燃料电池质子交换膜的最新发展

CHEMISTRYTHECHINESECHEM.SOC.,TAIPEIMarch.2004Vol.62,No.1,pp.123~138論料諸立類諸料來力力來不料不料率度ITIT料(mW)料(PEMFuelcell)料(DirectMethanolFuelCell)兩IT料年理不理念便利料料年來料料車更降力力車都見來不論力料流降料度料料料料了(PEM)料(Electrode)(BipolarPlate)料FuelStorage了料料---(PEM)年來離理量料(DMFC)料不行料不料路力124年六(1)(2)DMFCPEM度易離Proton不離裸烈DMFC料易PEM料流降(MethanolCrossover)DMFC率不PEM料良料1.料率料(crossover)2.率(10-2S/cm)3.4.度拉不裂5.料度不不6.良料不不不不料不不度料度量料料力類(Poly(perfluorosulfonicacid);PFSA)料了料1970年類NafionAsahiChemical料料離力良料料(Nafion)DMFC(Cross-Over)降DMFCCross-OverDMFC料3%5%量度不不度80流降了率Nafion(800~1000US$/m2)Nafion料料料料1.離(Ionomermembrane)2./(Organic-Inorganichybridmembrane)3./(Membranebasedonpolymerandoxo-acids).1.離(Ionomermembrane)Ionomer離類料離奈洞(Cluster)PercolatingNetwork()Ionomer奈洞離度離H3O+H5O2+奈洞來度聯度類量度烈Ionomer理料(1)(2)(3)(4)聯便CH3OH+H2O6H++6e-+CO23/2O2+6H++6e-3H2O年六1251.(PerfluorinatedPolymer)料(PEMFC)(PerfluoroSulfonicAcid,PFSA)PFSAPFSA列Table11AsashiGlassAsashiChemicalsDowChemicalTeflon了料Nafion料60,000PFSA狀度0.10S/cmPFSA了度度(90)度降不了PFSAPFSA(80)(100)度(i)PFSA(Thin,reinforcedPFSAmembrane)PFSAPEMFC理降料來說利料W.L.Gore2PTFEsheetPFSA洞洞microPTFEfibril(AsashiGlassCo)3polypropylene4expandedPTFE5Polysulfonemicroglassfiberfleece6來PFSA度降5~30m良度率度Table1CommericalPFSAMembranebyProducerTakeoYamaguchi,Journalofmembranescience214(2003)283.126年六Shim5利impregnatingNafionsolutionePTFE75%Nafion量度22mPEMFC0.4V流度2.65A/cm2量流Nafion量Stimming6polysulfonemicroglassfiberfleecesNafionPolysulfonefleece34%Nafion量度650m25度3.410-3S/cmMicroglassfiberfleece53%Nafion量度70m25度1.410-2S/cmH2/O2料PolysulfoneMicroglassfiberfleecePowerdensity2065mW/cm2Nafionsolution量度度離度度易裂類度度理Nafoin量(ii)(HygroscopicOxides)PFSA度度易度降來降路降DMFCPEMFC度力Watanabe71994年recastPFSANafionhygroscopicoxide(SiO2TiO2)量17wt%43wt%度Antonucci83wt%SiO2recastNafion145DMFC4.5atm(methanol-water)/5.5atm(air)力0.5V350mA/cm2PFSA降DMFCMiyake9,10利sol-gelNafion/silicasilica量量度降20wt%silica量Jung11Nafionresinmontmorillonite利meltintercalation降1253wt%montmorillonite0.4V流度290mA/cm2SiO2粒不粒了zirconiumphosphatesheteropolyacidsmetalhydrogensulfatePFSA來Bocarsly12Nafion/siliconoxide(zirconiumphosphateparticles)13050良度Yang13利(exchange-precipitationmethod)Nafion115in-situzirconiumphosphate150DMFC量度380mW/cm2260mW/cm2Staiti14(heteropolyacid)(phosphotungsticacid)(silicotungsticacid)silicaNafionrecast145DMFC量度400mW/cm2量度250mW/cm2Table2年來PFSAPFSA離奈粒(iii)Plasma-etchingandPalladium-Sputtering年來利PFSAWoo27了洞率利Plasmaetchingpalladium-sputteringNafion利降了洞路降Pu28Nafion115兩Pdfoil(25m)降了度降(iv)Nafion(Vehicle)H3O+H5O2+年六127CH3OH2+來Electro-osmoticdragNafionPBIGrottus()