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A kind of tertiary amino amphoteric ion exchange membrane and preparation method thereof

A technology of amphoteric ions and exchange membranes, applied in fuel cells, electrical components, electrochemical generators, etc., can solve the problems of high vanadium ion permeability and large surface resistance, achieve excellent battery performance, improve stability, and improve membrane The effect of vanadium barrier properties

Active Publication Date: 2021-03-26
DALIAN UNIV OF TECH
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

[0004] The most commonly used ion exchange membrane is proton ion exchange membrane (PEM). Although PEM has high proton conductivity, its vanadium ion permeability is relatively high.
The corresponding anion exchange membrane (AEM) has good resistance to vanadium because of its positively charged groups that can repel vanadium ions, but its surface resistance is relatively large.

Method used

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  • A kind of tertiary amino amphoteric ion exchange membrane and preparation method thereof
  • A kind of tertiary amino amphoteric ion exchange membrane and preparation method thereof
  • A kind of tertiary amino amphoteric ion exchange membrane and preparation method thereof

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0028] Under the condition of an ice-water bath, 5 g of polyether ether ketone (PEEK) was dissolved in 100 ml of concentrated sulfuric acid, and vigorously stirred. When the polymer was completely dissolved, the reaction temperature was increased to 50°C, and the reaction was carried out for 7 hours. After the reaction was completed, the reaction solution was poured into ice water in a stirring state, and a sulfonated polyetheretherketone (SPEEK) polymer with a sulfonation degree of 78% was precipitated. The product was washed with deionized water until neutral, and completely dried under vacuum environment;

[0029] Dissolve 0.15 g of the synthesized SPEEK in 4 ml of DMF and cast at 50°C for 24 hours to form a film. The membrane was soaked in deionized water for 12 h at room temperature to remove impurities. Then, the membrane was soaked in acid for 12h to make it fully ion exchanged. The membrane is then soaked in deionized water to remove excess acid. The SPEEK film is ...

Embodiment 2

[0031] Under stirring state, 3g PPO is dissolved in 25ml dichloromethane to make PPO solution, then in another three-necked flask, add 25ml dichloromethane, add 2.4g anhydrous aluminum chloride and vigorously stir under nitrogen protection, in 1.83ml of 4-fluorobenzoyl chloride was slowly added under ice-water bath conditions. Then the PPO solution prepared before was added into this mixed solution, and reacted at 60° C. for 10 h. After the reaction is completed, the reaction solution is poured into a large amount of ethanol, and the precipitate is an acylated PPO polymer with a substitution degree of 50%. Wash the polymer repeatedly with water and ethanol, and dry it in vacuum;

[0032] Dissolve 1g of acylated PPO synthesized above in 30ml of dimethylacetamide (DMAC), then add 1g of 2,4,6-tris(dimethylaminomethyl)phenol and 1.6g of cesium carbonate, and react at 110°C 10h. During the reaction, nitrogen gas was bubbled through the solution to facilitate the removal of water...

Embodiment 3

[0035] The main chain polymers SPEEK and PPO-TA were prepared as described in Example 1 and Example 2. 0.1425g SPEEK and 0.0075g PPO-TA were dissolved in 4ml DMF respectively, and cast at 50°C for 24h to form a film. The membrane was soaked in deionized water for 12 h at room temperature to remove impurities. Then, the membrane was soaked in acid for 12h to make it fully ion exchanged. The membrane is then soaked in deionized water to remove excess acid. Make SPEEK / PPO-TA (5%) membrane, this membrane water absorption rate is 41.8%, and surface resistance is 0.354Ωcm , vanadium ion permeability is 0.82 * 10 -8 cm 2 the s -1 , in the all-vanadium redox flow battery cell test, at 80mA·cm -2 At current density, CE is 90.04%, VE is 91.27%, and EE is 82.18%. At 1.5M VO 2 + / 3M H 2 SO 4 The mass loss after soaking in the solution for 45 days was 14%.

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Abstract

The invention belongs to the technical field of membranes, and provides a tertiary amine amphoteric ion exchange membrane and a preparation method thereof. The membrane material contains a tertiary amine group and a sulfonic acid group. The membrane has the beneficial effects that an uncharged tertiary amine group serving as a basic group and the sulfonic acid group are adopted to prepare an amphoteric ion exchange membrane, the tertiary amine group can form an 'acid-base pair' effect with the sulfonic acid group, so that the vanadium resistance performance can be effectively improved, conduction of protons can be promoted, the membrane has relatively high ion conductivity and ion selectivity, and the membrane stability is greatly improved by introducing the tertiary amine group.

Description

technical field [0001] The invention belongs to the field of membrane technology, and relates to an amphoteric ion exchange membrane and a preparation method thereof, in particular to a preparation method of a tertiary amine-based amphoteric ion exchange membrane. Background technique [0002] With the aggravation of environmental pollution and energy crisis, the development and utilization of renewable new energy such as solar energy and wind energy have attracted more and more attention. To improve the economics and stability of these renewable energy sources, a large-scale energy storage technology with high efficiency and high reliability is urgently needed. All vanadium redox flow batteries (VRBs) have become the focus of new energy industry research because of their long service life, deep charge and discharge, fast response, flexible design, and no pollution. [0003] As a key component of batteries, ion-exchange membranes play an important role in VRBs. It not only...

Claims

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Application Information

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Patent Type & Authority Patents(China)
IPC IPC(8): H01M8/1027H01M8/103H01M8/1032H01M8/1072
CPCH01M8/1027H01M8/103H01M8/1032H01M8/1072Y02E60/50
Inventor 焉晓明张华清贺高红郑文姬代岩阮雪华
Owner DALIAN UNIV OF TECH
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