Novel sulfonated polybenzimidazole copolymer, crosslinked membrane, preparation method and application thereof

A technology for sulfonating polybenzimidazole and polybenzimidazole, which is applied in the parts of fuel cells, renewable fuel cells, etc., can solve the problems of difficulty in precise control of crosslinking density, reduction in proton conductivity, and difficulty in popularization and application. Achieve the effects of excellent chemical stability, high mechanical strength and thermal stability, and simple preparation process

Active Publication Date: 2018-07-17
SHANGHAI JIAOTONG UNIV
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

However, the imidazole group in the polybenzimidazole structure is basic and neutralizes with the sulfonic acid group to form imidazolium sulfonate, which greatly reduces the proton conductivity of the membrane.
In order to obtain a higher proton conductivity, polybenzimidazole must be highly sulfonated, but too high a degree of sulfonation makes the polybenzimidazole membrane highly swellable or even dissolved in water
Covalent crosslinking is an effective method to inhibit membrane swelling. The literature (Polymer2007, 48, 5556-5564) reported that sulfonated polybenzimidazole was first doped with phosphoric acid, and then dried in vacuum at 180°C for 20 hours to prepare sulfonated polybenzimidazole. The method of polybenzimidazole cross-linked film, this method requires high temperature, vacuum, and long-term treatment of the film, and the cross-linking density is difficult to accurately control, and it is difficult to popularize and apply in industry

Method used

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  • Novel sulfonated polybenzimidazole copolymer, crosslinked membrane, preparation method and application thereof
  • Novel sulfonated polybenzimidazole copolymer, crosslinked membrane, preparation method and application thereof
  • Novel sulfonated polybenzimidazole copolymer, crosslinked membrane, preparation method and application thereof

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0035] Example 1: A side sulfonated polybenzimidazole SOPBI-NH 2 Synthesis of (9 / 1)

[0036] first step:

[0037]Add 100g polyphosphoric acid, 2.14g (10mmol) 3,3'-diaminobenzidine (DAB), 2.3220g (9mmol) 4 , 4′-diphenyl ether dicarboxylic acid (DCDPE) and 0.1812g (1mmol) 5-aminoisophthalic acid (APTA), under a nitrogen atmosphere, first heat up to 150°C for 2h, then continue to heat up to 190°C for 20h . After the reaction, the polymer solution was poured into 300g of ice water, and the precipitated product was washed three times with deionized water, then soaked in 2wt% sodium bicarbonate solution for one day, filtered with suction, and the obtained solid product was washed with deionized water until neutral, and finally dried at 60°C under vacuum for 20h.

[0038] Step two:

[0039] Under ice bath and nitrogen protection, 2 g of the product prepared by the first step reaction and 20 mL of fuming sulfuric acid (20% SO 3 ), stirred for 0.5 hours. The ice bath was removed...

Embodiment 2

[0041] Example 2: A side sulfonated polybenzimidazole SOPBI-NH 2 Synthesis of (5 / 1)

[0042] Control the molar ratio of 4,4'-diphenyl ether dicarboxylic acid (DCDPE) to 5-aminoisophthalic acid (APTA) to be 5:1, and the rest of the operating steps and conditions are exactly the same as in Example 1 to obtain DCDPE and APTA Sulfonated polybenzimidazole copolymer SOPBI-NH with a unit ratio of 5:1 2 (5 / 1). Its ion exchange capacity was measured by titration method to be 2.87meq / g.

Embodiment 3

[0043] Example 3: A polybenzimidazole SOPBI-NH containing side amino groups 2 Synthesis of (4 / 1)

[0044] Control the molar ratio of 4,4'-diphenyl ether dicarboxylic acid (DCDPE) to 5-aminoisophthalic acid (APTA) to be 4:1, and the rest of the operating steps and conditions are exactly the same as in Example 1 to obtain DCDPE and APTA Sulfonated polybenzimidazole copolymer SOPBI-NH with a unit ratio of 4:1 2 (4 / 1). Its ion exchange capacity was measured by titration method to be 2.76meq / g.

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Abstract

The invention discloses a sulfonated polybenzimidazole copolymer comprising pendant amino and a sulfonated polybenzimidazole crosslinked membrane obtained by crosslinking the copolymer as well as a preparation method therefor and application thereof. The prepared sulfonated polybenzimidazole crosslinked membrane has good mechanical property, very high ion exchange capacity, excellent chemical stability and extremely vanadium ion transmittance. An all vanadium liquid flow battery which takes the sulfonated polybenzimidazole crosslinked membrane prepared by the preparation method as a diaphragm has very high coulombic efficiency and energy efficiency, very low self discharge rate and good charge-discharge circulating performance. The comprehensive performance is remarkably superior to that of an all vanadium liquid flow battery which takes Nafion117 as the diaphragm.

Description

technical field [0001] The invention relates to the field of proton exchange membranes, in particular to a sulfonated polybenzimidazole crosslinked membrane and a preparation method thereof. Background technique [0002] A fuel cell is a device that directly converts the chemical energy of fuel into electrical energy. It has outstanding advantages such as high energy conversion efficiency, cleanliness, and no pollution. It has a wide range of applications in the fields of electric vehicles, distributed power stations, and electronic equipment. Application prospect. All-vanadium redox flow batteries are considered to be ideal energy storage devices for clean energy such as photovoltaic power generation and wind power generation due to their independent output power and storage capacity, fast response, deep discharge, room temperature working conditions, and long cycle life. Proton exchange membrane is the core component of fuel cell and all-vanadium redox flow battery. At p...

Claims

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Application Information

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Patent Type & Authority Patents(China)
IPC IPC(8): C08G73/18C08J3/24C08J5/18H01M8/02H01M8/18
CPCY02E60/50
Inventor 房建华郭晓霞夏子君应黎彬
Owner SHANGHAI JIAOTONG UNIV
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