateofthearttakesintoaccountboththeresearchandindustriallevels.Ontheacademiclevel,the
researchprogressofprintedbatteriesisdividedintolithiumionandZnmanganesedioxidebatteriesand
otherbatterytypes,withemphasisonthedifferentmaterialsforanode,cathode,andseparatoraswellas
inthebatterydesign.Withrespecttotheindustrialstateoftheart,materials,deviceformulations,and
manufacturingtechniquesarepresented.Finally,theprospectsandchallengesofprintedbatteriesare
discussed.

1Introduction
Printingelectronicsisatechnologythatinvolvestheprintingofelectroniccircuitsandcomponentssuchas
sensors,transparentelectrodes,andlightemittingdevices[1]ondifferentsubstratessuchaspaper,plastics,
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andtextilesusingstandardorspecificprintingprocessesandequipment.[2]Itrequiresthedevelopmentof
inksthataredielectric,semiconductive,orconductivebasedonpolymers,metalnanoparticles(NPs),or
composites,whichareusedtoprintactivedevices.[3]Inthissense,recentadvancesinconductiveinks
achievethroughtheirstabilizationindispersionsandnovelformulationsaswellasinflexiblesubstrates
promisetodelivernewapplicationsandopennewmarkets.[4]Themostimportantadvantagesofprinting
electronicsarelowcost,flexibility,andsimplicityofproductionandintegration.[5]
Printingelectronicstechnologycanfacilitatethedevelopmentofnovelandlowcostfunctionalelectronic
devicescomparedtotheconventionalelectronicstechnologybasedonSi.[5]Printingfabricationofelectronics
isparticularlyinterestingforlargeareadevicesthatdonotrequirehighdensitypatterning,suchasradio
frequencyidentification(RFID)tags,lightemittingdiodes(LEDs),healthmonitoringtags,memorystorage
devices,flexibledisplays,smartlabels,batteries,activeclothing,andphotovoltaics.[5,6]
Batterieshaveanincreasingtechnologicalimpactonoursocietyandhavebecomeanessentialpartofour
dailylives.[5]Bymovingawayfrombatteriesthatcontainheavymetalstoecofriendlybatteries,thebeginning
ofanewparadigmofpowerdevicescanbeobserved.[7]Foralongtime,conventionalbatterieswerebulky
andheavy.Nowadays,itispossibletoobtainprintedbatteriesthatarethinnerthanamillimeter,lighterthana
gram,andcanbeproducedcostefficientlythroughaprintingprocessandonalargescale.[8]
Allbatteriesfabricatedbyprintingtechnologiesaredenominatedprintedbatteries.[9]Inthissense,flexible
batteries[10]and/ormicrobatteries[11]canalsobeincludedinthisscopewhenobtainedbyprinting.
Printedbatteriesarebasedonsolidpolymerorcompositegelelectrolyteswithionicconductivitiescloseto
highperformanceliquidelectrolytesinadditiontoanodeandcathodematerials.[8]Thecombinationof
materialsbasedonconductiveinkswithhighthroughputprintingtechniquesinbatterysystemshasenabled
thefabricationoffunctionalsystemsthatarecustomizable,thin,lowcost,mechanicallyflexible,andhavea
largearea.[6,12]Theresultofthiscombinationisexpressedinsmall,highpower,flexible,andlightweight
rechargeableLibasedbatteries.[12]Furthermore,whencombinedwitharolltorollproductionmethod,it
enablesbatteriestobefabricatedathighspeedonrolltorollmachinerythatjointhevariouslayersofthe
batteryinacontinuousrunprocess,reducingproductionstepsandcosts.[12]
Anoverviewonprintedbatterycomponents,technologies,applications,andadvantagesisshowninFigure1.

Figure1.
Openinfigureviewer

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Overviewofmainissuesregardingprintablebatteries.
Recently,therehasbeenastronginterestinultrathin,flexible,andsafeenergystoragedevicestomeetthe
variousdesignandpowerneedsofmoderngadgets.Tobuildsuchfullyflexibleandrobustelectrochemical
devices,multiplecomponentswithspecificelectrochemicalandinterfacialpropertiesneedtobeintegrated
intosingleunits.[13]Theperformancecharacteristicsofenergydevicesareessentiallydeterminedbythe
structuralandelectrochemicalpropertiesoftheelectrodematerials.Anotherimportantcomponentisthe
electrolyte,whichcanlimitthehighpowercapabilityandpackagingdesigns.[13]Notethatthecharacteristics
oftheprintedbatteriesdiffersignificantlyfromthoseofconventionalbatteries(thekeydifferentiatingfactoris
itsintegrationinadditiontootherpropertiessuchascapacity,weight,dimensions,andsafety)[8]andtendto
bethinandecofriendly.Currently,researcheffortsaredevotedtoimproveperformanceofbatteriesand
developingnewfabricationprocesses.Therearealreadyseveralcompaniesonthemarket(seeTable7),
producingprintablebatteriessuitableforcostumerproductswithspecificdesignsandcharacteristics.
Fromsmartcardstoradiofrequencyidentification(RFID)securityandinformationdevicesandthinfilm
medicalproducts,printedbatteriescanprovidetherequiredpower.Newproductsandapplicationsthat
requireonboardbatterypowerareincreasinglyemerging.[14]Furthermore,transparentdevicesrecently
attractedsubstantialattention,butbecausebatteryelectrodematerialsarenottransparentandhavetobe
thickenoughtostoreenergy,thedevelopmentoftransparentprintedbatteriesisstillachallenge.[15]
Takingintoaccountthenewapplications(elabels,epackaging,eposters,medicaldisposables)thatresulted
fromthecombinationofprintingelectronicsandbatterytechnologies,theglobalmarketvalueexpectedin
2015is0.15billiondollars.[16]Althoughitwasdemonstratedthattheprintedbatterymarketisstrongly
increasing,themanufacturersofthesenewtypesofbatteriesstillfaceimportantchallenges.[17]ThisReview
showsthemostimportantdevelopmentsinprintedbatteries:theadvantagesanddisadvantagesofprinted
batteriesarehighlightedwithrespecttoconventionalbatteries,aswellastheirmainapplicationsandthe
printingtechniquesthatcanbeused.
ThestateoftheartinthisReviewisorganizedintwosectionsdevotedtoresearchandindustry
developments,respectively.Thestateoftheartregardingresearchissuesisfurtherdividedintothedifferent
batterytypesaswellasthemaincharacteristicsofthematerials.Finally,themainchallengesandfuture
researchanddevelopmentneedsarepresented.

2MainAdvantagesandDisadvantagesofPrinted
Batteries
2.1Advantages
Printingelectronicsoffersapotentialforhighvolumemanufacture,drivingdownproductioncostandallowing
largearea,flexible,compact,andportabledevices.[5]Furthermore,itfacilitatesproductionandintegration[5]
anditissuitableforlargeareadevicesthatdonotrequirehighdensitypatterningsuchasbatteries.[5,6]
Thereasonsforusingaprintedbatterywouldgenerallybeeithertolowerthecostortoenablespecificdesign
featuresthatonlyprintingcanprovide.[17]Printedbatteriesbasicallycombinetheadvantagesassociatedwith
thinfilmtechnologieslightweight,flexible,integration,amongotherswiththelowmanufacturingcost
typicallyassociatedwithprinting.[17]Itispossibletoobtainprintedbatteriesthatarethinnerthanamillimeter,
[6,8,12]lighterthanagram,[8]mechanicallyflexible,[6,12]customizable,[6,12]whichcanbeproduced
costeffectivelyonalargescale.[6,8,12]

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Manyprintingtechnologiesarecapableofproducingelectricalcomponentsusingfunctionalpolymersand
materialsonflexiblemedia,patterningtheminavarietyofways.[18]Ontheotherhand,throughtheuseof
specificallyformulatedconductiveinksforscreenprinting,flexography,orinkjettechnologies,avarietyof
productscannowbeproduced,[18]withtheemergenceofnovelinkformulationsandflexiblesubstrates
promisingtodelivernewmarketsandapplications.[4]
Itisonlyamatteroftimebeforethesetechnologiesandapplicationsadvancetoalevelatwhichtheycanbe
massproducedinmorecomplexforms,suchascarbatteriesandportableelectronics.[18]
ThemainadvantagesofprintedbatteriesarepresentedtheTable1.

Table1.Mainadvantagesanddisadvantagesofprintedbatteries.

