ABriefIntroductiontoFuelCells Overview Afuelcellisanelectrochemicaldevicewhichcombinesafuelandanoxidant,typicallyoxygenfrom air,todeliverpower.Unlikeabattery,whichisclosed,afuelcellisopenonatleastoneside,theair sidebeinginvariablyopen.Likeabattery,individualcellscanbecombinedtogethertoformastack andhencedeliveringwhateverpowerisneededforthegivenapplication.Thefuelatpointofuseis commonlyhydrogen,butcanbeahydrocarbonorotherhydrogencontainingfuel,decomposedby heat,catalytically,orsimplystoredatpressure.Thefuelcellstackcombinesfuelandairtoform waterandpotentiallyCO2,cleanlyandefficiently.Whilesimilartoabattery,afuelcellsystemisfar morecomplex,involvingpumps,blowers,condensers,etc.,(collectivelydenotedasthebalanceof plant)whichimpactoncostandreliability. Fuelcellscanbothcomplementandcompetewithbatteriesforportablepowersystems.Atthevery smallscale(AAADcell),batteriesarehardtobeat,especiallyforshorttimesastherequirementfor theelectrochemicalconverterandassociatedbalanceofplanttakesupalargeshareofthepower sourceinventory.

Asthepowerlevelandtimerequirementincreases,thedecouplingoffueland electrochemicalconverterbecomesincreasinglyadvantageous,andismanifestinlightweightpower sourceswithreducedrechargetimescomparedtobatteries.Theabilitytoinstantlyswapoutthe fuelratherthanwaitforrechargeisparticularlyadvantageousformostportableapplications. Whilefuelcellsofferadvantagesoverbatteries,theyalsobringissues,atleastatthepresentstateof development.Someareintrinsic(suchastheneedtobreatheair)andothersarebeingcontinuously improved(suchasstartupfromsubzerotemperatures,stackandcomponentlifetimes,cost),while yetmorearespecificonlytocertainstacktypes(suchasintoleranceofatmosphericCO2byalkaline fuelcellstacks,ororientationdependencefordirectmethanolfuelcells). Astheyimprove,fuelcellswillcertainlyreplacebatteriesinsomeapplicationsbutsealedcellswill continuetobeneededforstartup,forrapidloadfollowingandforshorttermpeaks,wherethe batteryischeaperthanalargerstack.ForcompanieslikeABSL,fuelcellsoffernewopportunities, thePPSProgrammebeingoneexampleofanexploitationpath,forsoldierpowerandbeyond. FuelCellDrivers Comparedtoaheatengine,whichisefficiencylimitedaccordingtotheCarnotcycle,fuelcellsoffer thepotentialforhighefficiencypowergeneration,inturnyieldingreduceddependenceonfossil fuelsandlowergreenhouseandlocalemissions.Fuelcellsofferlowernoisecomparedtoengines, butnotzeronoiselikeabattery,areapplicabletoawiderangeofpoweroutputsandapplication areasandaresometimestoutedasdeliveringalowlifetimecost,butthispotentialhasyettobe realised.Instationarygeneration,fuelcellsarebeingconsideredfordistributedgenerationand combinedheatandpower,fedfromexistingnaturalgasdistributionnetworks.Intransportation, fuelcellsareperceivedultimatelyasofferinghighreliability(fewermovingparts),lowmaintenance, goodaccelerationandlownoise,whileforportablepowerincreasedspecificenergyandlonger usefullifetimesareofferedcomparedtobatteries.Hence,fuelcellshavebeenconsideredbysome asapanacea,butthisneglectstheconsiderabledevelopmentassociatedwithexistingandemergent alternatives,suchasbatteries,engines,turbines,thermoelectricgenerators,etc,over100years.

FuelCellTypes Avarietyoffuelcellsexist,eachwiththeirownadvantages,challengesandspecificdesignfeatures. Broadly,fuelcellscanbedividedintolowtemperaturefuelcellsystems(PEM,DMFC,AFC)andhigh temperaturesystems(MCFC,SOFC).Thedesignationscomefromtheelectrolyteemployed,as showninFigure1below.

