Preparation method of polymer matrix proton exchange membrane (PEM) with cross-linked structure

A technology of proton exchange membrane and cross-linked structure, which is applied in structural parts, fuel cell parts, battery pack parts, etc., can solve the requirements of high film forming conditions, poor controllability of sulfonation degree and sulfonation position , easy to cause pollution and other problems, to achieve the effect of reducing methanol permeability, low methanol permeability coefficient, and meeting the requirements of use

Active Publication Date: 2014-01-22
BEIJING UNIV OF CHEM TECH
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  • Abstract
  • Description
  • Claims
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Problems solved by technology

The above-mentioned methods for preparing polymer-based proton exchange membranes have their own defects. For example, doping with inorganic acids or heteropolyacids, and doping oxide nanoparticles all have the problem of leakage of doping substances. The controllability of the degree of sulfonation and the position of sulfonation is poor, and the controllability of preparing proton exchange membranes by polymerization is the best, but the process is complicated
At present, most PEMs use resin as the matrix material, and use the method of solution film formation to prepare thin films with a certain thickness. Membrane conditions are high

Method used

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  • Preparation method of polymer matrix proton exchange membrane (PEM) with cross-linked structure
  • Preparation method of polymer matrix proton exchange membrane (PEM) with cross-linked structure
  • Preparation method of polymer matrix proton exchange membrane (PEM) with cross-linked structure

Examples

Experimental program
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Effect test

Embodiment 1

[0025] Preparation of SBR / NaSS composite film: Add 100g SBR to the open mill at room temperature to make it roll, then add 50g NaSS, 4g peroxide DBPMH, 1g crosslinking aid TAIC in turn; add all of them and mix for 10 minutes , make a triangular bag, and slice evenly to obtain a mixed rubber. Put the mixed rubber in the mold, pressurize and exhaust, press at 160°C for 15 minutes (the in-situ grafting reaction occurs within this period), take out the mold, and obtain the SBR / NaSS composite film.

[0026] The SBR / NaSS composite film was first soaked in deionized water for 24 hours at 50°C, and then soaked in a sulfuric acid solution with a mass fraction of 5% for 30 hours; then, the film was cleaned with deionized water at room temperature until the pH value is 6-7. The washed films were vacuum dried at 70 °C for 24 h to remove moisture. Finally, SBR-based PEM with cross-linked structure was obtained.

Embodiment 2

[0028]Preparation of EPDM / NaVS composite film: Add 100g EPDM to the open mill at room temperature to make it roll, then add 50g NaVS, 8g peroxide DCP, 2g cross-linking agent TAC in turn; add all of them and mix for 10 minutes , make a triangular bag, and slice evenly to obtain a mixed rubber. Put the mixed rubber in the mold, pressurize and exhaust, press at 170°C for 30 minutes (the in-situ grafting reaction occurs within this period), take out the mold, and obtain the EPDM / NaVS composite film.

[0029] The EPDM / NaVS composite film was first soaked in deionized water for 20 hours at 70°C, and then soaked in a sulfuric acid solution with a mass fraction of 15% for 24 hours; then, the film was cleaned with deionized water at room temperature until the pH value is 6-7. The washed films were vacuum-dried at 100 °C for 12 h to remove moisture. Finally, EPDM-based PEM with cross-linked structure was obtained.

Embodiment 3

[0031] Preparation of CSM / NaSS composite film: add 100g CSM to the open mill at room temperature to make it roll, then add 100g NaSS, 14g peroxide DCP, 3g crosslinking agent HVA-2 in turn; add all of them and mix After 30 minutes, make a triangular bag, and then slice evenly to obtain a mixed rubber. Put the mixed rubber in the mold, pressurize and exhaust, press at 170°C for 45 minutes (the in-situ grafting reaction occurs within this period), take out the mold, and obtain the CSM / NaSS composite film.

[0032] The CSM / NaSS composite film was soaked in deionized water for 30 hours at 60°C, and then soaked in a sulfuric acid solution with a mass fraction of 10% for 24 hours; then, the film was cleaned with deionized water at room temperature until the pH value is 6-7. The washed films were vacuum-dried at 100 °C for 12 h to remove moisture. Finally, a CSM-based PEM with a cross-linked structure was obtained.

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Abstract

The invention relates to a preparation method of a polymer matrix proton exchange membrane (PEM) with a cross-linked structure, belonging to the field of battery electrolyte materials. The PEM is prepared by carrying out mechanical blending dispersion on matrix polymer material, unsaturated metal organic sulfonate, peroxide and auxiliary crosslinking agent, carrying out reaction in situ at the temperature of 140-200 DEG C, treating the product of the reaction by deionized water and sulfuric acid solution, and drying; and the PEM comprises the components in parts by weight: (1) 100 parts of matrix polymer material, (2) 20-150 parts of unsaturated metal organic sulfonate, (3) 1-20 parts of peroxide and (4) 0-5 parts of auxiliary crosslinking agent. In the molding process, organic solvent is not needed; and the preparation method is simple, high in efficiency, environment-friendly and low in cost. The prepared PEM has the proton conductivity approximate to Nafion (reaching up to the order of magnitude of 10<-2> / cm) and the methanol permeability coefficient far less than Nafion at the temperature of 20-80 DEG C, thus meeting the using requirement of a direct methanoi fuel cell.

Description

(1) Technical field: [0001] The invention relates to a method for preparing a polymer matrix proton exchange membrane with a crosslinked structure, belonging to the field of battery electrolyte materials. (two) background technology: [0002] Proton exchange membrane (PEM) is one of the key components of direct methanol fuel cells, which is responsible for the dual functions of conducting protons and blocking fuel and air, and its performance is critical to the output performance of the battery. At present, the most representative ones are the Nafion series products produced by DuPont Company of the United States, which have high electrical conductivity, proton exchange capacity and outstanding chemical stability, but problems such as high price, low working temperature and high methanol permeability restrict their commercial use. application and promotion. Therefore, the development of PEM with simple process, low price and excellent performance has become a hot spot and m...

Claims

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Application Information

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Patent Type & Authority Patents(China)
IPC IPC(8): C08J7/14C08L51/04C08L51/06C08L51/00C08F279/02C08F255/06C08F255/02C08F291/02C08F287/00C08F212/14C08F228/02H01M8/02H01M2/16H01M8/1072
CPCY02E60/12Y02E60/50
Inventor 张立群魏征何少剑林俊刘鑫乔婧
Owner BEIJING UNIV OF CHEM TECH
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