Advantages
flexibilitycompactandportableeasyproductionandintegration
fabricationoflargeareadevicescustomizable

Disadvantages
currentlyhighercostnonoptimizedmanufacturing
processnewinksmaterialsneeded

2.2Disadvantages
Printablebatterieshavestillthedrawbacksofdevelopingtechnologiessuchasmaterialandprocess
optimizationtomaximizeperformance.However,themostseriousproblemforthesebatteriesiscost.[17]The
mainfactorretardingthemarketentrancefortheprintedbatteriesatthepresenttimeistheirhighcostwith
respecttoconventionalbatteries.However,someoftheseproblemswereaddressed.
Conventionalbatteriesareveryinexpensive,anditiscurrentlyimpossibleforprintablebatteriestocompete
withthem.[17,19]Thiswillchangeasproductionvolumesincreaseandtechnologyimproves.[19]Effortsin
thissensemustincludenewmanufacturingapproaches,[17,19]includingthesimplificationofthe
manufacturingmethodsthattranslatesintoareductionofcosts.[19]
Theaddressablemarketforthesetypesofnewbatterytechnologiesissmall(thepoweredsmartcardisa
goodexampleofprintablebatteryapplications).[17]Inthiscontext,manufactureshavealsotheneedto
developproductsinwhichthebatteriesareintegrated,suchascosmeticpatches.[17]
Inthiscontext,printedbatteryindustriesoftenusedoriginalequipmentmanufacturerstobuildanintegrated
applicationsystem.[19,20]However,itseemsdifficultatthepresentstagetobeabletocompeteonprice
alonewiththeconventionalbatterymarket.[19]Recentcommercialattemptstodevelopbatteryinkshave
highmanufacturingcostsandproducesmallnominalvoltages.[18]Improvementsintherefinementsinareas
ofprintabilityandmaterialqualityandperformancearethusessential.[18]Themostrelevantdisadvantages
ofprintedbatteriesareshownatTable1.

3PrintedBatteriesversusConventionalBatteries
Itwillbedifficultforprintedbatteriestocompetewithconventionalbatteriesinapplicationsthatdonothave
constraintswithrespecttosize,shape,oraccessibility.[20]Printedbatterytechnologyisthusmeanttofillthe
gapofconventionalbatteriesinwhichsizeandhighdensitypoweraremainrequirements,thatis,highly
advancedelectronicdevices.[20]Printedbatteriesaresuitableforavarietyofspecificapplicationsaswillbe
describedinthenextchapter,[19]manufacturedthroughprintingtechnologies,[21]attractiveduetotailorable
size,flexibility,andthepossibilityoflowcostmanufacturinginlargeareasturnthemeconomicallyattractive.[
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19]ThemainfeaturesofprintedbatteriesarepresentedinFigure2.Thekeyfactorsandfeaturesofprinted
batteriesare:

Figure2.
Openinfigureviewer
Mainfeaturesoftheprintedbatteries.

Smallthickness :
Conventionalbatteriesarenotadequateforseveralelectronicapplications,includingantennas,
[22]
biosensors, [23] orRFIDdevices. [24] Printedbatterieswithsmallthicknessandoptimizable
formsprinteddirectlyontovarioussubstratesareidealforhighperformanceprintedelectronics.
Lowcostofproduction :
Oneoftheadvantagesofprintedbatteriesistheprospectoflowcostdevices.After
optimizationoftheexperimentalprocedures,maskcostsareeliminated,thusenablingcost
efficientmanufacturingeveninlowvolumeproduction.Furthermore,itcanbealsointegrated
intothesameproductionlineusedforthefabricationofdevices. [25]
Flexibility :
Typically,polymersubstratesshowhighresistancetochemicals,arelightweightandflexible.
Thisflexibilityfacilitatesthemanufacturingprocess [26] andallowsnovelapplicationsareas.
Ecofriendly :
Printedbatteriesshowsafetyandecofriendlyadvantages.Ecofriendlymeansthattheyare
freeoftoxins,heavymetals,andrareearthelements.Furthermore,theyrequirelowenergy,
bothduringthemanufacturingprocessandduringoperation.Thereductionoftheamountof
solidmaterialwastegeneratedduringmanufacturingisakeyfeatureofprintedbatteries. [27]
Currently,theonlycomponentinaprintedbatterythatisnotsolidistheelectrolyte.Typically,thiscomponent
canbeacompositegelwheretheseparatorlayerissoakedwithanorganicliquidelectrolyte(saltdissolved
intoapolarorionicliquidtoproduceanionconductingsolutioninaninertpolymericmaterial),[28]the
processbeingdeterminedbyatimedependingswellingprocess.Withthedevelopmentofsolidstate
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electrolyteinks,thesebatteriescouldbecomeentirelyprinted,whichisstillmoreadvantageous[21]thanthe
currentmanufacturingprocesses.
Otherfundamentalstepsinprintedbatterymanufacturingisencapsulation,[29]usedforprotectionand,most
important,toreducehumidityandretaintheelectrolytesolutioninsidethebattery.[30]
Otherenergystoragedevicesthatcanbefabricatedbasedonprintingtechniquesaresupercapacitors.
Supercapacitorshaveahighspecificpower(Wperkg),rapidcharge/dischargerates,longcyclelife(>100
000cycles),fastdynamicsofchargepropagation,andlowmaintenancecosts.[31]

4RelevantApplications
Printedbatteriesaresuitableforawiderangeofapplications.Themostimportantapplicationsofprinted
batteriesareRFIDdevices,sensors,poweredcards,smarttoys,andmedicaldevices,whichalsoshowthe
highestpotentialmarketdemand.Thecommonrequirementsforprintedbatteriesfortheiruseinthese
applicationsarebeingthin,flexible,anddisposable.Printedbatteriescanalsobeappliedinproductsthat
requireonboardbatterypower,whicharecontinuouslyemerging.[9]
RFIDdevices(Figure3)useradiowavestocommunicatetoahostdevice,themainapplicationisthe
automaticidentificationandtrackingoftagsattachedtoobjects.[32]

Figure3.
Openinfigureviewer
GraphicalrepresentationofaRFIDdevice.
TherearetwotypesofRFIDdevices:activeandpassive.ThedifferenceamongthemisthatactiveRFID
devicesuseaninternalpowersource(battery)inthetagtocontinuouslypowerthetaganditsRF
communicationcircuity,whereaspassiveRFIDdevicesrelyonRFenergytransferfromthereadertothetag
topowerthetag.[33]ThelimitationsofactiveRFIDtagperformanceisdirectlyrelatedtoitsbattery.[34]
ThecombinationofprintedbatterieswithRFIDdevicesopenspossibilitiestoextendthereachofRFID
devicesandwillallowarapidexpansionofitsmarket(evaluatedtobe9.2billiondollars).[35]
Poweredcardsarealsoapplicationswhereprintedbatteriescanbeincreasinglyused.Figure4showsan
exampleofpoweredcardswithanincorporatedbattery.Thesecardscontainmemorychipsor
microprocessorsthatrequireanembeddedbattery,enablingapplicationssuchasonetimepasswordcards,
secureaccess,financialcards,andgiftcards.[36]

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Figure4.
Openinfigureviewer
Representationofapoweredcard.
Theminiaturizationofelectronicsallowedstrongadvancesinmedicine,withthedevelopmentofnovelmedical
devicesinwhichprintedbatteriesareadvantageoustakingintoaccounttheirsizeandflexibility.Oneexample
ofmedicaldevicesusingprintedbatteriesaretransdermaldrugdelivery(TDD)systemswherebatteries
powertheintegratedcircuitthatensurestheproperdosagecontroluntil.[37]Figure5showsoneexampleof
thesemedicaldevices.

