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Polymer electrolyte membrane, membrane electrode assembly using same, and solid polymer fuel cell

A polymer electrolyte, phase separation technology, applied in solid electrolyte fuel cells, fuel cells, fuel cell parts and other directions, can solve the loss of membrane mechanical strength, physical durability, difficulty in recycling and reuse of waste treatment materials, proton conduction It has the advantages of excellent mechanical strength and chemical stability, excellent proton conductivity, and excellent physical durability.

Active Publication Date: 2014-05-07
TORAY IND INC
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

As a result, the problem that the load on the humidifier is large can be cited, and the following problems can also be cited: at the freezing point, the water in the conductive membrane participating in proton conduction freezes, so the proton conductivity is greatly reduced, and the problem cannot be generate electricity
Nafion (registered trademark) shows high proton conductivity under low humidification through the proton conduction channel brought about by the cluster structure, but on the other hand, it is made through multi-step synthesis, so the price is very high, other than that In addition, there is a problem that the fuel crossover (the amount of fuel permeation) is large due to the above-mentioned cluster structure.
In addition, problems of loss of mechanical strength and physical durability of the film due to swelling and drying, problems of low softening point and inability to use at high temperatures, problems of disposal after use, and difficulties in recycling of materials have also been pointed out.

Method used

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  • Polymer electrolyte membrane, membrane electrode assembly using same, and solid polymer fuel cell
  • Polymer electrolyte membrane, membrane electrode assembly using same, and solid polymer fuel cell
  • Polymer electrolyte membrane, membrane electrode assembly using same, and solid polymer fuel cell

Examples

Experimental program
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Embodiment

[0233] The present invention will be described in more detail through examples below, but the present invention is not limited thereto. In addition, the measurement conditions of each physical property are as follows. In addition, although the chemical structural formula was inserted in this Example, this chemical structural formula was inserted for the purpose of helping the reader's understanding, and it is not limited thereto.

[0234] (1) Ion exchange capacity

[0235] Determined by neutralization titration. The measurement was carried out 3 times, and the average value was taken.

[0236] 1. Perform proton replacement, wipe off moisture from the membrane surface of the electrolyte membrane fully washed with pure water, and vacuum dry at 100° C. for 12 hours or more to obtain the dry weight.

[0237] 2. Add 50 mL of a 5% by weight sodium sulfate aqueous solution to the electrolyte, and let it stand for 12 hours to perform ion exchange.

[0238] 3. Titrate the generated...

Synthetic example 1

[0327] Synthesis of 2,2-bis(4-hydroxyphenyl)-1,3-dioxolane (K-DHBP) represented by the following general formula (G1)

[0328]

[0329] Put 49.5g of 4,4'-dihydroxybenzophenone, 134g of ethylene glycol, 96.9g of trimethyl orthoformate and 0.50g of p-toluenesulfonic acid monohydrate into a 500mL flask equipped with a stirrer, a thermometer and a distillation tube and dissolve. Then keep stirring at 78-82° C. for 2 hours. Furthermore, internal temperature was raised gradually to 120 degreeC, and it heated until distillation of methyl formate, methanol, and trimethyl orthoformate stopped completely. After cooling the reaction solution to room temperature, the reaction solution was diluted with ethyl acetate, and the organic layer was washed with 100 mL of a 5% potassium carbonate aqueous solution, separated, and then the solvent was distilled off. 80 mL of dichloromethane was added to the residue to precipitate crystals, which were filtered and dried to obtain 52.0 g of 2,2-b...

Synthetic example 2

[0331] Synthesis of 3,3'-sodium disulfonate-4,4'-difluorobenzophenone represented by the following general formula (G2)

[0332]

[0333] Make 109.1 g of 4,4'-difluorobenzophenone (Aldrich reagent) in oleum (50% SO 3 ) in 150 mL (Wako Pure Chemical Chemicals) for 10 hours at 100°C. Then, a small amount was poured into a large amount of water one by one, and after neutralizing with NaOH, 200 g of common salt was added to precipitate the composite. The resulting precipitate was separated by filtration and recrystallized from an aqueous ethanol solution to obtain 3,3'-sodium disulfonate-4,4'-difluorobenzophenone represented by the above general formula (G2). The purity is 99.3%. structure through 1 Confirmed by H-NMR. Impurities were quantitatively analyzed by capillary electrophoresis (organic matter) and ion chromatography (inorganic matter).

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Abstract

Provided is a polymer electrolyte membrane that has excellent proton conductivity even under low humidification conditions, has excellent mechanical strength and chemical stability, and can achieve high output and excellent physical durability when made into a solid polymer fuel cell. This polymer electrolyte membrane comprises a block copolymer including at least one each of a segment (A1) that contains an ionic group and a segment (A2) that does not contain an ionic group, the polymer electrolyte membrane being characterized by: forming a co-continuous (M1) or lamellar (M2) phase-separated structure; and having a crystallization heat quantity of 0.1 J / g or greater as measured by differential scanning calorimetry, or a degree of crystallinity of 0.5% or greater as measured by wide-angle X-ray diffraction.

Description

technical field [0001] The present invention relates to a practically excellent polymer electrolyte membrane that has excellent proton conductivity even under low humidification conditions and low temperature conditions, and can realize excellent mechanical strength, fuel barrier properties, and long-term durability, and use of the polymer electrolyte membrane Membrane electrode complexes and solid polymer fuel cells. Background technique [0002] A fuel cell is a power generation device that obtains electrical energy by electrochemically oxidizing fuels such as hydrogen and methanol, and has attracted attention as a clean energy supply source in recent years. Among them, the solid polymer fuel cell has a low standard operating temperature of about 100°C and a high energy density, so it is expected to be widely used as a power generation device for small-scale distributed power generation facilities, automobiles, ships and other moving objects. In addition, it is also attra...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): H01M8/02C08G65/40C08G81/00C08J5/00H01B1/06H01M8/10
CPCC08J5/2256H01B1/122H01M8/1023H01M2008/1095C08J2371/12C08G65/40C08G65/4012C08G65/4043C08G65/48C08G2650/40Y02E60/50H01M8/102
Inventor 梅田浩明出原大辅天野绘美
Owner TORAY IND INC
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