Imidazolium salt side group-containing poly(ether ether sulfone) anion-exchange membrane used for vanadium batteries, and preparation method thereof

An anion exchange membrane, polyether ether sulfone technology, applied in fuel cell parts, regeneration fuel cells and other directions, can solve the problems of high price, reduced vanadium ion permeability, no diaphragm material, etc., and achieves low cost and preparation process. Simple and easy effects

Active Publication Date: 2015-07-29
NINGBO INST OF MATERIALS TECH & ENG CHINESE ACADEMY OF SCI
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

[0004] Although there are many literature reports on VRB diaphragm research, there is no special diaphragm material suitable for VRB on the market.
At present, VRB mainly uses perfluorosulfonic acid ion exchange membranes that should be commercialized, such as Nafion series membranes produced by DuPont Company of the United States, Dow membranes produced by Dow Company of the United States, Flemion membranes produced by Asahi Glass Company of Japan, Canada Among the BAM membranes produced by Ballard, among them, the Nafion series membranes produced by DuPont have the best performance, are relatively stable in VRB strong acid electrolytes, and have relatively high ion conductivity, but the Nafion membranes have poor vanadium resistance. The important thing is that the price is relatively expensive, which greatly increases the production cost of VRB
[0005] The diaphragm materials in vanadium batteries can be mainly divided into anion exchange membrane and cation exchange membrane. Some commercialized cation exchange membranes have been modified and applied to vanadium batteries to show certain vanadium resistance performance, but due to the cation exchange membrane The negatively charged groups on the exchange membrane can attract positively charged vanadium ions, but cannot fundamentally reduce the permeability of vanadium ions; relatively speaking, the Donan between the positively charged groups on the anion exchange membrane and vanadium ions The effect can relatively prevent the penetration of vanadium ions, and then fundamentally prevent the vanadium electrolytes on both sides of the membrane from cross-contaminating each other and reduce the self-discharge effect of the vanadium battery.

Method used

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  • Imidazolium salt side group-containing poly(ether ether sulfone) anion-exchange membrane used for vanadium batteries, and preparation method thereof
  • Imidazolium salt side group-containing poly(ether ether sulfone) anion-exchange membrane used for vanadium batteries, and preparation method thereof
  • Imidazolium salt side group-containing poly(ether ether sulfone) anion-exchange membrane used for vanadium batteries, and preparation method thereof

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0048] A kind of synthetic method of the polyether ether sulfone that side chain contains imidazole, comprises the following steps:

[0049] (1) In a round bottom flask, add 32.03g (0.258mmol) of 2-methylhydroquinone, 19.48g (0.128mmol) of 2,3,5-trimethylhydroquinone, 111g (0.386mol) ) of dichlorodiphenyl sulfone, 64.8g (0.468mol) of potassium carbonate, 100ml (86.6g) of toluene and 180ml (226.8g) of sulfolane solution, feed nitrogen into the reaction system and set insulation measures, at 150 ° C React for 2 hours to completely remove the solvent and the water in the reactant, and the color turns yellow.

[0050] (2) Raise the temperature to 170°C for 2 hours, remove toluene, and when no toluene evaporates, add the remaining solvent (300ml sulfolane, 378g), and the color becomes dark brown; then continue to heat up to 200°C, react for 5h, and the system Become viscous, stop the reaction.

[0051] (3) Pour the solution into deionized water while it is hot, stir vigorously to...

Embodiment 2

[0061] A kind of synthetic method of the polyether ether sulfone anion membrane containing imidazolium salt, comprises the following steps:

[0062] (1) In a round bottom flask, add 29.37g (0.193mol) of 2,3,5-trimethylhydroquinone, 55g (0.193mol) of dichlorodiphenyl sulfone, and 32.4g (0.234mol) of potassium carbonate , 55ml (47.63g) of toluene and 90ml (113.4g) of sulfolane solution, nitrogen into the reaction system, reacted at 150 ° C for 2h to fully remove the water in the reaction system, the color turned yellow.

[0063] (2) After the temperature rises to 170°C, remove the toluene, remove the insulation layer when the toluene solvent evaporates, add the remaining 150ml (189g) of sulfolane, the color becomes dark brown, then continue to heat up to 200°C, and react for 5 hours, The system became viscous and the reaction was terminated.

[0064] (3) The solution was poured into deionized water while it was hot, stirred and precipitated, and washed three times in succession...

Embodiment 3

[0074] A kind of synthetic method of the polyether ether sulfone anion membrane containing imidazolium salt, comprises the following steps:

[0075] (1) In a round bottom flask, add 23.96g (0.193molmmol) of 2-methylhydroquinone, 55g (0.193mol) of dichlorodiphenyl sulfone, 32.4g (0.234mol) of potassium carbonate, 55ml (47.6g ) of toluene and 90ml (113.4g) of sulfolane, nitrogen gas was passed into the reaction system, and the reaction was carried out at 150° C. for 2 hours to fully remove the water in the reaction system, and the color turned yellow.

[0076] (2) After the temperature rises to 170°C, remove the toluene, remove the insulation layer when the toluene solvent evaporates, add the remaining 150ml (189g) of sulfolane, the color becomes dark brown, then continue to heat up to 200°C, and react for 5 hours, The system became viscous and the reaction was terminated.

[0077] (3) The solution was poured into deionized water while it was hot, stirred and precipitated, and ...

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Abstract

The invention discloses an imidazolium salt side group-containing poly(ether ether sulfone) anion-exchange membrane which can be used for vanadium batteries. The imidazolium salt side group-containing poly(ether ether sulfone) anion-exchange membrane possesses a structure represented by formula (I). According to a preparation method, a bisphenol monomer containing methyl and dichlorodiphenylsulfone are taken as raw materials; poly(ether ether sulfone) containing methyl is obtained via copolymerization; bromination reaction is carried out so as to obtain polymers with different bromination degrees; an imidazole agent is added for amination and quaternization so as to obtain poly(ether ether sulfone) containing imidazolium salt side groups; and at last the imidazolium salt side group-containing poly(ether ether sulfone) anion-exchange membrane is prepared. Poly(ether ether sulfone) main chains possess relatively excellent physical, chemical, and mechanical properties; the imidazolium salt side group possess relatively excellent chemical stability and ion exchange performance; so that using requirements of vanadium redox flow cell proton exchange membranes can be satisfied; the imidazolium salt side group-containing poly(ether ether sulfone) anion-exchange membrane possesses relatively high ionic conductivity, low vanadium ion permeability, and excellent battery cycling performance and chemical stability.

Description

technical field [0001] The invention belongs to the field of functional polymer materials and the field of electrochemistry, and specifically relates to a polyether ether sulfone anion exchange membrane containing imidazole side groups that can be used for vanadium batteries and a preparation method thereof. Background technique [0002] All-Vanadium Redox Flow Battery (VRB), referred to as vanadium battery, is a very promising large-scale energy storage battery. It was first developed by Professor Skyllas-Kazacos of the University of New South Wales in 1985. Year to V 5+ / V 4+ and V 2+ / V 3+ Vanadium ion solutions with different valence states were successfully developed as positive and negative electrode electrolytes, and the concept was first proposed. Vanadium batteries use redox reactions between vanadium ions in different valence states to realize the conversion between chemical energy and electrical energy. The advantages of good stability and pollution-free envi...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C08J5/22C08L71/10C08G65/40H01M8/02H01M8/18
CPCY02E60/50
Inventor 薛立新陆地聂锋温乐乐
Owner NINGBO INST OF MATERIALS TECH & ENG CHINESE ACADEMY OF SCI
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