Figure5.
Openinfigureviewer
ExampleofaTDDsystem.
Printedbatteriescanalsobeusedinotherhealthmonitoringsystems,woundcareandcosmeticuses,
wirelesspatchesforpatientmonitoring(electrocardiograms,monitoringofvitalsigns),andpatientwristbands.[
38]
Finally,otherpotentialapplicationsforprintedbatteriesincludesensorsandsmarttoys.Dependingonthe
applicationofthesensor,aprintedbatterycoupledtothesensorprovideslongtermremotemonitoringand
dataacquisition.[39]Otherimportantapplicationsofprintedbatteriesaresmallpowerelectronicdeviceswith
energyharvestingcapabilities.Energycanbeharvestedfromambientlight,thermalgradients,
vibration/motion,electromagneticradiation,orvibration.[16]
Inrelationtoperformanceparametersofprintedbatteriesintermsofpowerandenergyvalues,lifetime,and
dischargerates,parametersareestablisheddependingontheapplication.RFIDtagsrequireabout5.14W
duringtheactivestatewithacurrentconsumptionof700nAat1.5V,whichrepresentsafiveyearoperation
forabatterywithacapacitorof50mAh.[40]Theactiveandsleeppowerofsmartcardcomponentsare
around15.1mWand4.9W,respectivelyusingabatterydischargingat25A,theautonomyofasmartcart
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withadiabaticcircuitisalmost18months.[41]ForTDDsystems,thetypicalpumpingcapacityvalueis57A
cm 2 whenusingaprintedbatterywithacapacityof247mWh,thepumpingwillcontinuouslyworkfor12
days.[42]

5PrintingTechniques
Theprintingtechnologyisareproducibleprocessinwhichaninkisappliedtoasubstratewiththeobjectiveto
transferaspecificpattern.[4a,43]Theprintedobjectcanbeanimage,text,graphics,oradevice.[44]
Inthepastfewdecades,printingtechnologieshaveevolvedfromjustatooltoprintinformationintoa
generatoroffunctionalities,leadingtotheirwidespreadutilizationinprintingelectronics.[43]Generally,printing
technologiesareclassifiedintwoclasses:conventionalanddigitalprinting.Thedifferenceamongthesetwo
classesisthatconventionalprintingrequirestheuseofamask.[4,27]Figure6showsthemostimportant
printingtechniquesthatcanbeusedforprintingbatteries,dividedintothetwomainprintingclasses.

Figure6.
Openinfigureviewer
Techniquesforbatteryprintingdividedintothetwomainprintingclasses.FigureadaptedfromRef.[
4a].
Themainconventionaltechniquesarespray,flexography,andscreenprinting.Typically,thesetechniques
requiretheuseofaprintingplate(themask)tobereproducedandcanbeusedforrapidandlargescale
production.[43]Incontrasttoconventionalprinting,digitalprintingdoesnotrequiretheuseofaprintingplate
andtheprintedobjectreliesontheapplicationofindividualdropletsejectedfromanozzle.[45]
Independentoftheprintingtechnique,thecommoncharacteristicinalltechniquesistheuseofinks.Theinkis
thusthemaincomponentoftheprintingtechniques.Thefinecontrolofimportantcharacteristicsofinkssuch
asviscosityandsurfacetensionisessentialforsuitableprinting.Inkcharacteristicsalsoaffectingprintquality
areflow,wetting,andresolubilityproperties.[46]Typically,theinksforprintedbatteriesarecomposedof
solvent,binder,andasolidcomponent.Thissolidcomponentconsistsofoneormorecomponentsdepending
theapplication.[47]
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Thecuringprocessisessentiallyindependentofthetypeofink.Forsolutionbasedinks,thequalityofthe
printedobjectdependsonthevolatilityofthesolventusedandtheviscosityoftheink.[48]Asuspension
basedinkisalsoincreasinglyusedforprintedbatteriesandinvolvestheuseofcolloidalsuspensionsandNPs.
Themostoftenusedonesareconductiveinkscontainingconductivefillers .[47]
Table2showsthemostrelevantparametersrelatedtothedifferentprintingtechniquesincludingbothinkand
printingpatterncharacteristics.Inparticular,theinkviscosityiscriticalindefiningprintingtechniqueand
patternquality[49]witharangeofvaluesforeachprintingtechnique.Themostcommontypesofinkjet
printersarebasedonpiezoelectricheadsfromwhichadropletisejecteddirectlyonthesubstratethrough
piezoelectricactuators.[50]InrelationtotheotherparametersshowninTable2,itisparticularlyrelevantto
stressthehigherresolutionofinkjetprintingandthelargerthroughput(i.e.,thevelocity)ofprintingusingthe
spraytechnique.Table3showsthemostimportantadvantagesanddisadvantagesofthedifferentprinting
techniques.

Table2.Characteristicvaluesoftheviscosityandsurfacetensionoftheink,layerthickness,
resolution,andthroughputforthedifferentprintingmethods.[4,44,51]

Printing
technique

Viscosity[Pa
s 1 ]

Surfacetension[mN
m 1 ]

Layerthickness
[m]

Resolution
[m]

Throughput[m 2
s 1 ]

flexographic

0.050.5

13.923

0.042.5

3080

330

spray

<0.15

2520000

arealcoating

345

screen

0.550

3847

0.015100

20100

23

inkjet/piezo

0.0050.02

1525

<0.0520

15100

0.010.5

Table3.Mainadvantagesanddisadvantagesofthedifferentprintingtechniques.

Printing
technique

Mainfeatures
advantages

disadvantages

flexographic

lowplatepatternhighthroughputthinlayers

platedegradationduetosolvents

spray

highthroughputhighthicknessvariation

lowresolutionexcessiveoverspraypoorpainting
efficiency

screen

robustsimplethicklayers

resolutionhighinkviscositylowthroughput

inkjet/piezo

noncontactsmallinkquantitieslowviscosity
inks

lowthroughputnozzlereliability

Takingintoaccounttheadvantagesanddisadvantagesofeachprintingtechnique,thechoiceoftheprinting
techniqueforbatteriesmusttakeintoaccountthesizeofthebatteryandtheinkviscosityforeachcomponent
ofthebattery.Alltheaforementionedprintingtechniquesshowversatilityandareabletointegratetheexisting
manufacturinglinesofindustries.[4a]
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Screenandinkjetprintingarethemostoftenusedprintingtechniquesforprintedbatteriesbecauseofthe
rangeofmaterialsthatcanbeformulatedasinksandthepossibilitytoapplythemonvariousproduction
scales,rangingfromprototypestolargescaleproduction.

5.1Flexography
Flexographicprintingisareliefprintingtechniquewheretheimageisprintedfromprotrudingelementsona
platecylinder.Theimageistransferredtoanytypeofsubstrateincludingplastic,metallicfilmsandpaper,
amongothers.[52]Auniformcylinder,calledaniloxcylinder,isusedtoadjusttheamountofinktransferred
ontothesubstrate(Figure7).Theuniformthicknessoftheinkiscontrolledbythenumberofengravedcells
(mostlyinvertedpyramids),ensuringanevenandrapidtransferofacontrolledamountofinktotheprinting
plate.[52]Theaniloxrollisthemostsensitivepartoftheflexographicprocess,itistypicallyfabricatedusing
chromecoatedceramicsorstainlesssteel,andtheexcessofinkisremovedfromitusingadoctorblade
process.Theinkistransferredontotheraisedimageelementsoftheflexibleprintingplateandfurtheronto
thesubstrate.Thereliefsontheprintingcylinderpickupinkfromtheaniloxroll,andprintingoccursby
pressingthesubstrateagainsttheimpressioncylinder.[27]Themainadvantageofusingflexographyfor
printingelectronicsandbatteriesisthespeedandpotentialtoproduceintegratedsmartpackages.[18]

Figure7.
Openinfigureviewer
Schematicillustrationofflexographicprinting.

5.2Sprayprinting
Sprayprintingischaracterizedbyanumberofdropletsmovinginthedirectionofthesubstrate,resultingfrom
anatomizationprocess(Figure8).

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Figure8.
Openinfigureviewer
Schematicillustrationofsprayprinting.
Therearedifferentconventionalsprayprintingtechniquesbasedonairandelectricfield(electrostatic).[53]In
theelectrostaticsprayingtechnique,thedropletsareejectedinthedirectionofthesubstratebymeansofa
highvoltageappliedtoanozzle.Airspraying,ontheotherhand,isbasedonairpressureand,thus,used
moreoftenthantheothertechnique.Finally,therearealsohybridsprayingtechniquesbasedonboth
electrostaticandairpressuresprayingtechniques.
Sprayprintingallowstoprintarelativelywidevarietyofinkviscositiesandinkthicknessesthatmainly
determinethedropletsize.[54]Typically,theprinterlayersaredriedaftereveryprintingunit.Forthemass
productionofprintedelectronics,severalparameterssuchassubstratecharacteristics,humidity,and
temperature,mustbetakenintoaccount.Theuseofsprayprintingforbatteryprintinghasastrongpotential
owingtoitssimpleoperationandflexibilityinindustrialscalesystems.[4a,27]

5.3Screenprinting
Inprintedelectronics,screenprintingisthemostpopulartechnologyasitisfasterandmoreversatilethan
otherprintingtechnologies.Itfurtheraddssimplicity,speed,andadaptabilitytothefabricationprocess.[55]
Inscreenprinting,theinkispressedusingasqueegeethroughascreenontothesubstrate(Figure9).The
screenismadeofaporousmesh.Duetothesimplicityoftheprocess,awidevarietyofsubstratesandinks
canbeused,allowingahighlayerthickness,whichistypicalforscreenprinting.