Figure1MainFuelCellTypes Theabilityforinstantrecharge,coupledbyuserfrustrationinbatterylifetimeandrechargetimes, thehighcostofbatteriesandmarketpullforalternatives,allfavourfuelcells.Batteriestypically operatewith90%efficiencyoverawiderangeofconditions,whilefuelcellsoperatewithreasonable efficiency(4065%)overanarrowerrangeofconditions.Asthefuelcellsystemoperatesatthe lowerendoftherequiredpowerrange,theefficiencydropsoffmarkedlyasthebalanceofplant consumesrelativelymorepower.Forthisreason,andtoprovideimmediatestartupand instantaneousloadfollowing,fuelcellsystemsarecommonlyhybridizedwithbatteries.Theneed forhybridizationislessacuteforpowersourcesoperatingatcontinuousratedpoweroutputs. Forportable(<1kW)powersources,thePEM,DMFCandSOFChaveemergedasthemost appropriateanddominantofferings,withtheAFC,MCFCandlargerscaleSOFCsbeingappliedto stationarygeneration.Avarietyoffactorsinfluencethestackfootprint,efficiencyandfavoured applicationarea,asdescribedinthefollowingtables.Atsmallscale,thePEMandDMFC approximateinsizeatsystemlevelforagivenpoweroutput,thelargerDMFCstackoffsettingthe needforareformertoconvertthemethanolfeedintothehydrogenneededbythePEMstack.The hightemperaturePEMvariant(asutilizedbyUltraCell)isparticularlyadvantageous,asitremoves theneedforCOcleanuprequiredforlowertemperaturePEMvariants,andreducesthepinchgap betweenreformerandstack.

MainFuelCellTypes1 Type PolymerElectrolyte Membrane(PEMFC) Hightemperaturevariant (egPEMEAS) DirectMethanol(DMFC) 30% Efficiency 40%/80%with cogeneration OperatingTemp(C) 80110 (Nafion) 160180 5090 Use Transportationcars,buses,boats,trains,scooters,bikes Residentialhouseholdelectricalpowerneeds Portablelaptopcomputers,cellphones,medicalequipment Militarynightvision,communications,computingdevices Portablecellphones,laptopcomputers,vacuumcleaners,highway roadsigns NASAspaceprogramspacevehicles Premiumpowerbanks,hospitals,basepower Landfill/wastewatertreatmentfacilitiestogeneratepowerfrom methanegas SolidOxide(SOFC) 55%/85% 8501000 Commercialutilitypowerplants,airportterminals,publicand commercialofficebuildings,hotels,hospitals Militaryportable Transportation APUs MoltenCarbonate(MCFC) 55%/85% 550700 Commercialutilitypowerplants,airportterminals,schools,office buildings,hotels,hospitals

Alkaline(AFC) PhosphoricAcid(PAFC)

60%/80% 40%/80%

70200 150210

Others:ITFC,RFC,DBFC,DAFC,FormicAcidFC,MetalOxygen

MainFuelCellTypes2 Type BasicChemistry CellVoltage PowerDensityat cell(W/cm2)* 0.6 Notes

Polymer ThinplasticsheetpermeabletoH+s,coatedonbothsides Electrolyte withPtcatalystsupportedonsheetofcarbonnanoparticles Membrane Pt/RuAnode:H22H++2e (PEMFC) Cathode:O2+2H++2e H2O Direct Methanol (DMFC) ThinplasticsheetpermeabletoH+s,coatedonbothsides withunsupportedPtcatalystathigherloadingsthanPEM Pt/RuAnode:CH3OH+H2OCO2+6H++6e Cathode:3/2O2+6H++6e3H2O

0.5(pureH2)

Highpowerdensity (power/weight) Quickstartup.Scalable. LowCOtolerance(ppm)

