A kind of mixed matrix type cation exchange membrane and preparation method thereof

A cation exchange membrane and mixed matrix technology, applied in the field of mixed matrix cation membrane and its preparation, can solve the problems of poor ion selectivity, stretching resistance and swelling resistance, etc. The effect of vanadium resistance and good battery performance

Active Publication Date: 2022-04-12
DALIAN UNIV OF TECH
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

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Problems solved by technology

[0007] Aiming at the problems of poor ion selectivity, stretch resistance and swelling resistance of the cation exchange membrane used in all vanadium redox flow batteries, the present invention proposes a new mixed matrix cation exchange membrane based on covalent organic framework material and its preparation method

Method used

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  • A kind of mixed matrix type cation exchange membrane and preparation method thereof
  • A kind of mixed matrix type cation exchange membrane and preparation method thereof
  • A kind of mixed matrix type cation exchange membrane and preparation method thereof

Examples

Experimental program
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Effect test

Embodiment 1

[0052] Synthesis of 1,3,5-trialdehyde phloroglucinol: under nitrogen atmosphere, add 6.014g phloroglucinol, 15.098g urotropine and 90mL trifluoroacetic acid, react at 100°C for 2h, add 150mL 3mol / L hydrochloric acid aqueous solution, continue to react for 0.5h. After it was cooled to room temperature, it was filtered with diatomaceous earth, and the filtrate was extracted with 350 mL of dichloromethane. The organic phase was dried over anhydrous magnesium sulfate and rotary evaporated to obtain a yellowish powder, which was rinsed with an appropriate amount of hot ethanol and dried.

[0053] Synthesis of TpEB covalent organic framework material: weigh 63mg 1,3,5-trialdehyde phloroglucinol (Tp) and 177.5mg ethidium bromide (EB) in a ball mill jar, add 1 drop of mesitylene / The mixed solution of dioxane (volume ratio is 1:1) and 1 drop of 3mol / L hydrochloric acid solution are used as a catalyst, poured into some ball milling beads, and after grinding at a constant speed for 90 m...

Embodiment 2

[0057] Synthesis of 1,3,5-trialdehyde phloroglucinol: under nitrogen atmosphere, add 6.014g phloroglucinol, 15.098g urotropine and 90mL trifluoroacetic acid, react at 80°C for 2.5h, add 150mL of 3mol / L hydrochloric acid aqueous solution, continue to react for 1h. After it was cooled to room temperature, it was filtered with diatomaceous earth, and the filtrate was extracted with 350 mL of dichloromethane. The organic phase was dried over anhydrous magnesium sulfate and rotary evaporated to obtain a yellowish powder, which was rinsed with an appropriate amount of hot ethanol and dried.

[0058] TpBD-Me 2 Synthesis of covalent organic framework materials: Weigh 63mg 1,3,5-trialdehyde phloroglucinol (Tp) and 95.6mg bi-o-toluidine (BD-Me 2 ) in the ball mill tank, add 1 drop of mesitylene / dioxane (1:1 volume ratio) mixed solution to aid grinding, pour some ball mill beads, and grind at a uniform speed for 90 minutes, collect the resulting solids and use Soxhlet extraction with m...

Embodiment 3

[0061] Synthesis of 1,3,5-trialdehyde phloroglucinol: under nitrogen atmosphere, add 6.014g phloroglucinol, 15.098g urotropine and 90mL trifluoroacetic acid, react at 120°C for 2.25h, add 150mL of 3mol / L hydrochloric acid aqueous solution, continue to react for 0.75h. After it was cooled to room temperature, it was filtered with diatomaceous earth, and the filtrate was extracted with 350 mL of dichloromethane. The organic phase was dried over anhydrous magnesium sulfate and rotary evaporated to obtain a yellowish powder, which was rinsed with an appropriate amount of hot ethanol and dried.

[0062] TpBD-(OH) 2 Synthesis of covalent organic framework materials: Weigh 63mg 1,3,5-trialdehyde phloroglucinol (Tp) and 90.6mg 2,4-dihydroxybenzidine (BD-OH 2 ) in the ball mill tank, add 1 drop of mesitylene / dioxane (volume ratio: 1:1) mixed solution for grinding aid and 1 drop of 3mol / L hydrochloric acid solution as catalyst, pour some ball mill beads, and grind at a uniform speed fo...

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Abstract

A mixed matrix type cation exchange membrane and a preparation method thereof. The cation membrane is based on a sulfonated modified polymer material and doped with Schiff base type covalent organic framework materials loaded with different functional groups. During the preparation, the monomer preparation and polymerization of the covalent organic framework material, the sulfonation modification of the polymer, the uniform mixing of the covalent organic framework material and the sulfonated polymer, and the extension of the membrane are carried out, and finally the cation exchange membrane is obtained by acid treatment. . Based on its rigid porous structure, the covalent organic framework material can effectively improve the vanadium barrier performance of the membrane; the organic porous structure of the covalent organic framework and different functional modifications can partially compensate the loss of the proton conductivity of the membrane caused by the introduction of particles; its rigidity The framework can significantly inhibit swelling in the membrane and improve the tensile strength of the membrane; COFs are composed of organic structures, which can promote the compatibility between sulfonated polymers and covalent organic framework materials; polymers as substrates can improve the synthesis of covalent organic framework materials. Membrane performance, so that it has better mechanical strength.

Description

technical field [0001] The invention belongs to the field of battery membrane materials, and relates to a mixed-matrix cationic membrane and a preparation method thereof. Background technique [0002] With the intensification of environmental pollution, the development of renewable new energy sources such as solar energy, wind energy, and water energy has attracted widespread attention. However, traditional renewable energy power generation devices usually face problems such as the mismatch between power generation peaks and power consumption peaks, and often require large-scale energy storage devices to "shave peaks and fill valleys". As a new type of clean, high-response, long-life, electrolyte-renewable energy storage device, all-vanadium redox flow battery has great application potential in the field of new energy. [0003] As a key component in the all-vanadium redox flow battery, the ion-exchange membrane plays the role of isolating the negative and positive electrode...

Claims

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Application Information

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Patent Type & Authority Patents(China)
IPC IPC(8): H01M8/0221H01M8/0223H01M8/0226H01M8/18C08G12/08C08G12/26
CPCH01M8/188H01M8/0226H01M8/0223H01M8/0221C08G12/08C08G12/26Y02E60/50
Inventor 张凤祥李旅崔雯昱张华清马玲玲
Owner DALIAN UNIV OF TECH
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