Figure9.
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Openinfigureviewer
Schematicillustrationofflatbedtypescreenprinting.
Therearetwomaintypesofscreenprintingtechniques:flatbedandrotary.Theflatbedprocessisillustrated
inFigure9and,aspreviouslyindicated,theinkispressedusingasqueegeethroughaflatscreenontothe
substrate.Inrotaryscreenprinting,theinkispushedthroughaperforatedmetalorpolyesterscreencylinder
ontothesubstrateusingasqueegeeinmovement.[56]Thus,rotaryscreenprintinghasthehighest
throughput,edgedefinition/resolution,andachievablewetthickness.
Independentofthetype,screenprintingisaninexpensive,largeareaprintingtechniquewithgoodcontrol
overthedepositionarea.Thequalityofscreenprintedfilmshighlydependsonthenumberoffibersinthe
screenmesh,thetensionofthemask,thedistancefromthemasktothesubstrate,thecharacteristics
(hardness,edge)andprocessparameters(speed,pressure,angle)ofthesqueegee,thetemperature,the
humidity,andtheairflowaroundtheprintingarea.[27]Also,theinkviscosityislinkedtoallparameters
mentionedandhastobeacutelyadjustedtomatchthemeshusedinthescreenmask.
Finally,stencilprintingisverysimilartoscreenprintingandbothprocessesgenerallyusethesame
equipment.Thedifferencebetweentheseprintingtechniquesisthatinstencilprintingtheimageisasetof
openpatternsinasolidfoil.[44]

5.4Inkjetprinting
Inkjetprintingiscurrentlythemoststudiedtechniqueforproducinglowcostprintedelectronics.[45]Inkjet
printingreliesontheformationofindividualdropletsthatareejectedfromanozzledirectlyontothesubstrate.
Theinkjettechniquecanbebasedoncontinuousflowordropondemand(DODFigure10),whereadroplet
isejectedontothesubstrateonlywhenneeded.[57]Withrespecttothelatter,therearetwotypesofDOD
inkjetprinters:thermalandpiezoelectric.Thermalinkjetprintersdepositinkfromthenozzlebyheatingtheink
untilabubbleisformed,thusforcingasmalldropofinkoutfromthenozzle.Piezoelectricinkjetprintersuse
piezoelectricactuationtoforcetheinkoutofthenozzle.[55a,57]Piezoelectricinkjetprintinghasthelargest
potentialinprintedelectronicsastheinkviscosityisconstantduringjetting,leadingtoamorereliableand
accuratedropletformationandjettingandthustoincreasedprintqualityandspeedaswellasawiderrange
ofsuitablematerials.[27,51a]

Figure10.
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Schematicillustrationofinkjetprinting:a)continuousflowandb)DOD(piezoelectric).
Inkjetprintingisarelativelynewtechnologyonanindustrialscaleandhassomelimitationswithrespectto
processingspeedandinkformulation(viscosity)(Table2).[45,55a]Theprecisionofthistechniqueisthe
highestamongprintingtechniques,asitispossibletoobtainstructuresintherangeofnanometersby
increasingtheelectricfieldalongwiththedistancebetweennozzleandsubstrate.[52]
Insummary,theprintingtechniquesaffectthepropertiesofprintedbatteriesthroughthesizeandthicknessof
thedifferentprintedlayers.Thelargersizeofprintedbatteriesincreasesthecapacityvalue,themostrelevant
techniquesforobtaininglargebatteriesbeingscreenandsprayprinting.
Forapplicationsthatrequirelowcapacities(Ah),thatis,smallsizeandlowthickness,thebestprinting
techniqueisinkjetprinting.Generally,theidealprintedbatteryfordifferentapplicationsrequireslargeareas
andthicklayersofthedifferentcomponents.Tailoringofprintedbatteriesisnecessarytooptimizeits
performancebytakingintoaccounttheapplicationrequirementsandthebestprintingtechniquetoachieve
thedesiredlayers.

6PrintingBatteries
Batteries,inventedbyAlessandroVoltain1800,arenowadaystheessentialelectrochemicalpowersourcefor
theconsumerelectronicsmarketandoneofthekeysfortherevolutionoftheroadtransportationconcept
(electricandhybridvehicles).[58]
Typically,batteriesareclassifiedintoprimary(singleuse)andsecondarythedifferencebetweenthemisthat
secondarybatteriescanberechargedandusedseveraltimes.[59]Independentofthechemicalnatureof
materialmakinguptheelectrodesandthesizeofbatteries,themaincomponentsinabatteryarepositive
electrode(cathode),negativeelectrode(anode),andseparator(Figure11).Duringcharging,themovement
ofionsisfromthecathodefortheanodeelectrodeandduringdischarge,themovementisontheopposite
direction.[60]

Figure11.
Openinfigureviewer
Schematicrepresentationofthemaincomponentsandthechargeanddischargeprocessofa
battery.
Inprintedbatteries,themostoftenusedbatterytypesareLiandZnbasedandjusttheelectrodesareprinted.
Typically,theseparatorisnotprintedasitconsistsofaporousmembranewithelectrolytesolution(salts
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dissolvedintoapolarsolvent).Theelectrolytesolutionisintroducedintotheporousmembranethrough
uptake(soaked)orthroughaninjectionprocess.[28a]
Lithiumionbatteries(LIBs)haveadvantageswithrespecttoothertypesofbatteries[Zn,Nimetalhydride
(NiMH)],suchasbeingcompact,lightweight,highaveragedischargerate(3.7V),andhighenergydensities
(100265Whkg 1 ).[61]Materialsbasedoncarbon[i.e.,graphite,carbonnanotubes(CNT)andcarbon
nanofibers(CNF)]areusedasactiveanodematerials.[62]Forexample,foranodesbasedongraphite,the
electrochemicalreactionofaLIBsystemis:
(1)
wherecrepresentschargeprocessanddrepresentsthedischargeprocess.Forcathodematerials,many
activematerialshavebeenused,thatis,LiCoO 2 ,LiMnO 2 ,andLiFePO 4 .Forexample,forcathodesbasedon
LiFePO 4 ,theelectrochemicalreactionofaLIBsystemis:
(2)
InrelationtoZn/MnO 2 batteries,theyhaveadvantagessuchashighenergycontent,lowerinternal
resistance,largeshelflife,andlowcost,andthus,couldreplaceLIBsinmanyapplications.[63]
PrintedbatteriesbasedonMnO 2 orZnutilizelessexpensivematerialsincomparisonwithmaterialsforLIBs.
Onefundamentalprocessinprintedbatteriesistheirsealing,ofwhichthemainobjectiveistokeepthe
atmosphereconstantinsidethebattery,whichdirectlyinfluencestheirlifetime.Thesealconsistsofasealing
layerbasedonapolymergluethatcanbeprocessedbytheapplicationofheatorpressure.[64]Furthermore
,thesematerialscanbeformulatedintoinkstobeprintedbyscreenprintingontoavarietyofsubstratesin
linewithothermanufacturingsteps.
Thereareseveralotherbatterytypesthatresultfromthecombinationofthedifferentelementsdevelopedto
powersmallelectronicsdevices,aswewillshowinthefollowingsection.

6.1Stateoftheartinprintedbatterydevelopment
Thestateoftheartissubdividedintothreesections,eachdevotedtothedevelopmentinLIBs,Zn/MnO 2
batteries,andotherbatterytypes.Foreachsection,thematerialsandelectrolytesolutionswillbepresented
aswellasthemaincharacteristicsofthebattery,suchascapacityandrelatedpropertiesandtheprinting
techniqueused.Thisinformationischronologicallyordered,toevaluatetheevolutionofthearea,andfurther
discussed.

6.1.1Lithiumionbatteries
ThemaincharacteristicsofprintedbatteriesbasedonLiionsaresummarizedinTable4.Screenprintingis
usedforthepreparationofelectrodesbasedonLi 4 Ti 5 O 12 andLiMn 2 O 4 materialsinLIBswithhighcapacity
(150mAhg 1 )[65]andthickfilmelectrodes(6m)usingamixtureofacarboncoatedLiCoO 2 powder
andanepoxyresinwithhighadhesionstrengthbetweentheprintedcathodeandthecurrentcollector.[66]

Table4.DevelopmentofprintedbatteriesbasedonLIBsandtheirmainpropertiesand
components.

