Nonhumidified Intermediate Temperature Fuel Cells Using Protic Ionic Liquids

被引:424
作者
Lee, Seung-Yul [1 ]
Ogawa, Atsushi [1 ]
Kanno, Michihiro [1 ]
Nakamoto, Hirofumi [1 ]
Yasuda, Tomohiro [1 ]
Watanabe, Masayoshi [1 ]
机构
[1] Yokohama Natl Univ, Dept Chem & Biotechnol, Hodogaya Ku, Yokohama, Kanagawa 2408501, Japan
关键词
PHOSPHORIC-ACID; EXCHANGE MEMBRANES; ELECTROLYTE MEMBRANES; VINYL MONOMERS; CONDUCTIVITY; TRANSPORT; PERFORMANCE; NMR; STABILITY; POLYMERIZATION;
D O I
10.1021/ja102367x
中图分类号
O6 [化学];
学科分类号
0703 ;
摘要
In this paper, the characterization of a protic ionic liquid, diethylmethylammonium trifluoromethanesulfonate ([dema][TfO]), as a proton conductor for a fuel cell and the fabrication of a membrane-type fuel cell system using [dema][TfO] under nonhumidified conditions at intermediate temperatures are described in detail. In terms of physicochemical and electrochemical properties, [dema][TfO] exhibits high activity for fuel cell electrode reactions (i.e., the hydrogen oxidation reaction (HOR) and oxygen reduction reaction (ORR)) at a Pt electrode, and the open circuit voltage (OCV) of a liquid fuel cell is 1.03 Vat 150 degrees C C, as has reported in ref 27. However, diethylmethylammonium bis(trifluoromethane sulfonyl)amide ([dema][NTf2]) has relatively low HOR and ORR activity, and thus, the OCV is ca. 0.7 V, although [dema][NTf2] and [dema][TfO] have an identical cation ([dema]) and similar thermal and bulk-transport properties. Proton conduction occurs mainly via the vehicle mechanism in [dema][TfO] and the proton transference number (t(+)) is 0.5-0.6. This relatively low t(+) appears to be more disadvantageous for a proton conductor than for other electrolytes such as hydrated sulfonated polymer electrolyte membranes (t(+) = 1.0). However, fast proton-exchange reactions occur between ammonium cations and amines in a model compound. This indicates that the proton-exchange mechanism contributes to the fuel cell system under operation, where deprotonated amines are continuously generated by the cathodic reaction, and that polarization of the cell is avoided. Six-membered sulfonated polyimides in the diethylmethylammonium form exhibit excellent compatibility with [dema][TfO]. The composite membranes can be obtained up to a [dema][TfO] content of 80 wt % and exhibit good thermal stability, high ionic conductivity, and mechanical strength and gas permeation comparable to those of hydrated Nafion. H-2/O-2 fuel cells prepared using the composite membranes can successfully operate at temperatures from 30 to 140 degrees C under nonhumidified conditions, and a current density of 250 mA cm(-2) is achieved at 120 degrees C. The protic ionic liquid and its composite membrane are a possible candidate for an electrolyte of a H-2/O-2 fuel cell that operates under nonhumidified conditions.
引用
收藏
页码:9764 / 9773
页数:10
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