A kind of cation exchange membrane based on cyclodextrin crosslinked polymer and its preparation method and application

A technology of cation exchange membrane and cross-linked polymer, applied in the field of ion exchange membrane, can solve the problems of vanadium resistance ability, mechanical strength to be improved, low efficiency of vanadium battery, poor ion selectivity, etc., and achieves cheap raw material source and mechanical properties Improve and reduce the effect of membrane molecular porosity

Active Publication Date: 2020-07-14
DALIAN RONGKE POWER
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

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Problems solved by technology

[0002] At present, the ion-exchange membranes used in all-vanadium redox flow energy storage batteries are mainly produced by DuPont of the United States. A series of perfluorosulfonic acid ion exchange membranes, which can exist stably under strong oxidation and strong acidic conditions, have good chemical stability and high ion conductivity, but this membrane was originally designed and developed for the chlor-alkali industry. It is not developed and designed for all-vanadium redox flow energy storage batteries, so its application in this field has certain limitations, such as poor ion selectivity, poor vanadium resistance performance, and low efficiency of vanadium batteries. At present, a large number of researchers have begun to work on Research and development of non-fluorine ion-exchange membranes. The non-fluorine ion-exchange membranes for all-vanadium redox flow batteries that have been developed mainly include polyaryletherketone, polyarylethersulfone, polyimide, and polyetheretherketone. The main chain has a certain rigidity, ion exchange membranes with ion exchange groups, these types of ion exchange membranes have a certain vanadium resistance effect, mainly through the use of anion exchange groups to repel vanadium ions, or increase the gap between membrane molecules , means that the larger hydrated vanadium ions cannot pass through
However, the vanadium resistance and mechanical strength of the above films need to be improved.

Method used

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  • A kind of cation exchange membrane based on cyclodextrin crosslinked polymer and its preparation method and application

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0031] Disperse 113.5g of β-cyclodextrin (0.1mol) into 500mL of tap water with pH=1-2, stir well, add 81.1g of formaldehyde solution with a mass fraction of 37% (effective formaldehyde content is 1mol), and react at 40°C 8h, filter with suction, wash with deionized water, fully dry and pulverize to get powder; disperse the powder into anhydrous DMF, gradually add 10.86g of acryloyl chloride liquid under constant stirring, react at 65°C for 15h, and then pump it out with an oil pump The acryloyl chloride and the HCl gas generated in the system did not participate in the reaction, and the obtained dispersion liquid was gradually added dropwise to acetone to precipitate, washed three times with acetone, and dried to obtain a solid; to the obtained solid, add 3 times its mass (excess) Concentrated sulfuric acid, stirred at 0-5°C for 2 hours, then gradually added the reaction system to excess ice acetone (to precipitate the cyclodextrin polymer), then filtered and dried to obtain a ...

Embodiment 2

[0034] The difference between this example and Example 1 is that the amount of acryloyl chloride is 18.1 g, and the molar ratio of acryloyl chloride to β-cyclodextrin is 2:1.

Embodiment 3

[0036] The difference between this example and Example 1 is that the amount of acryloyl chloride used is 27.15 g, and the molar ratio of acryloyl chloride to β-cyclodextrin is 3:1.

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Abstract

The invention relates to the field of ion exchange membranes, in particular, a cation exchange membrane based on a cyclodextrin crosslinked polymer and a preparation method and applications thereof, and discloses an ion exchange membrane suitable for a flow battery, in particular, an ion exchange membrane suitable for a vanadium battery. Cyclodextrin is highly crosslinked and polymerized, the molecular gap of the cation exchange membrane is obviously reduced, and thus the cation exchange membrane has a strong vanadium inhibiting performance, good mechanical properties, and high vanadium battery efficiency, can replace a conventional ion exchange membrane, and is applied to the vanadium battery energy storage field. The invention provides a brand new non-fluorine ion exchange membrane and apreparation method. The raw material sources are wide, the raw material price is low, the cost is effectively controlled, moreover, the preparation technology is simple, the conditions are mild, andthe preparation method is suitable for large scale industrial production.

Description

technical field [0001] The invention relates to the field of ion-exchange membranes, in particular to a cyclodextrin cross-linked polymer-based cation-exchange membrane and a preparation method and application thereof, which are suitable for ion-exchange membranes for liquid flow batteries, especially ion-exchange membranes for vanadium batteries. Background technique [0002] At present, the ion-exchange membranes used in all-vanadium redox flow energy storage batteries are mainly produced by DuPont of the United States. A series of perfluorosulfonic acid ion exchange membranes, which can exist stably under strong oxidation and strong acidic conditions, have good chemical stability and high ion conductivity, but this membrane was originally designed and developed for the chlor-alkali industry. It is not developed and designed for all-vanadium redox flow energy storage batteries, so its application in this field has certain limitations, such as poor ion selectivity, poor va...

Claims

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Application Information

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Patent Type & Authority Patents(China)
IPC IPC(8): C08F251/00C08F220/06C08J5/18H01M8/18
CPCC08F251/00C08J5/18C08J2333/02C08J2405/16H01M8/188C08F220/06Y02E60/50
Inventor 李全龙张华民张涛徐鹤英王禛胡影梁加富
Owner DALIAN RONGKE POWER
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