Batterytype
Liion

Anode
Li 4 Ti 5 O 12

Cathode
LiMn 2 O 4

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Separatorandelectrolyte
40%PEG,25%PEO,20%Li

Printing
technique
screenprinting

Capacity/voltage
150mAhg 1

Ref
[65 ]
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saltand15%LiAlO
Liion

LiorFe/Si
multilayer

ZrLiCoO 2

1LiPF 6 inEC/DEC(1:1)

screenprinting

250Ahcm 2 /2V

[71 ]

Li
ion/HPE/MoOxSy
onSi

Li

MoS 2

1LiAsF 6 EC/DEC(1:1)

multiple
processes

[69 ]

Liion

SnO 2

Li

1LiPF 6 inEC/DMC(1:1)

inkjetprinting

812.7mAhg
1 @33Acm 2

[70 ]

Liion

Li

LiCoO 2

PPseparatorsoakedwith1
LiPF 6 inEC/DEC(1:1)

screenprinting

179Ahcm 2

[72 ]

Liion

Li

LiCoO 2

1LiPF 6 inEC/DEC(1:1,v/v)
inPPseparatorandLiPON
solidelectrolyte

screenprinting

125Ahcm 2

[66 ]

Liion

graphite
(MCMB6
28)

LiCoO 2

100mAh

[73 ]

Liion

Li

LiCoO 2

1LiPF 6 inEC/DMC(1:1)

inkjetprinting

120mAhg 1

[74 ]

Liion

Li 4 Ti 5 O 12

LiCoO 2

Xeroxpaperwith1LiPF 6 in
EC/DEC(1:1)

doctorblade
coated

120mAhg 1

[75 ]

Liion

Li

LiCoO 2

LLZONborLi 3 BO 3 solid
electrolyte

screenprinting

85mAhg 1 /34.1
V

[67 ]

Liion

Li

graphene
inkwith
0.1TiO 2
NPs

1LiClO 4

241mAhg 1

[76 ]

Liion

Li

Li 4 Ti 5 O 12

1LiPF 6 inEC/EMC(1:1)

microprinting

146mAhg 1

[77 ]

Liion

Li

LiCoO 2

UVcuredETPTApolymer
matrix,highboilingpointliquid
electrolyte(1LiPF 6 inEC/PC
(1:1 v / v ),andAl 2 O 3 NPs

mechanically
imprintedusing
mazepatterned
PDMSstamp

130mAhg 1

[78 ]

Liion

Li 4 Ti 5 O 12

LiCoO 2

PMMAwithSiO 2 +1LiPF 6 in
EC/DMC(1:1 v / v )

spraypainting
technique

100mAhg 1/3.91
V(LiCoO 2 )125
mAhg 1 /1.5V
(Li 4 Ti 5 O 12 )

[79 ]

Liion

Li 4 Ti 5 O 12

LiFePO 4

1LiClO 4 inEC/DMC(1:1)

3Dprinting

1.6mAhcm 2

[80 ]

Liion

graphite

LiCoO 2

PVDFHFP+SiO 2 +1LiPF 6 in
EC/PC/EMC(1.5:1.0:1.5
w / w / w ),

screenprinting

2.5mAhcm 2

[68 ]

Liion

graphite

1LiClO 4 inEC/DEC(1:1)
soakedonstandardWhatman

spray
deposition

350mAhg 1

[81 ]

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separator
Liion

Li

LiMn 2 O 4

1LiPF 6 inEC/DMC(1:1)
soakedonstandardWhatman
separator

laserprinting

[82 ]

Liion

Li

Li 4 Ti 5 O 12

1LiPF 6 inEC/EMC(1:1)

3Dprinting

[83 ]

Liion

Li 4 Ti 5 O 12

LiFePO 4

SiO 2 basedionogelsconfining
ionicliquid

inkjetprinting

300Ahcm 2

[84 ]

Liion

graphene/S LiMn 2 O 4

microporoustrilayermembrane
(PP/PE/PPCelgard2320)
soakedin1LiN(CF 3 SO 2 ) 2
and0.2LiNO 3 inDME/DOL
(1:1)

sprayprinting

1500mAhg 1

[85 ]

Li 3 BO 3 andLLZONbsolidelectrolyteswerealsofabricatedbyscreenprinting.[67]Limetalastheactive
anodematerialwasdepositedontheoppositesideoftheLLZONbpelletusingavacuumdepositionprocess.
Theprintedbatteryfabricatedshowshighcoulombicefficiency,andtheelectrochemicalperformanceofthe
batterywascomparabletothatofLIBsfabricatedbymeansofphysicalvapordeposition.
Sequentialscreenprinting(wet)wasappliedinthefabricationofapouchtypeflexiblethinfilmLIB,printing
consecutivelayersofthecurrentcollector,positiveandnegativeelectrodes,andthegelpolymerelectrolyte.[
68]Itwasshownthatoptimumconditionsofeachprocessweredeterminedbyadjustingthepasteorslurry
compositionstoachievealowersurfaceresistanceofeachlayer(currentcollectorandelectrodes)andhigher
ionicconductivityforthegelpolymerelectrolyte.[68]
3Dmicrobatteriesarefabricatedtoincreasebatterycapacity.[69]3DperforatedSisubstrateswithhigh
aspectratioverticalchannelshavebeenpreparedusinginductivelycoupledplasma(ICP)etching,resultingin
acoatingofanhybridpolymerelectrolyte.[69]
InkjetprintingwasusedforthepreparationofSnO 2 electrodes,thethicknessofthemonolayerthinfilm
electrodebeing770780nm.[70]Thisworkdemonstratedthatinkjetprintingissuitableforthepreparation
ofthinfilmelectrodesforLIBs.[70]
3DpatternedLi 4 Ti 5 O 12 electrodematerialswerefabricatedusingamicroprintingtechnology,[77]thecellwith
the3Dpatternedelectrodeshowingconsiderablyimprovedchargeanddischargecapacitiesathighratesthan
aconventionalcellwithaflatLi 4 Ti 5 O 12 electrode.[77]Bendablepolymerelectrolyteswithhighion
conductivitieswerefabricated,whichwerealsoconformableto3Dmicropatternedarchitecturesofelectrodes
overlargeareas.[78]Thisworkisparticularlyrelevantasitwasshownthatpolymerelectrolytesaredirectly
writableorprintableontocomplexandflexiblesubstratestakingintoaccounttheirrheologicalcharacteristics
(Figure12).Thechallengeinthedevelopmentof3Dstructuredand/orprintedflexiblebatteriesisthe
maintenanceofgoodcontacttofacilitateelectrochemicalreactionsattheinterfacebetweenpolymer
electrolytesandelectrodes.[78]

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Figure12.
Openinfigureviewer
a)Conceptualillustrationofaprintable,flexible,shapeconformablecgelpolymerelectrolyte(c
GPE).b)DrippingcharacteristicsofaliquidelectrolytethatdoesnotincorporateAl 2 O 3 NPs
(designatedasFsolution).c)NondrippingbehaviorofUVcurableelectrolytemixturebeforeUV
crosslinking(designatedasVsolution).d)Comparisonofviscosity(asafunctionofshearrate)
betweentheFandVsolution.[78]
Throughuseofpaintingtechnique,LIBswerefabricatedbysequentiallysprayingthecomponentpaintson
desiredsurfacesusinganairbrushoperatingat40psi(1psi=6895Pa)ofcompressedair.[79]Thepaintscan
besprayedthroughasetofmasksfabricatedaccordingtothedesireddevicegeometry.Thetemperatureof
thesubstratewascontrolledfrom90120Cusingaheatgunorhotplate.Theseparatorhadalowionic
resistance,withanionicconductivityof1.2410 3 Scm 1 .
InLiionpolymerbatteries,wellcontrolledmicroporosityofpolymerseparatorsisessentialforoptimal
electrolyteuptakeandfortheformationofamicroporousgelelectrolytewithhighionicconductivityand
retentionuponcycling.[79]BeforeassemblingtheLiioncell,sprayprintedLiCoO 2 /polymerand
Li 4 Ti 5 O 12 /polymerstacksweretestedinhalfcellconfiguration,showingtheexpectedplateaupotentials(3.91
VforLiCoO 2 and1.5VforLi 4 Ti 5 O 12 ),goodinitialcapacities(100mAhg 1 forLiCoO 2 ,125mAhg 1 for
Li 4 Ti 5 O 12 )andsuitablecapacityretentionuponcycling.[79]
Itwasalsodemonstrated[81]thatsprayprintingofaqueousslurriescanbesuccessfullyimplementedona
pilotpapermachineforrapidandreliablelargescaleproductionofselfstandingLIBelectrodesusingnatural
microfibrillatedcelluloseasabinder.Thefeasibilityoftheproposedprocessinproducingwellfunctioning
electrodeswasdemonstratedbyevaluatingthelongtermelectrochemicalbehavioratroomtemperature.In
Ref.[75],allcomponentsofaLIBwereintegratedintoasinglesheetofpaperbyasimplelaminationprocess.
Freestanding,lightweightCNTthinfilms(0.2mgcm 2 )wereusedascurrentcollectorsforbothanodeand
cathodeandwereintegratedwiththebatteryelectrodematerialsthroughasimplecoatingandpeeling
process.Li 4 Ti 5 O 12 /CNTandLiCoO 2 /CNTcoincellswerefabricatedforhalfcelltestsinwhichLifoilandXerox
paperwereusedasthecounterelectrodeandseparator,respectively.[75]
3DprintingwasusedforthefabricationofLIBsbasedonLi 4 Ti 5 O 12 (meanparticlediameter50nm)and
LiFePO 4 (meanparticlediameter180nmFigure13).This3Dbatteryshowshigharealenergydensityof9.7
Jcm 2 atapowerdensityof2.7mWcm 2 .[80]

