钙钛矿型固体氧化物燃料电池阳极材料-郑尧

:20074,:20076*(No120646002,20676061)**e-mail:[e-mail]钙钛矿型固体氧化物燃料电池阳极材料*郑尧周嵬冉然邵宗平**(南京工业大学化工学院省部共建材料化学工程教育部重点实验室南京210009)固体氧化物燃料电池(SOFCs)作为一种高效洁净的化学电源已经受到各国的重视钙钛矿型复合氧化物由于其较高的混合导电性和对燃料气较好的催化活性及超强抗积碳能力而越来越被广泛地应用于直接烃类SOFCs的阳极材料中本文对钙钛矿型固体氧化物燃料电池阳极材料的最新研究进展进行了较为全面的综述,从阳极的设计要求出发,着重比较了LaCrO3系列SrTiO3系列和双钙钛矿等阳极材料的稳定性电导率以及电催化活性,指出了其不足,并对其应用前景进行了展望固体氧化物燃料电池钙钛矿阳极材料:TM91114;O64612:A:1005-281X(2008)02P3-0413-09PerovskiteasAnodeMaterialsforSolidOxideFuelCellsZhengYaoZhouWeiRanRanShaoZongping**(KeyLaboratoryofMaterials-OrientedChemicalEngineeringofMinistryofEducation,CollegeofChemistryandChemicalEngineering,NanjingUniversityofTechnology,Nanjing210009,China)AbstractSolid-oxidefuelcells(SOFCs)haveattractedconsiderableattentionsduetotheirhighenergyconversionefficiency,highpowerdensityandextremelylowpollution.Perovskite-basedmaterialshavebeenwidelyusedasanodematerialsforSOFCsbecauseoftheirhighmixedionic-electronicconductivity(MIEC),favorablecatalyticactivityforfueloxidation,andsuper-carboncokingresistance.Therecentprogressontheperovskite-basedanodematerialsforSOFCsisreviewed.Inordertofindawaytosatisfythestrictrequirementsofanodewithhydrocarbonfuels,thisarticleisfocusedontheirphasestability,electronicandPorionicconductivity,andcatalyticactivityforfueloxidation.Themainproblemsofcurrentperovskite-basedanodesforpracticalapplicationarepointedoutandthepossiblefutureresearchdirectionsareproposed.Keywordssolid-oxidefuelcells;perovskite;anodematerials(SOFCs),,[1)3](),,,(),,H2+O2-H2O+2e-(1),CnH2n+2+(3n+1)O2-nCO2+(n+1)H2O+(6n+2)e-(2),,,202P320083化学进展PROGRESSINCHEMISTRYVol.20No.2P3Mar.,2008(500)1000e),,[4,5]1111[6,7],:(1);(2);(3),,;(4)SOFCs,;(5),;(6)SOFCs112SOFCs-N-iYSZ(8mol%Y2O3ZrO2)[8]N-iSDC(Sm2O3CeO2)[9](YSZ,SDC),YSZ,SDCGDC(Gd2O3CeO2)[10,11],,Ni,1000eYSZSDCLaCrO3N-iYSZN-iSDCSOFCs[12)14],,,Ni[15];,[16],,,,;,Ni[17],,Gorte[18,19]CuNiCu-YSZ,CuSOFC;CuC)C,Cu,NiCu,Cu-YSZ,,Cu-YSZ:(1)[20,21],,;;,;,||(TPB),(2)-(MIECs),||-,,(ABO3)(MO2)(MO2)(A2B2O7)(A016BO3)[22)26],90%,,2ABO3,A12,LaSrBaCa;B6,,TiVCrMnFeCoNiYNbMoAB#414#化学进展20,A,B,[27];B,,SOFCsLaCrO3SrTiO3,211LaCrO3SOFCs,LaCrO3,SOFCs[28,29]Cr,LaCrO3ACaSr,BMnFeCoNiCuV2%)10%1BLaCrO3(3)[30]CCH4=100%1-(pCH4)f(pCH4)i(3)(pCH4)i(pCH4)f,Vernoux[31]La018Sr012Cr0197V0103O3,(850e~108#cm2)Sauvet[32]PtRhRu[33],Ru-CeO2[34,35],,,,,RuLa1-xSrxCr1-yRuyO3-D(x=012013014;y=01020105),Ru,La017Sr013Cr0195Ru5O3-DCH4H2750e401BLaCrO3[30]Fig.1Conversionofmethaneinstreamat800)900ebylanthanumchromitewithB-sitelow-contentdoped[30]3178#cm2;,RuRuOx,[36],N-iYSZNi,Ni,