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Self-crosslinking alkaline anion exchange membrane and preparation method and application thereof

A basic anion and exchange membrane technology, which is applied in the direction of electrical components, circuits, fuel cell parts, etc., can solve the problem of unsatisfactory mechanical properties of basic polyarylether ionomer materials, reduced long-term chemical stability in the working environment, Highly ionized and loss of mechanical properties, etc., to achieve the effect of facilitating ion transmission, process environmental protection and easy operation, and improving the stability of the membrane structure

Active Publication Date: 2014-03-12
SOUTH CHINA UNIV OF TECH
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

Most of the basic polyarylether ionomer materials that have been developed are mixed with each other between the hydrophilic phase and the hydrophobic phase, resulting in a decrease in alcohol resistance, a decrease in the long-term chemical stability of the working environment, and a decrease in ion conductivity, and limited Due to the linear molecular structure, highly ionized and loses mechanical properties, it cannot be practically applied
Even though the introduction of a long sequence structure into the basic polyarylether ionomer material realizes the separation of the hydrophilic phase and the hydrophobic phase and enhances the membrane ion conductivity, it does not improve the mechanical properties of the basic polyarylether ionomer material. ideal

Method used

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  • Self-crosslinking alkaline anion exchange membrane and preparation method and application thereof
  • Self-crosslinking alkaline anion exchange membrane and preparation method and application thereof
  • Self-crosslinking alkaline anion exchange membrane and preparation method and application thereof

Examples

Experimental program
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Effect test

Embodiment 1

[0043] The following steps are used to prepare cross-linked basic multi-block polyarylether ionomer anion exchange membrane:

[0044] (1) Synthesis of hydrophilic segment: 2.5847g (0.0107mol) 3,3′,5,5′‐tetramethylbiphenylbisphenol, 2.5425g (0.01mol) 4,4′‐difluorodiphenylsulfone, 2.0729g (0.015mol) anhydrous potassium carbonate mixed in 20mL N-methylpyrrolidone, then add 20mL toluene, under the protection of nitrogen, carry water at 140°C for 4 hours, then remove the water-carrying agent, raise the temperature to 180°C for 12h , then add 0.1292g (0.000535mol) 3,3′,5,5′‐tetramethylbiphenylbisphenol, add solvent to dilute after reacting for 3h, drop into 300mL methanol containing 3mL hydrochloric acid, and obtain a flocculent precipitate, That is, the hydrophilic segment oligomer is detected by H NMR spectrum, such as figure 1 As shown, in the figure, a is the hydrogen corresponding to the methyl group, b is the hydrogen on the benzene ring connected to the methyl group, c and d...

Embodiment 2

[0061] (1) Synthesis of hydrophilic segment: 2.7261g (0.0113mol) 3,3′,5,5′‐tetramethylbiphenylbisphenol, 2.5425g (0.01mol) 4,4′‐difluorodiphenylsulfone, Mix 2.0729g (0.015mol) of anhydrous potassium carbonate in 17mL N,N-dimethylacetamide, then add 20mL of toluene, under the protection of nitrogen, carry water at 140°C for 4 hours, remove the water-carrying agent, and heat up to React at 180°C for 12 hours, then add 0.1363g (0.000565mol) 3,3′,5,5′‐tetramethylbiphenyl bisphenol, add solvent to dilute after reacting for 3 hours, drop into 400mL methanol containing 4mL hydrochloric acid, and obtain flocculation Like precipitate, that is, the oligomer of the hydrophilic segment, detected by hydrogen nuclear magnetic resonance spectrum, the length of the oligomer of the hydrophilic segment is 9, expressed as X9.

[0062] (2) Hydrophobic segment synthesis: 3.5243g (0.01mol) bis(4,4'‐hydroxyphenyl)diphenylmethane, 2.8603g (0.0113mol) 4,4'‐difluorodiphenylsulfone, 2.0729g (0.015mol) ...

Embodiment 3

[0073] (1) Synthesis of hydrophilic segment: 3.2681g (0.0107mol) bis(3,5-dimethyl-4-hydroxyphenyl) sulfone, 2.5425g (0.01mol) 4,4'-difluorodiphenyl sulfone, 2. Mix 0729g (0.015mol) of anhydrous potassium carbonate in 14mL of sulfolane, then add 20mL of toluene, under the protection of nitrogen, carry water at 140°C for 6 hours, then remove the water-carrying agent, raise the temperature to 200°C for 12 hours, then add 0.1634 g (0.000535mol) bis(3,5-dimethyl-4-hydroxyphenyl) sulfone, add solvent to dilute after reacting for 3 hours, drop into 500mL methanol containing 5mL hydrochloric acid, obtain flocculent precipitate, that is, hydrophilic segment oligomerization The product was detected by proton nuclear magnetic resonance spectroscopy, and the length of the oligomer in the hydrophilic segment was 17, which was expressed as X17.

[0074] (2) Hydrophobic segment synthesis: 3.5243g (0.01mol) bis(4,4'-hydroxyphenyl) diphenylmethane and, 2.7120g (0.0107mol) 4,4'-difluorodiphenyl...

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Abstract

The invention discloses a self-crosslinking alkaline anion exchange membrane and a preparation method and application thereof. The exchange membrane is prepared from a crosslinking alkaline segmented polyarylether ionomer. The preparation method comprises the following steps: dissolving the segmented polyarylether ionomer into a polar solvent; feeding segmented polyarylether, N-bromosuccinimide and azodiisobutyronitrile in a molar ratio of 1:(2-5):(0.1-0.25); reacting under nitrogen protection at the temperature of 80-85 DEG C for 2-6 hours; washing and drying in vacuum to obtain bromomethylated segmented polyarylether; performing solid self-crosslinking, ionization and alkalization to obtain the self-crosslinking alkaline anion exchange membrane. The method has the advantages of short reaction time and avoidance of the use of a carcinogenic reagent; the prepared alkaline self-crosslinking anion exchange membrane is high in ion conductivity, chemical stability and mechanical performance, can be taken as a fuel battery alkaline ion exchange membrane, and has a wide application prospect.

Description

technical field [0001] The invention relates to anion-exchange membranes, in particular to anion-exchange membranes based on cross-linked alkaline multi-block polyarylether ionomer materials and their application in alkaline fuel cells. Background technique [0002] Fuel cells are known as the preferred power generation technology in the 21st century due to their advantages such as high efficiency and low pollution. Compared with proton exchange membrane fuel cells, alkaline anion exchange membrane fuel cells (AEMFC) have the following advantages: (1) fuel oxidation speed is faster under alkaline conditions than under acidic conditions; (2) low fuel penetration and avoid Cathode accumulation of water; (3) There is no reaction intermediate product poisoning the electrode catalyst, the catalytic electrode can use some commonly used electrodes, such as silver, nickel, etc., thereby reducing the manufacturing cost of the battery system. [0003] Anion exchange membrane is a key...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): H01M8/02C08G65/48C08J5/22
CPCY02E60/50C08G65/48C08G2650/20C08G2650/46C08J5/2256C08J5/2287C08J2371/00H01M4/94
Inventor 李秀华王柳婵程珊珊陶进雄聂光辉
Owner SOUTH CHINA UNIV OF TECH