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Fluorine-containing network structure ion exchange membrane based on fluoroethyl vinyl ether polyalcohol and preparation method thereof

A technology of fluoroethyl vinyl ether and ion-exchange membrane, applied in the field of ion-exchange membranes, can solve the problems of difficulty in controlling the composite process of membrane materials, difficulty in large-scale batch production, and environmental pollution of sulfonating agents, and achieve the reduction of membrane protons. Excellent exchange resistance, strong electrochemical corrosion resistance, and simple film production method

Inactive Publication Date: 2011-09-28
SHANDONG DONGYUE POLYMER MATERIAL
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

1) The compounding process of membrane materials is difficult to control, the cost is high and the use of sulfonating agent is easy to cause environmental pollution; 2) The treatment process often includes multiple steps, which is difficult to apply to large-scale batch production

Method used

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  • Fluorine-containing network structure ion exchange membrane based on fluoroethyl vinyl ether polyalcohol and preparation method thereof
  • Fluorine-containing network structure ion exchange membrane based on fluoroethyl vinyl ether polyalcohol and preparation method thereof
  • Fluorine-containing network structure ion exchange membrane based on fluoroethyl vinyl ether polyalcohol and preparation method thereof

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0044] With 120g dry sulfonic acid resin (number average molecular weight 80,000, exchange capacity 1.27mmol / g, H + type) was dissolved in 880g N,N-dimethylformamide (DMF) under anhydrous conditions to obtain a sulfonic acid solution (casting solution), and anhydrous toluene-2,4-diisocyanate 4.5g, fluoroethyl Vinyl ether polyol (FEVE, such as structural formula 3, X is Cl, R 1 is ethyl, R 2 is propyl, R 3 for CH 2 CH 2 CH 2 , R 4 for CH 2 ) 4.0g (the ratio of the number of hydroxyl groups -OH to the number of cyanate groups -NCO is 1:1), after fully dissolving and stirring evenly, drool on a smooth and horizontal glass surface under anhydrous conditions, at 55°C After evaporating the solvent for 1 hour, the temperature was raised to 160° C. to form a film, which was peeled off from the glass to obtain an ion-exchange membrane, and treated with 5% sulfuric acid to obtain an ion-exchange membrane with an interpenetrating network structure with a film thickness of 50 micro...

Embodiment 2

[0046] With 45g dry sulfonic acid resin (number average molecular weight 160,000, exchange capacity 2.56mmol / g, Na + type) was dissolved in 880g N-methyl-2-pyrrolidone (NMP) under anhydrous conditions to obtain a sulfonic acid solution (casting solution), and anhydrous 4,4'-diphenylmethane diisocyanate (MDI) was added Anhydrous fluoroethyl vinyl ether polyol (FEVE, such as structural formula 3, X is Cl, R 1 is ethyl, R 2 is propyl, R 3 for CH 2 CH 2 CH 2 CH 2 , R 4 for CH 2 ) a total of 44g (the ratio of the number of hydroxyl groups-OH to the number of cyanate groups-NCO is 1:0.8), fully dissolved, stirred evenly, and salivated on the surface of a smooth and horizontal Hastelloy plate under anhydrous conditions. Raise the temperature to 150°C to evaporate the solvent for 1 hour to form a film, peel off the glass to obtain an ion-exchange membrane, fluoride with fluorine gas, and then treat with 5% hydrochloric acid to obtain an ion-exchange membrane with an interpenet...

Embodiment 3

[0048] With 420g dry sulfonic acid resin (number average molecular weight 240,000, exchange capacity 1.05mmol / g, Na + type) was dissolved in 880g N,N-dimethylacetamide (DMAc) under anhydrous conditions to obtain a sulfonic acid solution (casting solution), and anhydrous triphenylmethane triisocyanate (TTI), anhydrous fluorine Ethyl vinyl ether polyol (FEVE, such as structural formula 3, X is CF 3 , R 1 is ethyl, R 2 Cyclohexyl, R 3 for CH 2 CH 2 CH 2 , R 4 for CH 2 ) a total of 210g (the ratio of the number of hydroxyl groups - OH to the number of cyanate groups - NCO is 1: 1.5), fully dissolved, stirred evenly, and salivated on a smooth and horizontal glass surface under anhydrous conditions, at 100 ° C Evaporate the solvent for 2 hours to form a film, peel off the glass to obtain an ion exchange membrane, and treat it with 12% hydrochloric acid to obtain an ion exchange membrane with an interpenetrating network structure with a film thickness of 150 microns.

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Abstract

The invention relates to a fluorine-containing network structure ion exchange membrane based on fluoroethyl vinyl ether polyalcohol and preparation method thereof. Polar organic solvent is adopt to dissolve perfluorinated sulfonic acid resin and anhydrous poly isocyanate as well as anhydrous fluoroethyl vinyl ether (FEVE) polyalcohol; tape casting is adopted to form a membrane on smooth solid surface; then heating is carried out and poly isocyanate and anhydrous FEVE take polymerization, and products of the polymerization and perfluorinated sulfonic acid molecule chain form ion exchange membrane in macromolecule interpenetrating network structure. The membrane preparation method can obtain fluorine-containing ion exchange membrane material with favourable proton commutativity, overcomes the defect that the existing fusion mould pressing process can not prepare homogeneous cross linking ion exchange membrane and has the advantages of simple technological process and easy industrial scale-up.

Description

technical field [0001] The invention relates to an ion exchange membrane, in particular to a fluorine-containing network ion exchange membrane for an all-vanadium redox flow battery (VRB) and a preparation method thereof, belonging to the field of polymer functional membrane materials. Background technique [0002] As a large-scale energy storage system with a single metal ion, all-vanadium redox flow battery (VRB) avoids the electrolyte cross-contamination problem of traditional lead-acid batteries and Fe / Cr batteries, and is used in stationary energy storage devices for renewable energy. In terms of battery life, it shows great advantages. It is a new type of green secondary battery, which has the advantages of adjustable capacity and power, high current without damage and deep discharge, long service life, easy operation and maintenance, etc. It can be charged both by electricity and mechanically by exchanging electrolyte, which makes it attract people's attention in the ...

Claims

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Application Information

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Patent Type & Authority Patents(China)
IPC IPC(8): C08F14/18B01D71/58B01D69/12H01M10/36B01D71/48
CPCY02E60/12Y02E60/10
Inventor 王学军张永明张恒刘小宁
Owner SHANDONG DONGYUE POLYMER MATERIAL
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