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Electrochemistry III: Dye Sensitized Solar Cell Prelab Questions

1. Watchthevideobelowtogainanunderstandingoftheinnerworkingsandchemistryofa dyesensitizedsolarcell.HowistheexperimentyouwillbedoingdifferentfromtheDSSC showninthisvideo? http://www.youtube.com/watch?v=3KRHJSOgzcw 2. WatchthevideobelowtoseehowaDSSCisconstructed.Theprocessshownisverysimilar towhatyouareconstructing. http://www.youtube.com/watch?v=17SsOKEN5dE 3. Howmightsolarcellperformancebeaffectedifthepigmentwasextractedinan acidic/basicsolvent?(Hint:howmightthepropertiesofthepigmentchange?) 4. Whatvariablesdoyouexpecttohaveaneffectonsolarcellperformanceandwhy? 5. Thecoatedglassisexpensiveanddifficulttomake.Whatothermaterialscouldbeusedin itsplace?Whatpropertieswouldthesematerialsneed? 6. Whichwaydotheelectronsflow?Howwouldyoudefinethecathodeandtheanode? DescribeintwosentencestheflowofelectronsintheDSSC.

ElectrochemistryPartIII:SolarCells

Overview

Inthepastdecade,alternativeenergysourceshavegainedtractionforpracticaluseandhave beenanincreasinglyimportantfocusofresearch.Solarcellsarebecomingamorecommon andusefulsourceofenergy.Youhaveprobablyseenmanyoftheseintheformofsolar panels,whicharesimplyacollectionorarrayofsolarcells.Traditionalsolarcellsabsorblight usingasemiconductorplate,buttherebutinthisexperiment,youwillbeconstructingadye sensitizedsolarcellthatutilizesanorganicalternative.Dyesensitizedsolarcellusea photosensitivepigmentfoundinmanyberriesandleavestocapturelight.Iftimepermits, youwillexploreseveraldifferentdyesources.

LearningGoals

Applyfundamentalelectrochemistryprinciplestopracticalapplications Gaininsightintothegeneralworkingsofsolarcells Understandthechemicalandphysicalprocessesthatproduceacurrentinsolarcells Explorethefactorsthataffecttheperformanceofthesecells Learnaboutdifferenttypesofsolarcellsandtheirpotentialasalternativeenergysources

AdvancedApplicationsofElectrochemistry
SolarCells

Withgrowingconcernoverthelimitsoffossilfuelbasedenergy,greateffortshavebeenmade tofindrenewablesourcesofenergy.Oneofthesesourcesissolarenergy,whichutilizesthe energystoredinlightbyultimatelyconvertingittoanelectricalsignal.Thisprocessiscarried outbysolarcells,alsoknownasphotovoltaicorphotoelectriccells.Whiletraditionalsolarcells absorbenergyusingasemiconductorplate,thereisactiveresearchonorganicalternatives.

Solarorphotovoltaiccells,incontrasttofuelandgalvaniccells,operateontheprincipleof excitingelectronsfromamaterialthroughacircuitandthenhavingtheelectronsreturnbackto theoriginalmaterial.Traditionalsolarcellsareconstructedwithlayersofsemiconductors,like silicon,imbeddedwithtraceamountsofotherelements.Puresiliconisasemiconductorwith fourbondstoneighboringsiliconatomsandafulloctetforeachsiliconatom.Acrystalofsilicon withatraceamountofagroupIIImetallikeboronorgalliumwillhavenetfewerelectronsthan puresiliconitself.Thecrystalisconsideredptypeorpositivetypeindicatingthatthereisa+1 formalchargeonthegallium.Similarly,siliconcanalsobecrystallizedwithtraceamountsofa GroupVelementlikephosphorous.Thismakesanntypeornegativesemiconductorwithan extraelectronfora1charge(Figure1).

Figure1:nTypeandptypesilicon.pTypehasnetfewerelectronsandntypehasnetmoreelectronsthanpure silicon.
AccessedAugust30,2013fromhttp://www.redarc.com.au/solar/about/solarpanels/

