Preparation method of amphoteric functional PEEK (polyetheretherketone) ion exchange membrane

An ion exchange membrane, polyether ether ketone technology, which is applied in the field of preparation of high ion selectivity amphoteric functional ion exchange membrane of all-vanadium redox flow battery, can solve the problems of high price, poor ion selectivity, and limited membrane commercial application. , to achieve the effect of preventing permeation, high ion selectivity, high Coulombic efficiency and energy conversion efficiency

Active Publication Date: 2017-06-30
DALIAN UNIV OF TECH
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  • Abstract
  • Description
  • Claims
  • Application Information

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Problems solved by technology

At present, commercialized flow batteries mainly use Nafion membrane developed by DuPont of the United States. Nafion membrane has excellent performance in terms of electrochemical performance and service life, but due to its high price, it is especially used in all-vanadium flow energy storage batteries. There are disadvantages such as poor ion selectivity, which limits the commercial application of the membrane

Method used

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  • Preparation method of amphoteric functional PEEK (polyetheretherketone) ion exchange membrane
  • Preparation method of amphoteric functional PEEK (polyetheretherketone) ion exchange membrane
  • Preparation method of amphoteric functional PEEK (polyetheretherketone) ion exchange membrane

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Embodiment 1

[0028] Preparation of imidazole sodium salt: under nitrogen atmosphere, disperse sodium hydride in tetrahydrofuran, add dropwise imidazole / tetrahydrofuran solution, stir magnetically for 2 hours, remove solvent to obtain white solid which is imidazole sodium salt, (sodium hydride:imidazole:tetrahydrofuran=0.48 g:1.36g:40ml);

[0029] Polyetheretherketone halomethylation: prepare 1g of polyetheretherketone into a w / v concentration of 1% polyetheretherketone / concentrated sulfuric acid solution; add 18mL of chloromethyl octyl ether, stir and react at -13°C for 15min; Precipitate in water, wash repeatedly until neutral, and dry at room temperature to obtain chloromethylated polyether ether ketone;

[0030] Polyetheretherketone imidazole modification: Take 1g of chloromethylated polyetheretherketone (DC=0.76) and dissolve it in 20ml of N-methylpyrrolidone. After it is completely dissolved, add imidazole sodium 1.25 times the amount of chloromethyl substance , stirred at room tempe...

Embodiment 2

[0034] Preparation of imidazole sodium salt: under nitrogen atmosphere, sodium hydride was dispersed in acetonitrile, imidazole / acetonitrile solution was added dropwise, magnetically stirred for 2 hours, the solvent was removed to obtain a white solid which was imidazole sodium salt, (sodium hydride: imidazole: tetrahydrofuran = 0.48 g:1.36g:40ml);

[0035] Halomethylation of polymers: Prepare 1g of polyetheretherketone into a w / v concentration of 1.25% polyetheretherketone methanesulfonic acid solution; add 18mL of chloromethyl octyl ether and 0.6mL of tin tetrachloride, Stir and react for 45 minutes; pour into water to precipitate, wash repeatedly until neutral, and dry at room temperature to obtain chloromethylated polyether ether ketone;

[0036] Polymer imidazole modification: take 1g of chloromethylated polyetheretherketone (DC=0.76) and dissolve it in 20ml of N-methylpyrrolidone. ℃ for 8 hours, precipitated in deionized water, washed several times, and dried to obtain ...

Embodiment 3

[0040] Preparation of imidazole sodium salt: under nitrogen atmosphere, sodium hydride was dispersed in acetonitrile, imidazole / acetonitrile solution was added dropwise, magnetically stirred for 2 hours, the solvent was removed to obtain a white solid which was imidazole sodium salt, (sodium hydride: imidazole: tetrahydrofuran = 0.48 g:1.36g:40ml);

[0041] Halomethylation of polymers: Prepare 1g of polyetheretherketone into a w / v concentration of 1.25% polyetheretherketone methanesulfonic acid solution; add 18mL of chloromethyl octyl ether and 0.6mL of tin tetrachloride, Stir and react for 150 minutes; pour into water to precipitate, wash repeatedly until neutral, and dry at room temperature to obtain chloromethylated polyether ether ketone;

[0042] Polymer imidazole modification: Take 1g of chloromethylated polyetheretherketone (DC=1.04) and dissolve it in 20ml of N-methylpyrrolidone. After stirring for 24 hours, it was precipitated in deionized water, washed several times...

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Abstract

The invention discloses a preparation method of an amphoteric functional PEEK (polyetheretherketone) ion exchange membrane, and particularly relates to a preparation method of an ion exchange membrane having high ion selectivity and used for a VFB (vanadium flow battery). Side chains of a membrane material contain amphoteric functional groups. The preparation method comprises steps as follows: 1) preparation of sodium imidazolate; 2) halomethylation of PEEK; 3) imidazole modification of PEEK; 4) bifunctionalization of PEEK. The amphoteric functional groups are introduced into the ion exchange membrane, the vanadium resisting capability of the membrane is improved by use of the Donnan effect of electropositive groups, proton conduction can be guaranteed through contained sulfonate radical, and the ion exchange membrane having high ion selectivity is obtained. The preparation process is simple and low in cost, and the prepared amphoteric ion exchange membrane has high ion selectivity and is suitable for being applied to the VFB.

Description

technical field [0001] The invention relates to a method for preparing an amphoteric functionalized ion exchange membrane, in particular to a method for preparing an amphoteric functionalized ion exchange membrane with high ion selectivity for an all-vanadium redox flow battery. Background technique [0002] Flow battery energy storage technology is a new technology for large-scale and high-efficiency electrochemical energy storage. The battery pack realizes the electric energy storage function of "electrical energy-chemical energy-electrical energy" through the change of valence state of the reactive material. Compared with other energy storage technologies, liquid flow energy storage batteries have the following advantages: high energy efficiency (>75%), flexible system design, free site selection, no pollution, low maintenance and operation costs, safety and environmental protection, etc., can be widely used in Wind energy, solar energy and other renewable energy gene...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): H01M8/1025H01M8/1069H01M8/1072H01M8/1088H01M8/18
CPCH01M8/1025H01M8/1069H01M8/1072H01M8/1088H01M8/188Y02E60/50
Inventor 焉晓明张彩绵贺高红
Owner DALIAN UNIV OF TECH
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