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Sulfonated fluorene-containing polyether sulphone for proton exchange membrane of all-vanadium flow battery and preparation method and application thereof

An all-vanadium redox flow battery and proton exchange membrane technology, applied in fuel cell parts, battery pack parts, circuits, etc., can solve problems such as uncharacterized chemical stability, high vanadium ion permeability, and battery performance degradation. , to achieve high coulombic efficiency and energy conversion efficiency, avoid interaction, and low cost

Inactive Publication Date: 2011-01-26
SUN YAT SEN UNIV
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

However, due to the high vanadium ion permeability and high cost of the Nafion membrane, it is not suitable for application in all-vanadium redox flow batteries.
Qiu Xinping of Tsinghua University [Journal of Material Chemistry, 18 (1232) 2008] used Nafion film as a substrate to prepare a multi-layer film for all-vanadium redox flow battery by self-assembly method, but there are problems of high production cost and complicated process. features
M. Skyllas-Kazacos et al [Journal of Membrane Science, 107 (35) 1995] modified the low-cost commercial membrane Daramic by cross-linking and sulfonation as the proton exchange membrane of the all-vanadium redox flow battery, but its chemical stability is not as good as uncharacterized
Theresa Sukkar et al [Journal of Applied Electrochemistry, 34 (137) 2004] to the Gore Select L-570 of U.S. Gore Tex company, L-01009, L-01854 and L-03430 etc. membranes are used in all-vanadium redox flow battery anolyte The stability of these films has been studied, showing that the durability of these films is not good, and long-term use will lead to a decline in battery performance

Method used

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  • Sulfonated fluorene-containing polyether sulphone for proton exchange membrane of all-vanadium flow battery and preparation method and application thereof
  • Sulfonated fluorene-containing polyether sulphone for proton exchange membrane of all-vanadium flow battery and preparation method and application thereof
  • Sulfonated fluorene-containing polyether sulphone for proton exchange membrane of all-vanadium flow battery and preparation method and application thereof

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0039] Preparation of sulfonated polyaryl ether sulfone containing fluorene:

[0040] At room temperature, add 0.5 mmol of fluorene-containing polyaryl ether sulfone 1aa into a 150 mL single-necked flask, add 50 mL of dichloromethane, and magnetically stir to dissolve it. According to the number of moles of repeating units in the fluorene-containing polyaryl ether sulfone 1aa molecule The molar ratio to the chlorosulfonic acid molecule is 1:6 (raw material ratio). Weigh 0.133mL (2mmol, 0.234g) of chlorosulfonic acid, add 10mL of dichloromethane to prepare a solution, and slowly add dropwise with a constant pressure dropping funnel After reacting for 6 hours at room temperature, a brown precipitate formed. Pour out the dichloromethane, wash the product 3 times with 10 mL of cyclohexane, add 10 mL of DMAc, stir for 1-2 hours to fully dissolve, add 20 mL of 3wt% sodium hydroxide solution, Stir for 6 hours, add 100 mL of 5 vol% hydrochloric acid solution, stir for 6 hours, transfer t...

Embodiment 2～8

[0042] The sulfonation steps of Examples 2, 3, 4, 5, 6, 7 and 8 are the same as those of Example 1, except for the ratio of raw materials or the chemical structure of polyaryl ether sulfone containing fluorene, the degree of sulfonation (y Values) are different, as shown in Table 1:

[0043] Table 1 Results of sulfonation of fluorene-containing polyaryl ether sulfones with different molecular structures

[0044] Example

Embodiment 9

[0045] Example 9 Preparation of a single component film

[0046] Take the sulfonated fluorene-containing polyaryl ether sulfone 2aa 1g prepared according to Example 1, add 20mL DMAc, heat and stir to dissolve, filter, concentrate the filtrate to 10mL, and cast on a horizontally placed glass plate in a dust-free environment Dry at 80°C to obtain a single component film 2-1.

[0047] Fenton reagent (3wt.%H 2 O 2 +2ppm FeSO 4 ) To determine its anti-oxidation stability, and measure the time for the membrane to begin to decompose flocculent sediment in a water bath shaker at 80°C.

[0048] The prepared membrane was acidified with 1M sulfuric acid at 80°C for 24 hours, and then immersed in ultrapure water for 24 hours to wash off the excess acid adsorbed in the membrane. Use an AC impedance tester to measure its room temperature conductivity.

[0049] VO 2+ Permeability to characterize the resistance to vanadium ion penetration. One side of the membrane is 1MVOSO 4 +1M H 2 SO 4 Solution,...

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Abstract

The invention discloses sulfonated fluorene-containing polyether sulphone for a proton exchange membrane of an all-vanadium flow battery and a preparation method and an application thereof. The preparation method of the invention adopts fluorene-containing bisphenol with different structures and different dihalide monomers to perform copolymerization in non-proton polar solvent under the action of potassium carbonate catalyst, then uses chlorosulfonic acid to sulfonate the obtained polymer and finally adjusts the dosage of chlorosulfonic acid to prepare a kind of sulfonated fluorene-containing polyether sulphones with different degrees of sulfonation. The polymer can be directly casted to prepare single component film, mixed with other polymers to prepare composite film, mixed with inorganic matter to prepare doped film or combined with other ion exchange films to prepare multi-layer film. The films are characterized by low vanadium ion permeability, low water absorption, high proton conductivity, good stability, low cost and the like, thus being applicable to being used as proton exchange films of the all-vanadium flow battery.

Description

Technical field [0001] The invention relates to a sulfonated fluorene-containing polyaryl ether sulfone used for a proton exchange membrane of an all-vanadium redox flow battery, a preparation method and application thereof, and belongs to the technical field of proton exchange membrane materials for an all-vanadium redox flow battery. Background technique [0002] The all-vanadium flow battery is a new type of high-efficiency electrochemical energy storage system. It uses the redox reaction between four vanadium ions with different valences to provide the main power electromotive force. The two sides of the ion exchange membrane circulate respectively, and the current loop is completed by ion conduction. It has the following advantages: 1. There is no concentration polarization, deep discharge and instantaneous charging; 2. Because the positive and negative electrolytes are both vanadium ion electrolytes, there is no cross-contamination problem; 3. Rated power and rated energy a...

Claims

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Application Information

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Patent Type & Authority Patents(China)
IPC IPC(8): C08G75/23B29C41/24H01M2/16H01M8/02H01M8/0202
CPCY02E60/50Y02E60/12
Inventor 孟跃中陈栋阳王拴紧肖敏韩东梅
Owner SUN YAT SEN UNIV
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