Electro-osmoticdrag零Hobson29screenprintingNafion117PBI10wt%MeOHMEA2M3.2MMeOHPowerdensity21.717.8mW/cm2Nafion117Hsing30類PVANafionPVA聯(selective;)降(2)(PartiallyfluorinatedPolymer)Scherer31-32利/(poly(tetrafluoro-ethylene-co-hexafluoropropylene)(FEP)poly(ethylene-alt-tetrafluoroethylene))-raystyrene/divinylbenezene狀PEMFCBallard33-34Poly(,,-trifluorostyrene)andcopolymers,,-trifluorostyreneRgroup,,-trifluorostyrene料不,,-trifluorostyrenePoly(,,-trifluorostyrene)Sundholm35利PVDFPSPS量PS度度理離類立量數兩數量降料DMFC度5.9210-2S/cm1.0810-6cm2/sNafionstyrene/divinylbenzenetertiaryC-H易不Table2SummaryofModificationofPFSAMembranesPolymermodifiersremarksrefNafionH3PO40.05S/cmat15015NafionPTA-aceticacidH2/O2cell,110,660mA/cm2at0.6V,1/1atm,humidifier50/5016NafionPTA-TBACH2/O2cell,120,700mA/cm2at0.6V,1/1atm,humidifier50/5016NafionSiO20.2S/cm,100,100%RH17NafionSiO2DMFC,145,4.5/5.5atm(air),350mA/cm2at0.5V8NafionSiO2/siloxaneH2/O2,130,3/3atm18AciplexSiO2/siloxaneH2/O2,130,3/3atm19NafionTeflon+PTAH2/O2cell,120,400mA/cm2at0.6V,1/1atm,humidifier90/8420NafionZrPDMFC,150,4/4atm,380mW/cm2(O2),260mW/cm2(air)13NafionZrPH2/O2cell,1.5A/cm2at0.45V,130°C,3atm21Nafiondi-isopropylphosphate0.4S/cmat2522NafionSiP-PMA/PWA0.005S/cmat23,fullyhydrated23NafionSiWA(+thiophene)fuelcelltestat8024NafionSiO2,PWA-SiO2,SiWA-SiO2140,3/4atm,DMFC,400mW/cm2(O2),250mW/cm2(air)25NafionPMoA+SiO20.3S‚cm-1at9026128年六(3)(HydrocarbonPolymer)PFSA料RikukawaSanui度不類不類PFSA便易裂度度利類都PFSA來奈()來度(lowwateractivities)PFSA(wateruptake)100%度PFSA量PFSA狀更Polyaromatic料更度度奈度(lowwateractivities)度不度度立不Arylene良度C-H度(435kJ/mol)力了度都利離來(i)硫SO3SO3/tri-ethyl-phosphate(TEP)行(ii)lithiation-sulfonation-ozidation(iii)(iv)量(v)KawaharaAsensio36,37,38Poly(polybenzimidazoles)(PBI)(sulfopropyl)量度20~140度10-3S/cm力(PFSA)度狀度Nafion度度wateruptake度K.D.Kreuer,JournalofMembraneScience185(2001)29.年六129CH2CHmCH2CCH3CH3nCH2CHmSO3HSO3HNNNHNHO3SnSulfoproylatedPoly(polybenzimidazoles)(PBI)Poly(aryletherketone)(S-PEK)量度S-PEKimidazole200度210-2S/cm不量Wang39量Poly(aryleneethersulfone)AFM度10nm25nm220度度300.17S/cmOCCH3CH3OSO3HSOOnSulfonatedPoly(aryleneethersulfone)了polyimides(PI)40,41,42,poly(4-phenoxybenzoyl-1,4-phenylene)(PPBP)43,44rigidrodpoly(p-phenylenes)(PP)45,46(例polyphenylenesulfide(PPS)47,48,polyphenyleneoxide(PPO)49,polythiophenylene50,polyphenylquinoxaline51,polyphosphazene52)都露不(Nafion)理例IonHopping來零料來(4)聯(Blockcopolymer)類Blockcopolymer兩ionicnon-ionicblocks列不randomionomersionicgroup類PFSA兩non-ionicblockBlockcopolymerionomers奈不Elabd53Poly(styrene-isobutylene-styrene)(S-SIBS)聯不離量度(3.2010-3~