0.5(0.75M)

0.2

Moderatepowerdensity (power/weight,especiallywhen fuelstoreisincluded) Highactivationenergyofboththe anodeandcathodereactionsyield onlymodestefficiency

Alkaline (AFC)

ConcentratedKOH(3585wt%)inasbestosmatrix, requirespureH2stream.Cocatalyst Anode:H2+2OH2H2O+e Cathode:O2+H2O+2e2OH

0.8

0.16

LongusedbyNASAinspace. Cheap CO2poison:CO2+KOHproduces K2CO3cloggingelectrolyte Significantpressuredifferential requiredacrossmembrane

MainFuelCellTypes3 Phosphoric ConcentratedH3PO4inSiCmatrix, Acid(PAFC) highloadingPtelectrocatalyst(costly) Anode:H22H++2e Cathode:O2+2H++2eH2O 0.62 0.2 Formanyyears,theonlytruly commercialstack Upto100%concentratedH3PO4in SiCmatrix,Ptelectrocatalyst (expensive).PBIisavariant, utilizingapolymericcarrier 0.66 0.13 0.3morerecent (0.66) Variousgeometries,commonest aretubularandplanardiscs,can alsohavemixedreactantfeedif anodeandcathodeareonsame sideofelectrolyte.Scalable.High efficiency Sealingandthermalshockissues Slowstartup(hotstack) 0.78 0.13 Highfuel(LHV)topowerefficiency Tendstobeatlargescale(>500 kW) Nicknamedselfdigestingfuelcell

SolidOxide 8mol%Y2O3stabilizedZrO2electrolyte,NiZrO2anode, (SOFC) SrdopedLaMnO3cathode Anode:H2+O2H2O+2e Anode:CO+O2CO2+2e Anode:CH4+4O22H2O+CO2+8e Cathode:O2+2eO

2

Molten Carbonate (MCFC)

Mixtureofmoltenalkalicarbonatesinceramicmatrixof LiAlO2 Anode:H2+CO32H2O+CO2+2e Anode:CO+CO322CO2+2e Cathode:O2+CO2+2eCO32 Ni(anode)andlithiatedNiO(cathode)

ChallengesFacingPortableFuelCellStackDesigns PolymerElectrolyte(PEM) Cellssufferfromvoltagedegradationwithtime Pinholeleaksforminseparatormaterials/ion exchangemembranes Industrystandardionexchangemembraneslike NAFION(Dupont)andPRIMEA(GORE)have limitedlives<10,000hrs Hydrationofmembranesiscomplicated HightemperaturemembranessuchasPEMEAS polybenzimidazole(3M)haveevenmorelimited lifetimes<4,000hrsinpracticaluse Costofmachiningbipolarplates,ruggednessand weightofbipolarplates Gasketsfail Optimizationofcurrentcollection Electrocatalystsaredeactivatedbyfuel impurities,inparticularcarbonmonoxide,sulfur andphosphoruscompoundsreduceperformance DirectMethanol(DMFC) Methanolcrossover,reducingefficiency Weightandvolumeofdilutemethanolstore, recoveryofwaterathigher(>45C)ambient temperature Overallsystemenergydensity Lowpowerdensityofstack Managementofwasteheatandwater Orientationindependence(CO2bubbling) Anodecatalystcost SolidOxide(SOFC) Celldevelopment Lowtemperaturecathodes Sulfur/redoxtolerantanodes Materialscost

Stackbuilding Planarseals Ohmiccontact Brittleceramics Manufacturingcost

Stackoperation Slowstartup/cooldown Brokencells Thermalgradientsandsignificantheat lossesforsmallstacksformicropower Degradationcorrosion,interaction, instability Cokingfromheavyfuels

HydrogenStorage Hydrogenhasthehighestenergycontentbymassofanyknownfuel(nearlythreetimesthatof gasoline;120MJ/kgvs.44MJ/kgonanLHVbasis).Unfortunately,atambientconditions,hydrogen isagas,onlyliquefyingat20K,henceonavolumebasisthesituationisreversed(3MJ/litrecontent at5000psipressure;8MJ/litreforliquidhydrogenvs.32MJ/litreforgasoline).Thismakesphysical storageofH2bulky.Otherchallengingissuesincludeenergyefficiencyincreatingthehydrogen,cost andsafety.Figure2comparestheenergycontentofhydrogen,storedbyanumberofmeans,with commonroadtransportinfrastructureandalternativefuels.