Allthesetraceelementsmakeitmuch easiertoexciteelectronsinthe semiconductors.Inpnsolarcells,one semiconductorlayercanloseanelectron ifthematerialissuppliedwithphotonsof highenoughenergytoejecttheelectron. Thesecondlayercanacceptthiselectron. Theelectronistravelingfromabound stateinthevalencebandofthematerial intothemoreunboundstateofthe conductionband.Whentheelectronis tryingtoreachtheacceptorlayer,itcan beconductedthroughacircuit(Figure2). However,someelectronsdonotdothis andgodirectlytothenearest+1hole. Thisisoneofthemajorreasonsthatsolar cellshavereducedefficiency,sincenot everyphotonabsorbedresultsinan ejectedelectronpassingthroughthe circuit. Figure2:Electronflowinageneralsolarcell.Ntypesiliconhasfree electrons.Ptypesiliconhasfreeholestheabsenceofelectrons. Aswithfuelcells,therearemany Whenntypeandptypesiliconcomeintocontact,anelectricfield formswithinthecell. differentdesignsofsolarcells.Recently therehasbeeninterestinmimicking AccessedJuly30,2013fromhttp://www.solarpower2day.net/images/7.jpg naturalprocesseslikephotosynthesisin ordertomoreefficientlyharnessthe sunsenergy.Lightfromthesuncanfreeelectronstomovethroughthecircuitsandgenerate electricity.Thesunemitslightofavarietyofwavelengthsrangingacrosstheentire electromagneticspectrum.However,somewavelengthsaremoreprevalentthanothersare. Thesunsspectrumpeaksinthevisiblerange,whichindicateswhyweareadaptedtosee visiblelight.Earthsatmosphereabsorbsalargeportionoftheincomingradiation,withcertain moleculesandelementsabsorbingcertainwavelengthsoflight.Ozone,inparticular,absorbs mostoftheincomingultravioletlight.Thelightthatmakesitthroughtheatmospherereaches theearthsurfaceandeitherreflectsofftheearth,orpermeatesthroughtheearthsenergy cycle.Solarcellsharnessthisincominglight,concentratingonthemoreprevalentvisible spectra. Youwillbeconstructingadyesensitizedsolarcell(DSSC)thatwasoriginallydevelopedbyBrian O'ReganandMichaelGrtzelhereatUCBerkeleyin1988.DSSCsareinspiredbyphotosynthesis andutilizebothsemiconductorsandnaturalfooddyesfromberries,whichassistinthe absorptionoflightandejectionofelectronsintothecircuit.Thesedeviceshavetheadvantage ofseparatingtheprocessesofchargegenerationandchargetransportfromeachother.This meansthatitiseasiertodirectthefreeelectronstothecircuitofyourchoosing.Theberryjuice isthelightabsorbingspeciesinthecell.Whentheberryjuiceabsorbslight,anelectron
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becomesexcitedandcan beejectedfromthedye moleculesintheberry juice.Thesemiconductor thenconductsthis electronthroughthe circuit,rejoiningan electronacceptorspecies ontheothersideofthe solarcell.IntheDSSC module,theelectron acceptorhalfcellyouwill buildistheII3redox couple.Thesandwiching ofntypeandptype semiconductorsina regularsolarcellcreates anelectricfieldatthe interface.Becauseofthis attraction,thefreed electronssometimes proceeddirectlytoan electronholeandbypass thedesiredcircuit. TheDSSCyouwillbe synthesizingemploys anthocyanintofacilitate Figure3:(Top)Diagramshowingthevariouslayerofadyesensitizedfuelcell.(Bottom) energyabsorption. EnergylevelofDSSC.Whenthesensitizingdyeabsorbsaphoton,theelectronisinjected Anthocyaninisanatural intotheconductionbandofthetitaniumdioxideandtravelstothefrontelectrode.The oxidizeddyeisreducedbytheelectrolyte,whichisregeneratedatthecounter pigmentfoundinmany electrodetocompletethecircuit. darklycoloredplants, includingblackberries,raspberries,pomegranates,pansies,blackrice,andbluecorn.The specifichue,however,dependsonthepHofthesolution.Therearemanysubtypesof anthocyanin,butallcanbeusedforthepurposeofthisexperiment.Theanthocyaninisexcited bylightenteringthecell.Theexcitedelectronstransfertoasemiconductivelayeroftitanium dioxide,whichpassesthemalongtoaconductivesurface(thecoatedglassplatesforthis experiment).Thecounterelectrodeconsistsofanoscillatingsystemofiodideandtriiodideions catalyzedbyalayerofgraphite(Error!Referencesourcenotfound.).

Sources:
Smestad,G.P.;Gratzel,M.JournalofChemicalEducation1998,75,752.

PrelabQuestions
1. Watchthevideobelowtogainanunderstandingoftheinnerworkingsandchemistryofa dyesensitizedsolarcell.HowistheexperimentyouwillbedoingdifferentfromtheDSSC showninthisvideo? http://www.youtube.com/watch?v=3KRHJSOgzcw 2. WatchthevideobelowtoseehowaDSSCisconstructed.Theprocessshownisverysimilar towhatyouareconstructing. http://www.youtube.com/watch?v=17SsOKEN5dE 3. Howmightsolarcellperformancebeaffectedifthepigmentwasextractedinan acidic/basicsolvent?(Hint:howmightthepropertiesofthepigmentchange?) 4. Whatvariablesdoyouexpecttohaveaneffectonsolarcellperformanceandwhy? 5. Thecoatedglassisexpensiveanddifficulttomake.Whatothermaterialscouldbeusedin itsplace?Whatpropertieswouldthesematerialsneed? 6. Whichwaydotheelectronsflow?Howwouldyoudefinethecathodeandtheanode? DescribeintwosentencestheflowofelectronsintheDSSC.

