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High-oxidization-resistance and high-conductivity crosslinked type polybenzimidazole high-temperature proton exchange membrane and preparation method therefor

A technology of proton exchange membrane and polybenzimidazole, which is applied in fuel cell components, circuits, fuel cells, etc., can solve the problems of aggravated PBI membrane degradation and battery performance degradation, and achieve excellent dimensional stability and high oxidation resistance Performance, the effect of solving the loss of phosphoric acid

Active Publication Date: 2017-03-29
ZHANGJIAGANG IND TECH RES INST CO LTD DALIAN INST OF CHEM PHYSICS CHINESE ACADEMY OF SCI
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

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Problems solved by technology

These free radicals generated will aggravate the degradation of the PBI film, resulting in a significant drop in battery performance

Method used

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  • High-oxidization-resistance and high-conductivity crosslinked type polybenzimidazole high-temperature proton exchange membrane and preparation method therefor
  • High-oxidization-resistance and high-conductivity crosslinked type polybenzimidazole high-temperature proton exchange membrane and preparation method therefor

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Effect test

Embodiment 1

[0029] A method for preparing a cross-linked polybenzimidazole high-temperature proton exchange membrane with high oxidation resistance and high conductivity, comprising the following steps:

[0030] (1) Dissolve 2 g of 1-vinyl-1,2,4-triazole in 20 mL of N-methylpyrrolidone, and then add the chain initiator azobisisobutyronitrile, wherein the mass content of the chain initiator is 25% of the high boiling point solvent; put it in an oil bath, react for 48 h, and the reaction temperature is 50 °C;

[0031] (2) Add 1 g polybenzimidazole to the solution, stir to dissolve, then add vinylphosphonic acid, stir to dissolve, add azobisisobutyronitrile, stir at room temperature for 2 h, nitrogen protection, gas flow rate is 100 mL / min;

[0032] (3) Put the solution in an oil bath, stir at 100 °C, and react for 48 h;

[0033] (4) Continue to add 10 mL of N-methylpyrrolidone to the solution, stir for 30 min, add manganese dioxide as a free radical quencher, stir ultrasonically for 30 m...

Embodiment 2

[0039] A method for preparing a cross-linked polybenzimidazole high-temperature proton exchange membrane with high oxidation resistance and high conductivity, comprising the following steps:

[0040] (1) Dissolve 1.5 g of 1-vinyl-1,2,4-triazole in 15 mL of N-methylpyrrolidone solvent, then add the chain initiator azobisisobutyronitrile, the mass content of the chain initiator 38% of the high boiling point solvent, placed in an oil bath, reacted for 28 h, and the reaction temperature was 80 °C;

[0041] (2) Add 0.8 g polybenzimidazole to the solution, stir to dissolve, then add vinylphosphonic acid, stir to dissolve, add azobisisobutyronitrile, stir at room temperature for 2 h, nitrogen protection, gas flow rate is 100 mL / min;

[0042] (3) Put the solution in an oil bath, stir at 50 °C, and react for 48 h;

[0043] (4) Continue to add 8 mL of N-methylpyrrolidone solvent to the solution, stir for 30 min, add the free radical quencher ceria, stir ultrasonically for 30 min, pou...

Embodiment 3

[0049] A method for preparing a cross-linked polybenzimidazole high-temperature proton exchange membrane with high oxidation resistance and high conductivity, comprising the following steps:

[0050] (1) Dissolve 0.8 g of 1-vinyl-1,2,4-triazole in 10 mL of N-methylpyrrolidone solvent, then add the chain initiator azobisisobutyronitrile, the mass content of the chain initiator 30% of the high boiling point solvent, placed in an oil bath, reacted for 36 h, and the reaction temperature was 70 °C;

[0051] (2) Add 0.5 g polybenzimidazole to the solution, stir to dissolve, then add vinylphosphonic acid, stir to dissolve, add azobisisobutyronitrile, stir at room temperature for 1.5 h, protect with nitrogen, and the gas flow rate is 100 mL / min;

[0052] (3) Put the solution in an oil bath, stir at 80 °C, and react for 24 h;

[0053] (4) Continue to add 5 mL of N-methylpyrrolidone solvent to the solution, stir for 30 min, add the free radical quencher ceria, stir ultrasonically for...

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Abstract

The invention discloses a high-oxidization-resistance and high-conductivity crosslinked type polybenzimidazole high-temperature proton exchange membrane and a preparation method therefor. The crosslinked membrane takes polybenzimidazole as a polymer framework; through polymerization, a crosslinked net-shaped structure is formed in the membrane by taking vinyl phosphonic acid and vinyl triazole as a crosslinking agent; and a free radical quenching agent which can improve the oxidization resistance of the membrane is doped in the membrane to prepare the high-oxidization-resistance and high-conductivity high-temperature proton exchange membrane. The crosslinked high-temperature proton exchange membrane disclosed by the invention has relatively high proton conductivity and excellent dimensional stability in a non-humidifying condition, and has high oxidization resistance, so that the problem of phosphoric acid loss of a polybenzimidazole / phosphoric acid membrane is completely solved, and the bottleneck that the polymer membrane is degraded under attack of free radicals is overcome; and therefore, the proton exchange membrane can be applied to a high-temperature proton exchange membrane fuel cell, a direct alcohol type fuel cell, an electrochemical sensor or other electrochemical apparatuses as the proton exchange membrane.

Description

technical field [0001] The invention belongs to the technical field of fuel cell materials, and in particular relates to a cross-linked polybenzimidazole high-temperature proton exchange membrane with high oxidation resistance and high electrical conductivity and a preparation method thereof. Background technique [0002] Proton exchange membrane fuel cell (PEMFC) is a high-efficiency, clean and environment-friendly power generation device. It is an ideal power source for electric vehicles. application prospects. However, perfluorinated sulfonic acid membrane fuel cells represented by Nafion® are widely used at present, but the proton conductivity of this type of proton exchange membrane is greatly affected by the water content and temperature in the membrane, and the alcohol resistance performance is poor. The working temperature cannot exceed 80 ℃. Because PEMFC is limited by the operating temperature, it faces problems such as poor CO tolerance and difficult water and h...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): H01M8/02H01M8/0239
CPCH01M8/0243Y02E60/50
Inventor 于书淳张燕燕何春霞郭会娟李慧
Owner ZHANGJIAGANG IND TECH RES INST CO LTD DALIAN INST OF CHEM PHYSICS CHINESE ACADEMY OF SCI
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