Figure2Energycontentofstoredhydrogenandliquidtransportfuels (Jorrdanger,2002) Itisquiteclearlyapparentthathydrogen,evenwhencompressedto700bar,requiresafarlarger storagevesselforthesamegravimetriccontentasgasoline(petrol),diesel,liquefiednaturalgas (LNG)ormethanol.Moreover,thesituationiscompoundedbythevolumeoccupiedbythestorage vessel,especiallyforsmallerfuelcellsystems.Forpracticalapplication,thelargervolumerequired forhydrogenstorageresultsinshortertimesbetweenrefillsfortransportation,andshorteruseful periodsforportableuses,wherethefuelistypicallycontainedwithinreadilyreplaceablecartridges.

HydrogenStorageApproachesandCharacteristics (ModifiedfromWalker,1999)
Gaseous Hydrogen Simplest storage method but poor weight efficiency at 172 bar (1 wt%, assuming steel cylinder). Can increase wt% by an order of magnitude by use of composite carbon wound cylinder with an Al or polymeric inner liner and use of higher pressures (700 bar) when in bulk, less so for small portable applications.. Requires low temperature, well-insulated container & vent for boil off; complex & dormancy issues. Efficient on weight and volume basis, inefficient in terms of energy consumption on liquefaction. 50-100 m diam. spheres with high heat and high pressure. Upon cooling, H2 trapped until heated again. Theoretically, can store up to 40 wt% H2. In research stage, technical and cost difficulties remain. Force hydrogen into interior space under high temperature and pressure. Hydrogen trapped upon cooling. Release hydrogen with heat. Small amount of H2 stored based on weight (0.08%). High surface area material (carbon) is used to store hydrogen at modest pressure and low temperature (150 to 77 K). Good system on weight (7 wt% storage) and volume basis at large scale. Complex. Graphite nanofibres hydrogen trapped between planes of graphite nanofibres. Up to 50 wt% H2 storage (claimed) at high pressure; 4-7 wt% appears more credible. H2 released at low pressure. Carbon nanotubes hydrogen trapped in tubes. Poor kinetics and costly; claims dubious. Probable capacity is 1.5 wt% at room temp., and similar levels to activated carbon at lower temps. Carbon fullerenes store up to 6 wt%, but high temps. needed to release hydrogen expensive.

Liquid Hydrogen

Glass Microspheres

Zeolites

Cryoadsorbed Hydrogen

Carbon Sorption at Room Temperature

Reversible Metal Hydrides

Reversible Aluminium Hydrates (Alanates) Hydrolysis of Non-Reversible Chemical Hydrides Organosilanes Thermolysis of Chemical Hydrides Short Chain Hydrocarbon Gases, Gasoline and Diesel Hydrogenated Organic Liquid Catalytic Oxidation of Hydrocarbons

Hydrogen reversibly adsorbed by metal alloys at low temperature and released by heating. Good volumetrically but heavy & costly. Wide variety of alloys & preparative methods have been studied. Mg alloys require high temperature. FeTi alloys inexpensive but difficult to activate and susceptible to poisoning. LaNi5 alloys easier to activate, resists poisoning, but poor cycling stability. Decomposition of metal aluminium hydrides. Capacity limited to chemical composition of hydrides. Issues of achieving theoretical capacities, kinetics, cycle life and tolerance to impurities. Metal hydrides (e.g., LiH, NaBH4, LiAlH4) store high amount of hydrogen based on weight, react with water to release H2. Half of released hydrogen comes from the water. Kinetics inhibited by high pH and insoluble reaction products. Start-up and intermittent use issues. Ethenyl, ethynyl, & phenyl silanes store 6-10 wt % H2. React with water & catalyst to produce H2. Stabilize hydride with halide salt and polymer binder; ignite with high temperature. Reaction is highly exothermic and cannot readily be stopped.