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Figure13.
Openinfigureviewer
a)Opticalandb)SEMimagesofprintedandannealed16layerinterdigitatedLi 4 Ti 5 O 12 LiFePO 4
electrodearchitectures.[80]
LiMn 2 O 4 compositematerialwaslaserprintedontoflexibleAlsubstratesforthedevelopmentofporousthick
filmcathodeswithathicknessof60m.Thelaserprintedcathodefilmswerecalenderedand/orlaser
structuredtomanufacture3DmicrostructureswithimprovedelectricalcontacttotheAlsubstrateandto
improvetheelectrolytewettingbehavior.[82]
The3Dpatternedelectrodecharacterizedbylinedpatternswithahighaspectratiowasprepared.[83]The
cellusing3Dpatternedelectrodeshowedmuchbetterratecapabilitythanthatpreparedusingaconventional
flatelectrode.
InRef.[84],itisshownthatjetprintedmicrobatteriesusingallsolidstateinkissafewithcompetitive
performancesincomparisontostandardallsolidstatemicrobatteries.Highionicconductivitiesand
compatibilitywithporouscompositeelectrodesallowgoodelectrochemicalcyclingperformancethus,afullLi
ioncellwithLiFePO 4 andLi 4 Ti 5 O 12 porouscompositeelectrodeshasasurfacecapacityof300Ahcm 2 for
morethan100cycles.[84]
Highcapacity(1500mAhg 1 )wasfoundinLIBsusinganodesbasedongrapheneandSmaterials
preparedusingthesprayprintingmethod.[85]

6.1.2Zn/MnO 2 batteries
ThemaincharacteristicsofprintedbatteriesbasedonZn/MnO 2 aresummarizedinTable5.Printedthinfilm
batteriesareparticularlycompellingaspowersourcesforprintedelectronicsastheycanbemanufacturedon
thesameprintingline.Achallengeinthisintegrationhasbeenthetypicallylowcellpotentialofabattery
(maximumof4.2V),whichalonedoesnotmeetthehigherpotentialrequirementsofprintedthinfilm
transistors(1030V).[6]Addressingthisissue,Zn/MnO 2 batterieswerefabricatedusingMnO 2 inkbasedon
amixture(byweight)of45.3%MnO 2 particles(Tronox),10.6%graphite(KS6,Timcal),12.1%KOH(9),
1.8%styrenebutadienebinder(LICOTechnologyCorp.),and30.2%deionizedwaterassolvent.[6]TheZn
inkwasfabricatedbymixing(byweight)69.3%Zn,7.3%ZnOnanopowder(Inframat),10.9%Bi 2 O 3 (Alfa
Aesar),1.6%styrenebutadienebinder,and10.9%ethyleneglycolassolvent.

Table5.DevelopmentofprintedbatteriesbasedonZn/MnO 2 andtheirmainpropertiesand
components.

Battery
type

Anode

Cathode

Separatorandelectrolyte

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Capacity/voltage

Ref
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Zn/MnO 2

Zn

MnO 2

separatorsoakedinaqueous
solutionofNH 4 ClandZnCl 2

printingprocess

1525mAh/1.45V

[86 ]

Zn/MnO 2

Zn

MnO 2

[4.6NH 4 Cl(aq.)]/13.7wt%
PEI/3.7wt%Carbopol940

screenprinting

25mAh

[87 ]

Zn/MnO 2

Zn

MnO 2

fibroussubstrate

stencilprinting

/14V(ten
batteriesinseries)

[6 ]

Zn/MnO 2

Zn

MnO 2

PAAbasedKOHgelelectrolyte

stencilprinting

4mAhcm 12

[88 ]

Zn/MnO 2

Zn

MnO 2

polyvinylalcohol/cellulosewetlaid
nonwovenmaterialsoakedin
solutionof5.6KOHand0.37
ZnO

membrane
embeddedusing
electrochemically
activeink

3mAhcm 2 /1.5V

[89 ]

Zn/MnO 2

Znwire

MnO 2 /carbon
fiber

158mAhg 1

[90 ]

Zn/MnO 2

Zn

MnO 2

paperseparatorsoakedin
saturatedZnAcelectrolyte

[91 ]

Zn/MnO 2

Zn

MnO 2

mixture(1:1)ofPVDFHFP/0.5
solutionofZn+Tfdissolvedin
BMIM+Tf

flexography

0.13mAhcm 2 /1.8
V

[92 ]

BatteriesusingarandomnetworkofCNTsservebothaschargecollectorandtheinterfacewiththeactive
components.[86]Devicesfabricatedbylayerbylayerinanallsolutionphaseapproacharesuitableforlarge
scaleproductionsuchasrolltorollprinting.TheproofofconceptdeviceisbasedonaZnfoilanode,which
alsoactsasachargecollector,aseparatorsoakedinasolutionofNH 4 ClandZnCl 2 electrolytes,anda
cathodefabricatedfromapasteofMnO 2 ,CNTs,andintheelectrolytemixture.ArandomCNTnetworkontop
servesasthechargecollector,althoughanyconductingnanowirecouldservethesamepurpose.Inaddition,
thedevicescanbefabricatedusingarolltorollorinkjetprintingprocess.[86]
Foradifferentapproach,a1.5VclassfilmtypeLeclanchbatterywasdesignedbyadoptingamultilayered
packagingfilmandNH 4 Clbasedadhesiveaqueouselectrolytesfabricatedbyscreenprintingtechniqueto
improvethebarrierandselectivepermeation,ionicconductivity,andshelflife.[87]InRef.[88],aflexible
printedbatterywithameshsupportispresented(seeFigure14).

Figure14.
Openinfigureviewer
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a)SchematicdiagramofthecrosssectionofanassembledZn/MnO 2 alkalinebatterywithsandwich
typearchitectureandb)opticalimageofaflexibleZn/MnO 2 batterylaminatedinsideapolyethylene
pouch.[88]
Themeshsupportenablestheseflexiblebatteriestoexhibitahighcapacitybecauseofanincreased
thicknessoftheelectrode.Thisbatterydesigncanbecustomizedtopowerdeviceswithvariouspowerand
energyrequirements,andtheprocesscanbereadilyintegratedwithcurrentlargescalemanufacturing
techniques.Themesharchitectureisnotlimitedtoalkalinebatterysystemsandcouldbeusedwithother
batterychemistries.Readilycustomizedflexiblebatteries,suchasthosedescribedhere,willhelptorealizethe
potentialofflexiblemobileelectronicdevices.[88]
Atechniquetoreinforcebatteryelectrodeswasdevelopedbysupportingthemwithmechanicallytough,low
costfibrousmembranes,whichalsoserveastheseparator.[89]Thistechniquewasusedtofabricateahigh
energydensity,nontoxicZn/MnO 2 batterywithprintedcurrentcollectors.TheZnandMnO 2 electrodeswere
preparedbyasolutionbasedembeddingprocess(Figure15).Thecellhadanominalpotentialof1.5Vand
aneffectivecapacityofapproximately3mAhcm 2 .Theeffectofbendingandfatigueontheelectrochemical
performanceandmechanicalintegrityofthebatterywasinvestigated.Thebatterymaintaineditscapacity
evenafter1000flexcyclestoabendradiusof2.54cm.Thebatteryshowedanimprovementindischarge
capacity(ca.10%)iftheMnO 2 electrodewasflexedtotensionasaresultoftheimprovementofparticleto
particlecontact.TheflexiblebatterywasusedtopoweraLEDdisplayintegratedwithastrainsensorand
microcontroller.

