New membranes for direct methanol fuel cells

Jörissen, Ludwig; Gogel, Viktor; Kerres, Jochen; Garche, J.

doi:10.1016/s0378-7753(01)00952-1

Cited by 272 publications

(135 citation statements)

References 34 publications

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“…Compared to some blend membrane systems based on acid-base interactions that have been investigated in the literature [18,19,31,32], the SPEEK/PSf-BTraz blend membranes presented here show higher proton conductivity than plain SPEEK membrane despite a decrease in the IEC values due to acid-base interactions. We believe this is mainly due to the insertion of the heterocyclic groups of PSf-BTraz into the ionic clusters formed by the sulfonic acid groups of SPEEK as indicated by the SAXS data and the consequent widening of the ionic cluster size compared to that in plain SPEEK.…”

Section: Liquid Uptake Iec and Proton Conductivity Under Humidity Cmentioning

confidence: 64%

“…The brittleness is possibly caused by the inflexibility of the covalent networks [12][13][14][15]. Because of this reason, more attention is being directed towards the development of ionomer networks containing ionically cross-linked blend systems such as SPPO (poly(2,6-dimethyl-1,4-phenylene oxide))/PBI (polybenzimidazole respectively), SPEEK/PBI, and SPSf/aminated PSf, which are more flexible [16][17][18][19]. Our group reported recently [20][21][22][23] that blend membranes based on acid-base interactions between the sulfonic acid groups of SPEEK and the N-heterocycle groups (benzimidazole (BIm), amino-benzimidazole (ABIm), nitrobenzimidazole (NBIm), and 1H-perimidine (PImd)) tethered to PSf show improved DMFC performance compared to plain SPEEK membranes due to both suppressed methanol crossover and enhanced proton conductivity.…”

Section: Introductionmentioning

confidence: 99%

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Acid–base blend membranes consisting of sulfonated poly(ether ether ketone) and 5-amino-benzotriazole tethered polysulfone for DMFC

Manthiram

Guiver

2010

Journal of Membrane Science

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Low cost, acid-base blend membranes have been synthesized by blending sulfonated poly(ether ether ketone) (SPEEK) (an acid polymer) and various amounts of polysulfone tethered with 5-aminobenzotriazole (a basic polymer). The blend membranes have been characterized by ion-exchange capacity (IEC), liquid uptake, proton conductivity, methanol crossover, and fuel cell performance measurements. The blend membranes exhibit superior performance in direct methanol fuel cells (DMFC) compared to plain SPEEK and Nafion 115 membranes due to enhanced proton conductivity and much suppressed methanol crossover while preserving good swelling stability. The maximum power density of the blend membrane is two times higher than that of Nafion 115 membrane at 80 • C with 1 M methanol feed. Additionally, the effects of the size, pK a , and the number of nitrogen atoms of the tethered heterocycle groups on the properties of the blend membranes have also been investigated by comparing the properties of the blend membranes consisting of SPEEK and different basic polymers.

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Section: Liquid Uptake Iec and Proton Conductivity Under Humidity Cmentioning

confidence: 64%

Section: Introductionmentioning

confidence: 99%

Acid–base blend membranes consisting of sulfonated poly(ether ether ketone) and 5-amino-benzotriazole tethered polysulfone for DMFC

Manthiram

Guiver

2010

Journal of Membrane Science

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“…51 There have been much attention for development of alternative membranes that have lower methanol permeability with minimal loss of proton conductivity. [62][63][64] The SPI membranes dealt in this review have high tolerance against methanol. They don't swell in methanol rather than in water.…”

Section: Direct Methanol Fuel Cellmentioning

confidence: 99%

On the Development of Naphthalene-Based Sulfonated Polyimide Membranes for Fuel Cell Applications