y h P

l a c si

t S

a r o

ge

Steam reforming yields highest conversion of any reformer approach. Fuel must be desulphurised. Heavy hydrocarbons use partial oxidation to produce H2 and CO, then CO water-gas shifted to H2 and CO2. Reforming involves high temperatures. Systems are large, heavy, and expensive. Hydrogenated unsaturated hydrocarbon, such as toluene to methylcyclohexane and hydrogen. Requires heat, noble catalyst, and lot of equipment. More applicable for large-scale storage. Methanol easy to store & transport, but DMFC cell voltage & current less than that from direct H2 due to crossover to cathode; CO by-product poisons the anode catalyst. Trimethoxymethane higher BP and lower toxicity than methanol; complete oxidation with methanol as an intermediate. Ammonia oxidized at high temperature to nitrogen and water. Toxicity and handling issues. Hydrazine (N2H4) decomposes easily to hydrogen and nitrogen but is toxic and expensive. Bacteria or immobilized enzymes can convert fuel into useful gases or liquids. Complex controls needed & small amount of H2 produced. Enzymes can also directly produce electrons but at very small currents.

l a c i m e h C

t S

r o

g a

Biochemical

FuelProcessing Thelimitationsinefficientlystoringhydrogenhasledtosignificanteffortsinforminghydrogenfrom infrastructurefuels(propane,gasolineanddiesel)forcommercialmarketsorlogisticfuels(suchas JP8)formilitarymarkets.Thecomplexityofconversionisdependentonthenatureofthefeed (dieselbeingmoredifficultthanpropane)andthestacktype,withhighertemperaturefuelcells beingtoleranttoCO,forexample.Figure3illustratesthegenericstepsinfuelconversion.

Figure3FuelCellProcessingStepsforDifferentFuelCellSystems(Steele,1999) Ascanbeseen,moreprocessingstepsareneededforthePEMFCthanotherfuelcelltypes.The greatercomplexityandassociatedcostofPEMfuelprocessingmustbebalancedagainstthelonger startuptimeandexactingmaterialsrequirementsoftheSOFC.Thefuelprocessorsneededforthe PEMFCmustbeoflowcost,possessassmallafootprintaspossible,andofferfaststartupandgood loadfollowingwithoverallunitdurabilitybetween2,000hoursminimumforportableapplications toasmanyas40,000hourstocompetewithembeddedgeneration.Thisisfarfromeasy. WhileFigure3showsthegenericstepsinfuelprocessing,thereareanumberofvariationspossible withintheindividualstepsandbetweenthem,eachwiththeirspecifictradeoffs.Invariably,aliquid fuelneedstobevaporised.Thehydrocarbonvapourcantheneitherbereactedwithsteamto generateamixtureofH2andCO,orwithair.Theadvantageofthesteamreformingrouteisthata higherlevelofhydrogeniscreated.Thedisadvantageforaportableapplicationistheneedtocarry thewateralongwiththefuel.Whenreactingwithair,thepartialoxidationofthehydrocarbonis lessefficient,meaninglesshydrogenisformedpermoleofhydrocarbonfeedstock,andthisis exacerbatedbytheinherentdilutionoftheH2/COproductbynitrogen.Athirdoptionistocombine thetwoprocesses,theendothermicsteamreformingreactionbeingdrivenbytheheatliberated fromthepartialoxidation,thesocalledautothermalroute.