Figure15.
Openinfigureviewer
Schematicoftheprocessusedtoreinforceflexiblebatteryelectrodes.[89]
AnovelfibertypeZncarbonbatterybasedoncarbonfiberwasproposed.[90]Thefiberbatteryconsistedof
twocarbonfiberbasedelectrodes,oneinsulatedwireastheseparator,andanelectrolytesealedinaflexible
plastictube.Thefiberbatterydidnotexhibitanylossincapacityduringthebendingtests,illustratinggood
flexibility.
ThedevelopmentforallothercompositeslurrycomponentsoftheZnbasedbatterysystemforflexographic
printinginshowninRef.[92],includingawaterbasedZnanode,Nicurrentcollectoraswellasaninert
particlebasedionicliquidslurryelectrolyte.Itwasalsosuggestedthatthroughfurtheroptimizationoftheink
formulationsitispossibletoachievebetterprintingqualityonavarietyofnonconductiveandconductive
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substrates.Specifically,theeffectsofthepolymerbindercontentsaswellasthetypeandamountof
surfactantadditivesontheprintabilitymustbeaddressed.[92]

6.1.3Otherbatterytypes
Intheprevioustwosections,thedevelopmentofprintedLiionandZn/MnO 2 batterieswasshown,takinginto
accounttheprintingtechniqueandcapacities.Therearealsootherbatterytypestheirmaincharacteristics
aresummarizedinTable6.

Table6.Mainpropertiesandcomponentsofdifferentprintedbatteries.

Battery
type

Anode

Cathode

Separatorand
electrolyte

Printing
technique

Capacity/voltage

Ref

Ni/H 2

Ni

Ni

Celgardseparator(3501)
soakedwith26wt%KOH

microfabrication

1.7
mAh@C/12/1.48V

[93 ]

Zn/air

Zn/carbon/polymer

PEDOT|Au|Gore
Tex

0.1MLiOHsolutionin
deionizedwaterand12M
ofsolutionofLiCLin50
mLofthe0.1MLiOH
solution

screenprinting

1.4mAhcm 2

[94 ]

Ag/Zn

Zn

Ag

1to10KOHwith57g
L 1 dissolvedZnO

inkjetprinting

[95 ]

Ag/Zn

Zn

Ag

57:29:14H 2 O/KOH/PEO
( M v =600000)

printing
technique

1.8mAcm 2

[96 ]

Ag/Zn

Zn

Ag

PAAcontaining6
KOH+1LiOH

screenprinting

1.32.1mAhcm
2 /1.5V

[97 ]

Ag/Zn

Zn

Ag 2 O

PAAelectrolytein
aqueousKOH

stencilprinting

5.4mAhcm 2

[98 ]

organic
radical

0.1solutionofNBu 4 BF 6
inPC

inkjetprinting

[99 ]

organic
radical

0.01AgNO 3 and0.1
solutionofNBu 4 ClO 4 in
CH 3 CN

screenprinting

[100 ]

AconventionalNiH 2 batteryreliesonhighpressureH 2 (5.57MPa)toprovidethenecessaryhydrogen

capacitytomatchthepositiveelectrodecapacity.Inlightofthisdemand,thepossibilityofmicrofabricatinga
NiH 2 batteryusingthickfilmprintingwasevaluated.[93]NiOHpowder(KansaiCatalystCoparticlesize12
m)wasusedasthepositiveactivematerial.Thepowderwascoatedwith2.5wt%Coandhad4.5wt%Zn
and0.7wt%Comixedinsolidsolution.AninkbasedonPtblackinPVDF/DMFslurrywasdevelopedand
printed.APtblackbasedinkwasshowntobeanacceptablenegativeelectrodeinkwithreasonablereactivity
towardsH 2 oxidationandreductionandnegligiblemasstransferresistance.Afullcellwasassembledusing
theprintedpositiveassemblyandtheprintednegativeassemblyusingaconventionalelectrolytesoaked
separator.Suddenupwardshiftsinchargingcurvesandacorrespondingrapidincreaseinthetotalcell
impedancewereobservedduringcycling.Theincreaseincellimpedanceisrelatedtopooroxygen
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recombination/waterredistributionwithinthecell.However,animprovementintheutilizationpercyclewas
alsoobserved,showingthepossibilityofacceptablecyclingbehaviorifbettercontrolofthetotalcell
impedancecouldbeachieved.[93]
AtwostepprintingtechniquetodepositanalkalineelectrolyteforahighenergydensityAg/Znprintedbattery
isshownin[96].Ananalysisofelectrolytesconsistingofpolyethyleneoxide(PEO M v =600000)andmethyl
cellulosewasperformed,showingthatadried57:29:14H 2 O/KOH/PEOelectrolyteshowedthehighestareal
energydensityof4.10.3mWcm 2 and943%ataC/2dischargerateof1.8mAcm 2 .Usingasynthesized
polyacrylicacid(PAA)separator,astencilprintedAg 2 Obatterywasprepared,whichexhibitedarealcapacities
of5.4mAhcm 2 andvolumetriccapacitiesof7.1mAhcm 3 (Figure16).[98]Thebatteriesshowno
differencesindischargebehavioruponflexingatabendradiusof1.0cm,indicatingtheirpotentialforflexible
applications.Theprocessesarescalabletolargescalemanufacturingandallowtailoringfortheapplication.

Figure16.
Openinfigureviewer
a)Stencilprintingofslurrytoformprintedelectrodes,b)crosssectionofaprintedbatterystack,c)
topdownviewofbatterystackandd)SEMimageofafullyprintedbatterystack.[98]
Organicradicalbatterieswithcarbonfibersincompositeelectrodeswerefabricatedbyscreenprinting.[100]It
isshownthatthecharge/dischargeperformanceofthisbatteryisdominatedbyinterfacialelectrontransfer
processesatthecurrentcollector/carbonfiberinterface.

6.2Commercialprintedbatteries
Batteriesmanufacturedbymeansofprintingtechniquesarealreadyonthemarket.Suchproductsareoffered
bycompanies(seeTable7)thatcurrentlyservenichemarkets.AdvancedMaterialsInnovationCenter(AMIC)
developedaLipolymerbatterythatcanbemanufacturedbyprintingtechnology.[101]TheprintedLipolymer
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batteryisflexibleanddesignedforflexibledisplaysorattachmenttocurvedsurfaces.Itismanufacturedusing
screenprinting,withdimensionsaround500mbutwithahighersurfaceareacomparedwithother
conventionalbatteries.Inadditiontothisfact,itcanbeproducedatlowcostanditisrechargeable.[101]

Table7.Commercialprintedbatteries.

Voltage
[V]

Company

Chemical
System

Anode

Cathode

Capacity
[mAh]

Electrolyte

Productiontechnique

PowerPaper

1.5

Zn/MnO 2

Zn

MnO 2

ZnCl

1530

screenprinting/silk
screenprinting

Solicore

Li/MnO 2

Li

MnO 2

LiTFSi

1025

BlueSpark

1.5

Zn/MnO 2

Zn

MnO 2

ZnCl

3054

Enfucell

1.53

metal/MnO 2

Zn

MnO 2

ZnCl

1090

allprintedbyrolltoroll

Cymbet
Corp

3.63.8

Liion

Li

LiCoO 2

LiPON

130

FrontEdge
Technology

Li/LiCoO 2

Li

LiCoO 2

LiPON

15

Infinite
Power
Solutions

XLiCoO 2

Li

LiCoO 2

LiPON

0.7

OxisEnergy
Ltd

Li 2 S

Li

Li 2 S+S

aprotic
electrolyte
withLisalt

Ion
Technology

3.5

graphiteAl

Al

graphite

solid
polymer

7.5mAhcm

Leeds
Lithium

Clithiated
metaloxide(gel
electrolyte)

LiMn 2 O 4

polymer
electrolyte

Varta
Microbattery

Li/MnO 2

Li(metal,
alloy,
Li/graphite)