Yin

Yamada

Tanaka

et al. 2006

Polym J

176

109

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ABSTRACT:This article reviews the recent progress made over the past years based on naphthalene-based sulfonated polyimides (SPIs) in terms of proton conductivity, membrane swelling behavior, membrane stability toward water, and fuel cell performance in polymer electrolyte fuel cells (PEFCs) or direct methanol fuel cells (DMFCs). The structure-property relationship of SPI membranes is discussed in details with respect to the chemical structure of various sulfonated diamines and morphology of SPI membranes from the viewpoints of viscosity, mechanical strength and proton conductivity. Ion exchange capacity (IEC), basicity of sulfonated diamine, configuration (para-, meta-, or ortho-orientation) and chemical structure of polymer chain (linear or net-work) show great influence on the water stability and mechanical strength of SPI membrane. The SPIs with a branched/crosslinked structure and derived from highly basic sulfonated diamines display reasonably high water stability of more than 200-300 h in water at 130 C, suggesting high potential as PEMs operating at temperatures up to 100 C. The SPI membranes have fairly high proton conductivity at higher relative humidities and low methanol permeability. The water and methanol crossover through membrane under the fuel cell operation conditions is not controlled by electro-osmosis due to proton transport but by diffusion due to activity difference. This is quite different from the case of perfluorosulfonated membranes such as Nafion and results in the advantageous effects on fuel cell performance. SPI membranes displayed high PEFC performances comparable to those of Nafion 112. In addition, SPI membranes displayed higher performances in DMFC systems with higher methanol concentration (20-50 wt %), which is superior to Nafion and have high potential for DMFC applications at mediate temperatures (40-80 C In the past decades, great interest has been focused on the development of polymer electrolyte fuel cells (PEFCs) and direct methanol fuel cells (DMFCs) as a clean power source of energy for transportation, stationary and portable power applications.1,2 Fuel cells with high performance, high durability and potentially lower cost are greatly required. Polymer electrolyte membrane (PEM) is one of the key components in PEFC and DMFC systems. Perfluorosulfonic acid copolymer membranes, such as DuPont's Nafion membrane, are the state-of-the-art PEMs commercially available due to their high proton conductivity and excellent chemical stability.3,4 However, because of their high cost, low operational temperature below 80 C and large methanol crossover, there has been much interest in alternative PEMs. Many efforts have been done in the development of PEMs based on sulfonated aromatic hydrocarbon polymers. [5][6][7][8][9] The main problem existed in the hydrocarbon PEMs is the membrane stability under fuel cell conditions and low conducting performance at low moisture atmosphere. The balance between ion exchange capacity (IEC), proton conductivity and mechanical stability of a PEM ...

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“…Sulfonated poly(ether ether ketone) (SPEEK, Figure 1) is an anionic polymer that finds wide use as high-performance membrane polymer that can be applied in water purification, [1][2][3] in proton exchange membrane (PEM) fuel cells, [4][5][6] and in dehydration of industrial gases. [7][8][9] For multiple reasons, SPEEK membranes are exposed to higher temperatures.…”

Section: Introductionmentioning

confidence: 99%

Thermal Stability of Sulfonated Poly(Ether Ether Ketone) Films: on the Role of Protodesulfonation

Koziara

Kappert

Ogieglo

et al. 2015

Macromol. Mater. Eng.

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Thin film and bulk, sulfonated poly(ether ether ketone) (SPEEK) have been subjected to a thermal treatment at 160–250 °C for up to 15 h. Exposing the films to 160 °C already causes partial desulfonation, and heating to temperatures exceeding 200 °C results in increased conjugation in the material, most likely via a slight cross‐linking by H‐substitution. It is well‐known that the sulfonate proton plays a major role in the desulfonation reactions, and exchanging the protons with other cations can inhibit both protodesulfonation as well as electrophilic cross‐linking reactions of the sulfonate group with other chains. Yet, the implications of such ion‐exchange for the thermal processing of sulfonated polymer films has not been recognized. Our study demonstrates that the ion exchange stabilizes thin films and bulk SPEEK up to temperatures exceeding 200 °C, opening up ways for the thermal processing of SPEEK in the temperature range of 160–220 °C without adverse effects.

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New membranes for direct methanol fuel cells

Cited by 272 publications

References 34 publications

Acid–base blend membranes consisting of sulfonated poly(ether ether ketone) and 5-amino-benzotriazole tethered polysulfone for DMFC

Acid–base blend membranes consisting of sulfonated poly(ether ether ketone) and 5-amino-benzotriazole tethered polysulfone for DMFC

On the Development of Naphthalene-Based Sulfonated Polyimide Membranes for Fuel Cell Applications

Thermal Stability of Sulfonated Poly(Ether Ether Ketone) Films: on the Role of Protodesulfonation

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