Overview of DSSC construction:

Procedure:

Materials
Equipment: Hotplate Two2.52.5cmindiumtinoxide(ITO)plates Multimeter Bananaplugs Maskingtape Glassrod Threeplastictransferpipettes Smallbeakers(~5) Kimwipes Alligatorclips Binderclips Lightsource Filterpaper Bunsenburner Ironring Wiregauze

Chemicals: 23frozenblackberries, blueberries,orraspberries 1mL,0.6g/mLTiO2in10%acetic acid 5mL,95%ethanolsolution Graphitestick Iodinesolution(0.5MKI,0.05MI2) inethyleneglycol

PartI:Preparingtheanode

PreparetheglassplatewithTiO2
1. Obtainapproximately1mLof0.6g/mL
titaniumdioxidein10%aceticacidandtwo 2.5cm2.5cmindiumtinoxide(ITO)coated glassplates.

AnnealingTiO2
1. Useamultimeteronsetting(2K)inohms (Figure4)andmeasuretheresistanceon eachside.Thesidethatgivesyouazero valueofresistanceisconductive.Cover theedgesoftheconductivesideofone oftheplateswithfourstripsoftape,as showninFigure5.Eachpieceoftape shouldcover45mmoftheplate.Ensure thatthetapeisverytightlysecuredto preventtitaniumdioxidefromleaking underneath. 2. TheridgesofthetapewillformashallowmoldfortheTiO2tobedepositedinto.Itis essentialthatthetapedarearemainsuncoated,sincethisiswhereyouwillattachthe voltmeter. 3. Apply23dropswithaplastictransferpipetteofTiO2solution/pastetothecenterofthe tapedplate. 4. SpreadtheTiO2evenlyovertheuntapedportionoftheglassplatebyrollingoverthe solutionwiththesideofaglassstirringrod.Makesuretospreadthetitaniumevenlyso thatitwillcoattheentirecenteroftheplate.Ifanyofthesolutiongetsunderthetape, thetitaniumdioxidecanbewashedoffwithwaterintoawastebeakerandtheplating canberepeatedwiththesameplateifnecessary. 5. Letyourplatedryfor12minutesandthen carefullyremovethetape. 6. ToannealtheTiO2totheplate,youwillneed toheatit.Attachanironringtoaringstand andplacewiregauzeontopofthering.Place theBunsenburnerunderneaththewire gauzeandadjusttheflamesothatitisnot touchingtheplate.Suspendtheplate (titaniumdioxidesideup)overtheBunsen
Switch setting

Dial setting

Figure4:Multimetersettingsformeasuringresistance

Figure5:Covertheconductivesideoftheplate withfourstripsoftape.

burnerflameonthewiregauzefor10minutes. 7. Usingtongs,carefullyremovetheplatefromtheflame.Cooltoroomtemperature(510 minutes).Whileyourplateiscooling,preparetheanthocyaninsolutionfromblackberry juice.

Preparingtheanthocyaninsolution
1. Obtain23frozenberries(blackberries,raspberries,orblueberries)andplacethemina 100mLbeaker. 2. Usingahotplateonalowsetting(<3),heattheblackberriesuntilyouobtainadarkly coloredjuice.Thisshouldtakeapproximately1015minutes.Usinggravityfiltration, straintheberrysolidsthroughafilterpapertogetberryjuice.Pressgentlyonthe berriestoextractthejuice.

Stainthetitaniumdioxidewithanthocyanin
1. Add34dropsoftheberryjuicetotheTiO2coatedplateusingaplasticpipette.Letthe platesitforapproximately10minutes.Checktomakesurethatthetitaniumdioxide layerisstained;itshouldnotbewhite.Ifitisstillwhite,addafewmoredropsof blackberryjuiceandletitsitfor5minutes. 2. Ifyouwouldlike,youcaninsteadimmersetheplateintheberryjuiceandletitsoak TiO2sideupinthejuice.Makesuretorecordthetimeyoulettheplatesoakand compareyourfinalresultstoothergroupsthatlettheirplatessoakformoreorless time.Howmightthestainingtimeoftheplatesaffectyoursolarcell? 3. Tiltyourplateata45angleoverawastebeakeranduseaplasticpipettetogently washtheplatewithdistilledwater.StartaddingthewaterfromtheedgeoftheITO glass.DonotdirectlyapplythewatertotheTiO2layer,asthiswillcausethefreshly annealedlayertowashoff.Obtainapproximately5mLof95%ethanolinasmallbeaker. Repeatthegentlewashwiththe95%ethanol.Continuewashinguntilthereareno chunksofberriesleft.DrytheplatecarefullybygentlyblottingwithaKimWipe.Your plateshouldremainstainedwithanthocyaninsbutnosolidsshouldbepresent.