Sauvet[37]NiLa1-xSrxCr1-yNiyO3(x=011)014;y=0105011)(LSCN)BNipO210-15atmp,Sr;Ni5mol%,Ni10mol%LSCN,Ni,,La017Sr013Cr0195Ni0105O3(750e28%)[38]La0185Sr0115Cr019Ni011O3-D-Ce018Sm012O119(50:50wt%),SDCLSCN,,Ni,B1BLaCrO3900e,NiLaCrO3,#415#2P31BLaCrO3900e[39]Table1Conversionofmethaneinstreamoroxygenat900ebylanthanumchromitewithB-sitedoped[39]catalystconversion(%)CH4BArBH2O=56B20B24CH4BO2=5B1La0185Sr0115Cr019Mg011O310190122La0185Ca0115Cr019Mg011O311120104La0185Ca0115Cr019Ni011O336171817LaCr019Mg011O313110105LaCr019Mn011O311120179LaCr019Fe011O313110162LaCr019Co011O311150121LaCr019Ni011O332111616Sfeir[40]MnNiCoFeCuLaCrO3850e116@10-263116@10-16119@10-141126@10-23118@10-6atm1000)1300KNiCoCu,BMnFeLaCrO3La0175Sr0125Cr015Fe015O3[41],900eO2BCH4=1B12B168%96%,(850e5%H2PArH2117911158#cm2)Fe,MnFe,,MnMn3+,TaoIrvine[42]2003NatureMaterialsBMnLa0175Sr0125Cr015Mn015O3(LSCM)-,900e5%H2P3%H2OP92%Ar120h,1300eYSZ(La0175Sr0125)019Cr015Mn015O3A,SrCo018Fe012O3-D,YSZ(La2Zr2O7,GDC),H25%H2PAr900e470290mW#cm-2,YSZ,NiLSCM,2LSCM,2LSCM,Table2ThepeakpowerdensityofsinglecellsusingLSCMasanodewithvariedcathodesandelectrolytescathodePelectrolytePanodetemp1(e)Pmax(mW#cm-2)H25%H2CH4ref.LSM-YSZPYSZPLSCM(1)-YSZ90047029020042GSCPLSGMCoPLSCM(2)90035043LSMPLSGM(1)PLSCM80057042544LSCMPYSZPLSCM95054632634745LSCM(2)PYSZPLSCM(2)90030017023046SCFPLSGM(2)PLSCM80043047SCFPLSGM(2)PLDCPLSCM(1)80057769SCFPLSGM(2)PLDCPLSCM+Cu85084052048LSCM:La0175Sr0125Cr015Mn015O3-D;LSCM(1):(La0175Sr0125)019Cr015Mn015O3-D;LSCM(2):(La0175Sr0125)0195Cr015Mn015O3-D;LSM:La018Sr012MnO3;GSC:Gd014Sr016CoO3-D;LSGM(1):La019Sr011Ga018Mg012O3-D;LSGM(2):La018Sr012Ga0183Mg0117O21815;LSGMCo:La019Sr011Ga018Mg01115Co01085O3;SCF:SrCo018Fe012O3-D;LDC:La014Ce016O118,Tao[43]LSGMCoLSGM,,CoLSCM,Ruiz-Morales[45]Bastidas[46]LSCM,(950e)LSCMLSCM,Wan[48]Cu,CH4850e520mW#cm-2,LSCM(900e5%H2PAr115S#cm-1),10%H2S[49],Zha[50]CrLa0175Sr0125Cr1-xMnxO3(x=014015016),Cr,H2-10%#416#化学进展20H2SPlint[51]LaSrLa1-xSrxCr015Mn015O3(x=0120125013),5%H2PArLa,La,(5%H2PAr)Jiang[52]La0175Sr0125Cr015Mn015O3,YSZ1200eLSCM-YSZ(50:50wt%)(900e,CH4113)1168#cm2),[53]LSCM-GDC(800e,CH401448#cm2)Raj[54]A(La0175Sr0125)0195Cr015Mn015O3-D,1000eD*4@10-10cm2#s-13@10-8cm2#s-1,K*5@10-8cm#s-14@10-8cm#s-1,LaCrO3,BNiMnFe,LSCM,10S#cm-1,212SrTiO3SrTiO3,SrTiO3Ti4+yTi3+,SrTiO3,Hui[55](7%H2PAr)Sr1-115xMxTiO3(M=YLaPrSmNdGdYb)ASrTiO3,3(pO2=10-19atm)800e,YSrTiO3,Sr0188Y0108TiO364S#cm-1,ASr0186Y0108TiO3(SYT)82S#cm-1YSZLSGM1400eTao[56]ScSr0186Y0108Ti019Sc011O3,SYT(900e,5%H2PAr1)2S#cm-1)Sc3+Irvine[57]NbSr1-xTi1-xP2NbxO3(x014)