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Mixed matrix type cation exchange membrane and preparation method thereof

A technology of cation exchange membrane and mixed matrix, which is applied in the field of mixed matrix cation membrane and its preparation, can solve the problems of poor ion selectivity, tensile resistance and swelling resistance, and achieves inhibition of water absorption and swelling and good tensile properties. Effect

Active Publication Date: 2019-10-15
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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  • Mixed matrix type cation exchange membrane and preparation method thereof
  • Mixed matrix type cation exchange membrane and preparation method thereof
  • Mixed matrix type cation exchange membrane and preparation method thereof

Examples

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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

The invention relates to a mixed matrix type cation exchange membrane and a preparation method thereof. The cation exchange membrane takes a sulfonated modified polymer material as a substrate and isdoped with Schiff base type covalent organic framework materials loaded with different functional groups. The preparation method comprises the following steps of: sequentially performing monomer preparation and polymerization of a covalent organic framework material, sulfonation modification of a polymer, uniform mixing of the covalent organic framework material and a sulfonated polymer, and flow-spreading film formation; and finally, performing acid treatment to obtain the cation exchange membrane. The covalent organic framework material can effectively improve the vanadium resistance of themembrane based on the rigid porous structure; the organic porous structure of the covalent organic framework and the different functional modifications can partially compensate the loss of membrane proton conductivity caused by the introduction of particles; the rigid framework can obviously inhibit the swelling in the membrane and can improve the tensile strength of the membrane; COFs is composedof organic structures and can promote compatibility between sulfonated polymers and covalent organic framework materials; and moreover, the polymer as the substrate can improve the film forming performance of the covalent organic framework material, so that the covalent organic framework material has the 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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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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