A side chain type high temperature proton exchange membrane for fuel cells and its preparation method

A proton exchange membrane, fuel cell technology, applied in fuel cells, circuits, electrical components, etc., can solve the problems of poor membrane toughness, difficult membrane production, peeling of reinforcing fibers and membrane matrix materials, etc., to achieve high proton conductivity and Mechanical properties, effect of great application potential

Active Publication Date: 2021-01-26
BEIHANG UNIV
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Problems solved by technology

These improved methods can indeed improve the mechanical properties of high-temperature membrane materials to a large extent, but at the same time bring some new problems: for example, fiber-reinforced composite high-temperature membranes are prone to peeling off of reinforcing fibers and membrane matrix materials after absorbing phosphoric acid ;Using the ion cross-linking method, when the acidic polymer and the basic polymer are dissolved in the same solvent, it is easy to produce polymer salt precipitation, which makes it difficult to make a membrane; and chemical cross-linking will cause the membrane material to lose part of the phosphoric acid adsorption sites, Thereby reducing the membrane conductivity to a certain extent, and the toughness of the membrane becomes worse

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  • A side chain type high temperature proton exchange membrane for fuel cells and its preparation method
  • A side chain type high temperature proton exchange membrane for fuel cells and its preparation method
  • A side chain type high temperature proton exchange membrane for fuel cells and its preparation method

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preparation example Construction

[0034] The preparation method of the present invention mainly includes three steps of synthesis of side chain modified polymer, solution casting membrane and post-protonation treatment, and its preparation process route diagram is as follows: figure 1 As shown, the details are as follows:

[0035] (1) Chloromethylation reaction of polymer

[0036] Dissolving engineering plastic polymers with excellent thermal stability and chemical stability in suitable organic solvents (such as dichloroethane, tetrachloroethane, chloroform) to form a polymer solution to be reacted, the concentration is 5-20wt% , the preferred concentration is 8-15wt%, and the optimum concentration range is 9-12wt%.

[0037] Then add a certain amount of zinc powder and trifluoroacetic acid, usually with a mass ratio of 1:0.5 to 1:3, and the best ratio is: 1:1.2 to 1:1.5.

[0038] The reaction system was stirred at 20-50°C (according to the selected engineering plastics, the reaction temperature should be adj...

Embodiment 1

[0048] Polysulfone (PSf) is selected as the high molecular polymer, and its chloromethylation process is as follows:

[0049] Polysulfone, which has excellent thermal stability and chemical stability, was dissolved in dichloroethane at a concentration of 10 wt%. Then add zinc powder and trifluoroacetic acid, the mass ratio of the two is 1:0.5. After the reaction system was stirred at 35°C for 0.5 hours, 25 mL of chloromethyl ether was added dropwise, and the reaction was continued for 0.5 hours after the dropwise addition was completed. The reaction mixture after the reaction was poured into a precipitant for precipitation, and then filtered sequentially. After washing and drying, a polymer containing chloromethylation is obtained. The degree of chloroformation of polysulfone is obtained from the ratio of the integral of methylene hydrogen on the benzyl group to the integral of benzene ring hydrogen on the main chain in the nuclear magnetic spectrum, and the selected degree o...

Embodiment 2

[0056] Polyphenylsulfone is selected as the polymer, and its chloromethylation process is as follows:

[0057] Polyphenylsulfone, which has excellent thermal and chemical stability, was dissolved in chloroform in a concentration range of 13 wt%. Then add zinc powder and trifluoroacetic acid, the mass ratio of the two is 1:1. After the reaction system was stirred at 45°C for 1.1 hours, 35 mL of chloromethyl ether was added dropwise, and the reaction was continued for 1 hour after the dropwise addition was completed. The reaction mixture after the reaction was poured into a precipitant for precipitation, and then filtered sequentially. After washing and drying, a polymer containing chloromethylation is obtained. The degree of chloroformation of polyphenylsulfone is obtained according to the ratio of the integral of methylene hydrogen on the benzyl group to the integral of benzene ring hydrogen on the main chain in the nuclear magnetic spectrum, and the selected degree of chloro...

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Abstract

The invention discloses a side chain type high-temperature proton exchange membrane for a fuel cell and a preparation method thereof. The method comprises the following steps of: chloromethylating anengineering plastic polymer; grafting vinyl imidazole to a polymer side chain through atom transfer radical polymerization reaction to obtain a polyvinyl imidazole side chain type polymer, dissolvingthe obtained polymer by adopting a solvent, casting or coating a solution to form a membrane, stripping the membrane, and carrying out acidizing treatment to obtain the polymer electrolyte membrane material with high-temperature proton conductivity. The high-temperature proton exchange membrane material is homogeneous, transparent and compact, has excellent mechanical properties, high-temperatureproton conductivity and chemical stability, and can meet the application requirements of a high-temperature proton exchange membrane fuel cell (100-200 DEG C). The proton exchange membrane can also beused as a diaphragm material of flow batteries, high-temperature batteries, supercapacitors and other devices.

Description

technical field [0001] The invention belongs to the technical field of fuel cells, and in particular relates to a side-chain high-temperature proton exchange membrane and a preparation method thereof. Background technique [0002] As an energy conversion device, the proton exchange membrane fuel cell can directly convert the chemical energy in the fuel into electrical energy, and has the advantages of fast start-up speed, high energy conversion efficiency, high energy density, and no pollution. Compared with low-temperature proton exchange membrane fuel cells, high-temperature proton exchange membrane fuel cells have faster electrode reaction kinetics and better resistance to impurity gases such as carbon monoxide (CO) due to their operation at higher temperatures (100-200°C). Poisoning ability and simplified water heat management system have become one of the important development directions of proton exchange membrane fuel cells. High temperature proton exchange membrane ...

Claims

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Application Information

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Patent Type & Authority Patents(China)
IPC IPC(8): H01M8/124C08F283/00C08F283/08C08F226/06C08J7/14C08L51/08
CPCC08F283/002C08F283/08C08J7/14C08J2351/08H01M8/124C08F226/06Y02E60/50Y02P70/50
Inventor 卢善富白慧娟相艳王海宁张劲
Owner BEIHANG UNIV
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