设计并组装单电池寿命测试系统,测试直接甲醇燃料电池(DMFC)的运行寿命,获得不同运行时间下单电池的极化和功率曲线.测试结束后,分别对运行过的膜电极(MEA)催化剂(铂黑和铂钌黑)和Nafion117(膜作XRD,HRTEM,FTIR及Raman等表征.考察在长期运行条件下电池寿命性能与膜电极中催化剂的颗粒大小、分布、形态、表面物种以及膜的结构之间的关系.寿命测试结果表明,单电池在不同运行阶段其性能变化也不同.运行前200 h,电池性能衰减较显著;运行200~704 h性能较稳定,运行1 002 h后电池性能恶化.波谱实验发现,单电池长期运行后,其膜电极的阴、阳极催化剂颗粒变大.电池寿命性能的衰退伴随膜电极微结构、表面组成、催化剂/膜界面结构的变化以及Nafion 117(膜的老化.
程璇
,
彭程
,
游梦迪
,
刘晶
,
张颖
. DMFC寿命测试过程中膜电极的表面和结构研究(英文)[J]. 电化学, 2005
, 11(3)
: 254
-261
.
DOI: 10.61558/2993-074X.1650
The lifetime and performance of a direct methanol fuel cell (DMFC) were investigatedto understand the correlation between thestructure of catalysts /membrane and cell performanceversus time.The cell polarization and performance curves were obtained during the DMFC operation with the time.The catalysts and Nafion~ membrane of the membrane electrode assembly (MEA) from the lifetime test were comprehensively examined by XRD, HRTEM, FTIRand Raman spectroscope techniques.The results revealed that there was significant performance degradation during the first 200 hours operation; while the degradation was slowing down between 200 and 704hours operation.The degradation became worse after 1 002 h operation.The increases of the catalyst particle size from both anode and cathode catalysts wereobserved after the DMFC lifetime test.The changes of microstructure, surface composition, the interfacial structure of the MEA, and the aging of Nafion~ under the DMFC lifetime tests were also observed.
[1]D illon R,Srin ivasan S,AricòA S,et al.Internationalactivities in DMFC R&D:status of technologies and po-tential app lications[J].J.Power Sources,2004,127:112~126.
[2]Haile S M.Fuel cellm aterials and components[J].Ac-ta M aterialia,2003,51:5 981~6 000.
[3]Costam agna P,Srin ivasan S.Quantum jumps in thePEMFC sc ience and technology from the 1960 s to theyear 2000,Part I.Fundam ental sc ientific aspects[J].J.Power Sources,1999,84:167~172.
[4]W ak izoe M,Velev O A,Srin ivasan S.Analysis of pro-ton exchange m embrane fuel cell perform ance w ith alter-nate m embranes[J].E lectroch im ica Acta,2002,40:335~344.
[5]AricòA S,CretìP,Antonucc i P L,et al.Optim ization ofoperating param eters of a d irect m ethanol fuel cell andphysico-chem ical investigation of catalyst-electrolyte in-terface[J].E lectroch im ica Acta,1998,43,3 719~3 729.
[6]Kn ights S D,Colbow K M,St-P ierre J,et al.Agingm echan ism s and lifetim e of PEFC and DMFC[J].J.Power Sources,2004,127:127~134.
[7]Staiti P,AricòA S,Baglio V,et al.Hybrid nafion-sil-ica m embranes doped w ith heteropolyac ids for app lica-tion in d irectm ethanol fuel cells[J].Solid State Ion ics,2001,145:101~107.
[8]L im a A,Coutanceau C,Léger J M,et al.Investigationof ternary catalysts for m ethanol electroxidation[J].J.App l.E lectrochem.,2001,31:379~386.
[9]G tzM,W endtH.B inary and ternary anode catalyst for-mu lations inc lud ing the elem ents W,Sn and Mo forPEMFCs operated on m ethanol or reform ate gas[J].E lectroch im ica Acta,1998,43:3 637~3 644.
[10]Roth C,Goetz M,Fuess H.Synthesis and character-ization of carbon-supported Pt-Ru-WOxcatalystsby spectroscop ic and d iffraction m ethods[J].J.App l.E lectrochem.,2001,31:793~798.
[11]Kad irgan F,Beden B,Léger J M,et al.Synergisticeffect in the electrocatalytic oxidation of m ethanol onp latinum+pallad ium alloy electrodes[J].J.E lectro-anal.Chem.,1981,125:89~103.
[12]Antolin i E.Form ation of carbon-supported PtM alloysfor low temperature fuel cells:a review[J].M ateri.Chem.Phys.,2003,78:563~573.
[13]Cheng X,Chen L,Peng C,et al.Catalystm icrostruc-utre exam ination of PEMFC m embrane electrode assem-b lies vs.tim e[J].J.E lectrochem.Soc.,2004,151:A48~52.
[14]AricòA S,Antonucc i P L,Mod ica E,et al.E ffect ofPt-Ru alloy composition on h igh-temperature m etha-nol electro-oxidation[J].E lectroch im ica Acta,2002,47:3 723~3 732.
[15]G rugerA,AndréRégis,Schm atko T,et al.Nanostruc-ture of nafion m embrane at d ifferent states of hydra-tion:an IR and Ram an study[J].V ibrational Spec-troscopy,2001,26:215~225.