PartII:Preparingthecathode

Preparethecounterelectrode

1. Identifytheconductivesideofyoursecondglassplateusingthesamemethodasnoted above. 2. Usingagraphiterod,thoroughlyandevenlycoattheconductivesideoftheplatewith graphite.Covertheglasswithalayerofgraphiteasifwritingwithapencil.Itisessential thatyoucompletelycoattheplatewithgraphiteforaccuratevoltagereadings.

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PartIII:AssemblingtheDSSC

1. Obtainabottleofstockiodinesolutioninethyleneglycol(0.5MKI,0.05MI2).Thestock bottlemustbesharedsoputitbackinthehoodimmediatelyafteruse.Iodine(KI electrolyte)solutionistoxic;makesuretowearglovesandbecarefulhandlingthe solution.CleanupanybenchtopareaorglasswarethattouchedKIelectrolytesolution.

2. PlacethegraphitecoatedplateontopoftheTiO2plate,graphitesidedown,withthe uncoatededgesslightlyoverhanginginbothdirections,asshowninFigure6.The uncoatededgesarewhereyouwilllaterattachtheelectrodes. 3. Cliptheplatestogetherwithbinderclips,asshowninFigure6. 4. Tiltthecellata45angleanduseadroppertoplacethreedrops(right,center,andleft) oftheKIelectrolytesolutioninthecreviceoftheTiO2coatednonoverlappinghanging edge,asshowninFig.6.Itisveryimportantthatyoudonotapplytoomuch electrolytesolution.Usethebinderclipstoworkthesolutionthroughthemiddleofthe platesothatallsurfacesarecovered.Dothisbyunhookingoneofthebinderclips,and alternatingthem,sothatthesolutioncanmovethroughthecell,asseenintheprelab video. 5. Besurethereisenoughroomontheedgestoattachanalligatorclips.
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6. Attachalligatorclipstoeachvoltmeterelectrode,andthenattachthealligatorclipsto thesidesoftheplates,asshowninFigure6.Theblackvoltmeterelectrodeshouldbe attachedtotheplatecoatedwithgraphite.Makesureneitherprobetouchesthe stainedTiO2.

Figure6:Assemblyofsolarcell.(Left)Assemblyoftwoplateswithoverhangingedges.(Center)ApplicationofKIelectrolyte solution.(Right)Attachmentofalligatorclipstosolarcell.

NOTE:ITISPOSSIBLETHATTHEKISOLUTIONWILLLEAKOUT.IFSO,WIPETHEEDGESOFTHESOLARCELLWITHAKIMWIPETO REMOVEALLOFTHEEXCESSELECTROLYTESOLUTION.THISISESSENTIALFORACCURATEVOLTAGEREADINGS.

1. Measurethevoltageusingthefollowing settings:DCcurrent,Volts(V)onthe2 dial,asshowninFigure7. 2. Shinealightontotheplates.Recordany changesinvoltage.Ifyoureceiveda constantnegativereading,checkthat yourblackvoltmeterelectrodeis connectedtothegraphitecoatedplate. 3. Measurethevoltageofthecellovertime. Recordreadingsuntilthevoltage plateaus.Thisshouldtakeapproximately 10minutes.

Switch setting

Dial setting

Figure7:Multimetersettingsformeasuringvoltage

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Cleanup
Washofftheplatesandbinderclipsthoroughlywithwaterintoawastecontainerinthehood. Returnthecleananddryplatestotheinstructor.Returnbinderclipsandallmaterialsbackto itsoriginalplace. Rinseallglasswareandequipmentthattouchedanysolutionusedforthislabanddisposeofall solutionsintothewastecontainerinthehood.

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Name_____________________________________GSI_______________________________ LabPartners___________________________________

Electrochemistry III: Dye Sensitized Solar Cell Postlab Questions

1. Whatdoesthetitaniumdioxidecoatingfacilitateinthisexperiment?Howwouldthe experimentworkifthecoatingdidnotcontainmetal? 2. Predicthowthedatawouldlookifthisexperimentwereconductedingrapefruitjuice instead.Whatwouldthedatabeinajuicethatisdarkerthanblackberries? 3. Whatisthepurposeofwashingtheplatewithwaterfollowedbyethanol?(Considering intermolecularforcesandbondingpropertiesofmoleculeswhywouldtheorderofthe rinsesbeimportant?) 4. Whatvoltagedidyoumeasurefromyoursolarcellinthelabsnaturallightsetting?What didyouobservewhenyoushinedtheincandescentlightontothecell? 5. Proposetwochangestothislabprocedurethatcouldbemadetoachievebetterdye sensitizedsolarcells.

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