Irrespectiveoftheprimaryreformingroute,theproducthydrogenneedstobestrippedofCOfor thePEM.Inhighvolumehydrogenproductionplantsorlargestationaryfuelcellsystems,theCO canbeshiftedwithsteamtogeneratemoreH2andCO2.ForthePEM,theresidualCOalsoneedsto beremoved,traditionallybyselectiveoxidationoftheCOtoCO2.Suchcomplexandbulkyprocesses arepoorlysuitedtoportablefuelcellapplications.Oneworkaroundistouseahydrogenselective Pdalloyseparator.Anotheristousemethanolasafeedstock,asutilizedintheUltraCellXX25.A furtherapproachistodirectthefuelprocessorproducttoaSOFC,whichcanutilizetheCOasafuel. Thislatterrouteisparticularlyappropriatetoheavierfuels,suchaspropane,keroseneanddiesel. ThedisadvantageofthisapproachisthatthedurabilityofsmallSOFCsystems(typically1000hrs) currentlylagbehindPEMfuelcells(typicallyupto5000hrs). Afinalproblemforprocessingofheavierfuelsisthattheycommonlycontain50ppmormoreof sulfur,whichimpairsfuelcellperformance.Thesulfurcanberemovedbyadsorption,butwithpoor efficiencyofcaptureyieldinglarge,unwieldytraps,orthefuelcellcanbedesignedwithsulfur toleranceinmind.Examplesincludesulfurtolerantanodematerials,ortheliquidtinanodeconcept utilizedbyCellTech.ThepresenceoflargelevelsofsulfurinJP8(upto0.3%)ispresentlyamajor impedimenttodeploymentofpracticalportablefuelcellsutilizingthisfuelinthemilitaryspace. SystemCostandDurability Thecostsoffuelcellsystemscanbesplitroughlythreewaysbetweenthefrontendfuelprocessing, stackandthebalanceofplant(controls,pumps,blowers,etc).Costreductionsandimprovementsin durabilityareneededinallthreeareasatsubsystemandcomponentlevel.Furthermore,hydrogen storageandextractionneedtobeasefficientaspossibleifthepresumptivebenefitsoffuelcellsare toberealised.Atasystemlevel,portablefuelcellstypicallyare20%ormoreefficient,dependent onplatformandoutput,whichtranslatesintofueldemandandrequiredfuelcartridgesize. FuelCellsandBatteries Therequirementforafuelcellconvertercoupledwithafuelcartridge,neitherbythemselves providingpower,meanthatbatteriesremainsuitedtolowpowerdemandsovershorttimescales (typicallylessthan12hours).Moreover,batteriesareideallysuitedtorapidresponse,andare cheaperwhenusedasahybridpowersourcetomeetpeaks.Fuelcellsareairbreathing,making waterproofinganddustandsandresistancedifficult.Hence,whilefuelcellswillcertainlyhavearole infuturepower,batterieswillbebothcompetedwithandcomplementedbyfuelcells.Therateof penetrationwillbedependentontheprogressincostreductionandinenhancingdurability. References EJordanger,SMllerHolst,OMaurstadandDABrevik,Hydrogensomenigibrer:Energiog utslippsregnskapforutvalgteenergikjeder,SINTEF,TRA5713,October2002, www.sft.no/nyheter/dokumenter/hydrogen_energibaerer.pdf BCHSteele,Runningonnaturalgas,Nature,1999,400,619620 CWWalker,RJiangandDChu,Anoverviewofhydrogengenerationandstorageforlow temperaturePEMfuelcells,ARLTR2091,November1999,handle.dtic.mil/100.2/ADA372504

FurtherInformation www.udomi.com Marketanalyses(outdated)forallfuelcelltypes Shortsurveys,marketreports,techsummaries Fuelcellreferencecharts(micro,portable,transport,etc.) Monthlyfuelcellreview,Portablefuelcellmarketstudy Monthlyhydrogenandfuelcellreviews Annualfuelcellseminar,onlineproceedings

www.fuelcelltoday.com www.fuelcells.org www.hyweb.de

www.fuelcellseminar.com StuartJones ABSLPowerSolutionsLtd August2008