DMFC用磺化聚醚醚酮聚苯胺共混型质子交换膜的研究

231Vol.23,No.120071POLYMERMATERIALSSCIENCEANDENGINEERINGJan.2007DMFC/蔡雨泉,黄绵延,王宇新,许　莉(,,300072):磺化聚醚醚酮膜(SPEEK)是直接甲醇燃料电池(DMFC)用质子交换膜的候选材料之一,但是当温度和磺化度(DS)较高时,该膜在甲醇水溶液中溶胀非常严重,甚至溶解,其使用温度受到限制。将磺化度为50.11%的SPEEK和聚苯胺(PANI)共混制膜,希望利用酸碱之间的相互作用对SPEEK进行改性。研究结果表明,PANI的加入使SPEEK/PANI共混膜的使用温度有较大提高,并且该膜还具有较高的电导率和较好的阻醇性能。:;;;;;:TB383:A:1000-7555(2007)01-0246-04DMFC,[1],DMFC,DMFC[2],,[3],DMFC,DMFC[46],(SPEEK),,DMFCDSSPEEK,DSSPEEK[4,7,8],PANISPEEK,SPEEKSPEEK,PANI,,SPEEK11.1SPEEKSPEEK(PEEK)[9]10gPEEK(),95%98%100mL,60,2.5h,SPEEKSPEEK,SPEEK60,,[7]1.2PANIPANI[10]0.4mol650mL2mol/L,-20,0.4mol,20h,,PANIPANI2.5%12h,,,20:2005-11-10;:2006-03-06:(033183111)(05YFZJC00600):,,E-mail:[e-mail],PANI,1.3SPEEK/PANI1.1SPEEK(50.11%)N--2(NMP),,SPEEKH+[8]PANI,5minSPEEK/NMP,15min,5%,100,1mol/L,1001h,24h,Fig.1ArrheniusplotsofprotonconductivityforSPEEK,Nafion115andSPEEK/PANImembranes:SPEEK(DS=50.11%);:SPEEK/PANI(10%);:SPEEK/PANI(20%);:Nafion115.250.11%SPEEKPANIPANIFig.1,Nafion115,,()Arrhenius=0exp(-Eact/RT):;0;Eact;R;TArrhenius(Tab.1)Tab.1,Nafion115,7.24kJ/mol,SPEEKSPEEK/PANISPEEKSPEEK/PANI,PANI,,,SPEEK/PANI,NafionTab.1ProtonactivationenergiesindifferentmembranesMembraneNafion115SPEEK(DS=50.11%)SPEEK/PANI(10%a)SPEEK/PANI(20%b)Eact(kJ/mol)7.2437.3445.8247.70a,b:PANIcontents.Fig.2FT-IRspectraofSPEEKandSPEEK/PANImembranesPANISPEEK/PANI,PANISPEEKSPEEKPANI10%SPEEK/PANI(Fig.2)2028cm-11918cm-1C=N+-H,PANIC=N-SPEEK-SO3H,,SPEEK,,,SPEEK/PANI2471:DMFC/SPEEK,SPEEKPANI,,,,,SPEEKSPEEK/PANI,,T*,Fig.3SPEEK/PANIT*PANI,SPEEK/PANIT*SPEEK,PANI,T*PANI,PANISPEEK,,PANI,Fig.3HightolerabletemperatureofSPEEKandSPEEK/PANImembraneswithdifferentPANIcontentsTab.2Electronicconductivities()ofSPEEKandSPEEK/PANImembranesMembraneSPEEK/PANI(10%)aSPEEK/PANI(20%)bSPEEK(DS=50.11%)(S/cm)1.910-102.110-101.7510-10a,b:PANIcontentsPANI[11],,Tab.2,10%20%PANI,SPEEK/PANI,SPEEK69PANI[11]SPEEK/PANI,PANI,,SPEEK/PANISPEEKNafion115,SPEEK/PANIPANI(Fig.4)10%PANI,SPEEK/PANI4.3210-8cm2/s,SPEEK96.9%,Nafion11597.6%;SPEEK/PANIPANI20%,1.8010-8cm2/s,SPEEKNafion11598.7%99.0%Fig.4MethanolpermeabilityofSPEEK,Nafion115andSPEEK/PANImembraneswithdifferentPANIcontentsPANIPANISPEEK,PANISPEEK/PANI,PANI24820073SPEEK,PANISPEEK/PANI,PANIPANI10%20%,SPEEK4060PANIPANI10%20%SPEEK/PAN,SPEEK96.9%98.7%,SPEEK/PANIPANI10%SPEEK/PAN,1400.074S/cm,Nafion115,SPEEK/PANISPEEK,,DMFC:[1]WasmusS,KuverA.J.Electroanal.Chem.,1999,(461):14.[2]SammaSR,WasmusS,SavinellRF.J.Electrochem.Soc.,1996,143(5):1498.[3]WangJT,WasmusS,SavinellRF.J.Electrochem.Soc.,1996,143(4):1233.[4](LILei),(XULi),(WANGYu-xin).(ActaPolymericaSinica),2003,(3):452.[5]ZaidiSMJ,MikhailenkoSD,RobertsonGP,etal.J.Membr.Sci.,2000,173:17.[6](XINGDan-min),.(Poly.Mater.Sci.&Eng.),2005,21(3):282.[7]LeiL,JunZ,YuxinW.J.Membr.Sci.,2003,226:159.[8]KerresJ,TangCM,GrafC.Ind.Eng.Chem.Res.,2004,43:4571.[9]HuangRYM,ShaoPinghai,BurnsCM.J.Appl.Polym.Sci.,2001,82:2651.[10]HuangWS,HumphreyBD,MacDiarmidAG.J.Chem.Soc.FaradayTrans.I,1985,(82):2385.[11]WenguangL,MeixiangW.Synth.Met.,1998,(92):121.SulfonatedPolyetherEtherKetone/PolyanilineMembranesforDirectMethanolFuelCellsCAIYu-quan,HUANGMian-yan,WANGYu-xin,XULi(StateKeyLaboratoryofChemicalEngineering,ChemicalEngineeringResearchCenter,SchoolofChemicalEngineeringandTechnology,TianjinUniversity,Tianjin300072,China)ABSTRACT:Sulfonatedpolyetheretherketone(SPEEK)isaveryhopefulalternativemembranematerialfordirectmethanolfuelcells.However,withfairlyhighdegreeofsulfonation(DS)andwhenapproachinghightemperature,SPEEKmembranescanheavilyswellorevendissolve.Thisrestrictsthemembranesfromworkingaboveahightolerabletemperature,whichotherwiseenableshighprotonconductivity.Todealwiththiscontradictory,polyaniline(PANI)wasemployedtoblendwithSPEEK,withtheattempttotakeadvantageoftheinteractionbetweenacidandbasegroupsofthetwopolymers.ResultsshowthatthetemperaturetoleranceandthemethanolresistanceoftheSPEEK-blend-PANmembranesisgreatlyimproved.Highprotonconductivityoftheblendmembranescanbealsoachievedduetoincreasedhightolerabletemperature.Keywords:sulfonatedpolyetheretherketone;polyaniline;directmethanolfuelcells;protonexchangemembranes;protonconductivity;methanolpermeability2491:DMFC/