MnO 2 ,
LiCoO 2 ,
Li x MnO 2

organic
electrolyte

25
mAh(@0.03
mA

ThinBattery
Technology

1.5

Zn/C/MnO 2

Zn

C/MnO 2

ZnCl 2 ,
Zn(OAc) 2

Imprint
Energy

Zn

metal
oxide

solid
polymer(Zn
ions)

screenprinting

PowerID

1.5

Zn/MnO 2

Zn

MnO 2

electrodelayers
fabricatedfrom
proprietaryinkprinted
ontoanysubstrate

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1.5

Zn/MnO 2

Zn

MnO 2

screenprinting

AflexibleMnandZntypebatterywasalsodevelopedbytheFraunhoferResearchInstitutionforElectronic
NanoSystems[102]2020mm 2 insize,with20mAhcapacityat1mAdischargecurrent.
Enfucellcreatedathin,flexible,andecofriendlysoftbattery.Duringthemajorityofthe20thcentury,batteries
werecylindricalorrectangularinshapeandcontainedheavymetals.Enfucelltakesadifferentapproach.The
companyfocusesontheenvironmentalimpactofitsbatteriesinindustry.Enfucell'sbatteriesaremadeoflow
cost,environmentallyfriendlymaterialsbasedonZn/MnO 2 withZnCl 2 asanelectrolyte.[103]Enfucell[103]
andBlueSpark[5]preparedflexibleandsoftnotrechargeablebatteriesbyprintingonplasticsubstrates.On
theotherhand,SolicoreCompany(SolicoreisnowBrightVolt)producesultrathin,flexible,safe,andhigh
energydensityLipolymerbatteriestomeetpoweranddesignneeds.[14]Theyusescreenprintingto
manufacturethisbattery,replacingliquid,gel,andpasteelectrolytescommonlyfoundinmostrechargeable
batteriesbyapolymerelectrolyte.
Thedeliveredcapacityvaluealsodependsonthesizeofthebatteryand,forexample,theSoftBatteryof
Enfucellwithdimensionsof6072mm 2 exhibitsacapacity90mAhat0.6mAdischargecurrent,compared
withthesamebatterywithdifferentdimensions(3646mm 2 )whichshowsacapacityof18mAhat0.2mA
dischargecurrent.[103]
Table7showsthattherearedifferentcommercialprintedbatterieswithcapacitiesvaryingbetween0.7and
90mAh,themaindifferenceoftheprintedbatteriesbeingtheelectrolyte.Theformulationofthismaterialis
extremelyimportantasitdeterminesionicconductivitiesanddiffusion.Pleasenotethelackofprecise
informationprovidedbythemanufacturerswithregardtothisissueaswellasabouttheprice.Thepriceofthe
batterydependsofthemanufacturingcompanyandsize,beinginthe$2to$5rangeforeachbattery.

7ConclusionsandChallenges
ThisReviewshowsageneraloverviewofdifferenttypesforprintedbatteries.Thesuccessofprintedbatteries
isrelatedtotheircharacteristics,thatis,theyarethin,flexible,andproducibleatlowcostandtheyconsistof
ecofriendlymaterials.Theinkformulationofthedifferentmaterialsforprintedbatterieshasbeenlittle
exploredwithregardtothedevelopmentofenergystoragesystemswithhighcapacitiesandvoltages.The
maintypesofprintedbatteryaredividedintolithiumionbatteries(LIBs)andZn/MnO 2 batteries.Thechoiceof
thebatterytypedependsontheapplicationandthecapacityrequired.Themanufacturingofprintedbatteries
isnottrivialandrequiresaninkformulationoptimizedforeachprintingtechnique.Theinkformationiskeyfor
printingtechniquesasrheologyofeachinkmustbeoptimizedtoensurereliableflow,promoteadhesion
betweentheprintedfeatures,andprovidethestructuralintegrityneededtowithstanddrying.Itisforthis
reasonthatmanyresearchersfocusonthedevelopmentofinksforspecificcomponentsofthebattery.Inks
optimizedforcathodeandanodematerialsarereportedintheliterature,buttheseparatorisstillachallenge
thatrequiresfurtherresearch.
Thechallengesforfutureprintedbatteriesaredividedintodevelopinginksforeachcomponent,completely
printedbatteries,anddifferentarchitectures.
Withregardtotheinks,theirphysicalchemistrypropertiesshouldbeadjustedtakingintoaccounttheprinting
technology.Theparametersofthesolvent,suchasboilingpoint,viscosity,surfacetension,solubility,density,
andspecificgravityarealsorelevantfortheprintingprocess.Themostcriticalinkistheonefortheseparator
becauseofitsneedofhighionicconductivity,electrochemicalstability,andhighmechanicalstrength.The

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incorporationofionicliquidsinthepolymersolutionsispromisingtodevelopmoreenvironmentallyfriendly
batteryseparatorswithhighionicconductivityatroomtemperatureandwiderelectrochemicalwindows.
Anotherchallengeistodevelopfullyprintedbatteries,thatis,layerbylayer,inwhichthecompatibilityofinks
foreachcomponentisessential.Ideally,aprintedbatteryshouldbeflexibleandbasedonecofriendly
materials(Figure17).

Figure17.
Openinfigureviewer
Summaryoftheprintedbatteryresearch.
Finally,knowingthepotentialofprintingtechnologies,newarchitecturesofdevicesshouldbeenvisagedto
obtainprintedbatterywithhighdeliveredcapacityandvoltagesuitableforspecificapplications.Thenewinks
developedshouldallowthescalabilityofthesematerialsforlargescaleprintingtechnologies.Themostused
printingtechnologiesinprintedbatteriesarescreenandsprayprintingwhentakingintoaccountthescalability
forindustrialprocesses.Inkjetprintingisaverypromisingtechniqueforbatteryprintingbecauseofthelow
materialwasteproducedandpositioningofspecificdepositionpointsfordropletsandlowviscositycompared
toothertechniques.
Despitethesechallenges,itcanbeconcludedthatprintedbatteries,throughtheuseofnewinksanddevices
withtailoredproperties,enableanewgenerationofportableandflexibleapplications.

Listofsymbolsandabbreviations
BMIM+TF
1butyl3methylimidazoliumtrifluoromethanesulfonate
DEC
diethylcarbonate
DEM
1,2dimethoxyethane
DMC
dimethylcarbonate
DOL
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1,3dioxolane
EC
ethylenecarbonate
ETPTA
ethoxylatedtrimethylolpropanetriacrylate
GPE
gelpolymerelectrolyte
LiPON
Lithiumphosphorousoxynitride
LLZONb
NbdopedLi 7 La 3 Zr 2 O 12
LiTFSi
Lithiumbistrifluoromethanesulfonimide
MoOxSy
Molybdenumoxysulfide
PVDFHFP
poly(vinylidenefluoride co hexafluoropropylene)
PAA
polyacrylicacid
PC
propylenecarbonate
PDMS
polydimethylsiloxane
PE
polyethylene
PEDOT
poly(3,4ethylenedioxythiophene)
PEG
polyethyleneglycol
PEI
polyethyleneimine
PEO
polyethyleneoxide
PMMA
poly(methylmethacrylate)
PP
polypropylene
PS
polystyrene
Zn+Tf
Zinctrifluoromethanesulfonate

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Acknowledgements
ThisworkisfundedbyFEDERfundsthroughtheProgramaOperacionalFactoresdeCompetitividade
COMPETEandbynationalfundsfromFCTFundaoparaaCinciaeaTecnologia,intheframeworkof
thestrategicprojectStrategicProjectsPESTC/FIS/UI607/2014andgrantSFRH/BPD/112547/2015(C.M.C.).
TheauthorsarethankfulforfundingfromMateproOptimizingMaterialsandProcesses,ref.NORTE070124
FEDER000037,cofundedbytheProgramaOperacionalRegionaldoNorte(ON.2ONovoNorte),under
theQuadrodeRefernciaEstratgicoNacional(QREN),throughtheFundoEuropeudeDesenvolvimento
Regional(FEDER).

BiographicalInformation
RicardoE.SousaisaPh.D.studentattheUniversityofMinho,DepartmentofPhysics.Priortohiscurrent
appointment,hespentsomeyearsworkinginthehightechindustryofsemiconductors.HereceivedhisM.Sc.
inPhysicsofAdvancedMaterialstoFunctionalMaterialsforMicroandNanotechnologyin2011andhisB.Sc.
inPhysicsin2006fromthePhysicsDepartmentattheUniversityofMinho.Hisresearchfocusesonpolymer
basedbatteriesfabricatedusingprintingtechnologies.

BiographicalInformation
CarlosM.CostagraduatedinPhysicsin2005andobtainedhisMastersdegreeinMaterialsEngineeringin
2007.In2014,hereceivedhisPh.D.inPhysicsfromtheScienceSchooloftheUniversityofMinho.The
currentfieldresearchisthedevelopmentelectroactivepolymerbasedporousmembranesandcathode
materialsforenergystorageapplications,thatis,lithiumionbatteries,sodiumionbatteries,andprinted
batteries

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BiographicalInformation
SenentxuLancerosMendezgraduatedinphysicsattheUniversityoftheBasqueCountry,Leioa,Spain.He
obtainedhisPh.D.degreeattheInstituteofPhysicsoftheJuliusMaximiliansUniversittWrzburg,Germany.
HewasResearchScholaratMontanaStateUniversity,Bozeman,MT,USA,PennsylvaniaStateUniversity,
USAandUniversityofPotsdam,Germany.SinceSeptember1998hehasbeenatthePhysicsDepartmentof
theUniversityofMinho,Portugal,whereheisassociateprofessor.Hisworkfocusesontheareaofpolymer
basedsmartmaterialsforsensorsandactuatorsandenergyandbiomedicalapplications.

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