Phosphorylated polymer composite film for full vanadium flow battery and preparation method thereof

An all-vanadium redox flow battery and polymer technology, which is applied in the direction of fuel cells, electrochemical generators, battery components, etc., can solve the problems of high vanadium ion permeability, short service life, and high price, and achieve high Effect of voltage efficiency and energy conversion efficiency, cost reduction, and promotion of commercialization process

CN102167785AInactive Publication Date: 2011-08-31GUANGZHOU CHEM CO LTD CHINESE ACADEMY OF SCI +1
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Patent Information

Authority / Receiving Office
CN · China
Patent Type
Applications(China)
Current Assignee / Owner
Publication Date
2011-08-31
Estimated Expiration
Not applicable · inactive patent

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Abstract

The invention discloses a phosphorylated polymer composite film for a full vanadium flow battery and a preparation method thereof. The polymer composite film has a structure shown as a formula (I). The preparation method comprises the following steps of: mixing a monomer mixture, chloromethylate polysulfone, cuprous chloride, genin and a solvent; performing deoxidization; perfomring polymerization; dissolving the obtained polymer into dioxane; adding triethylamine and the cuprous chloride; adding diethyl chlorophosphate dropwise; reacting and filtering; adding filtrate into norml hexane to precipitate; redissolving the precipitate into chloroform; adding the solution into the norml hexane again to precipitate; washing the precipitate; drying to obtain the phosphorylated polymer; dissolving the phosphorylated polymer into a high-boiling-point solvent to obtain phosphorylated polymer solution; forming a film on a glass plate; demoulding in water to obtain a phosphorylated polymer film; placing the phosphorylated polymer film into concentrated hydrochloric acid to perform reflux and hydrolysis; taking out the phosphorylated polymer film to wash with water; and drying to obtain the product. The phosphorylated polymer composite film has low vanadium ion permeability, high proton conductivity, stable mechanical and chemical properties and low cost.
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Description

technical field

[0001] The invention belongs to the field of polymer functional battery membrane materials, and in particular relates to a phosphorylated polymer composite membrane for an all-vanadium redox flow battery and a preparation method thereof. Background technique

[0002] Today, as environmental and energy issues are increasingly troubling the world, the use of renewable energy such as solar energy and wind energy has become the direction of development for various countries. In order to make better use of these renewable energy sources, the development of energy storage systems has become more and more important. . The all-vanadium redox battery (VRB) is prepared based on the principle of electrochemical oxidation and reduction of two completely soluble redox couples on an inert electrode, and the redox couple is composed of different valences of the same metal vanadium. composed of ions. Vanadium redox flow battery (VRB; referred to as vanadium battery), becau...

Examples

Embodiment 1

[0036] (1) Add 14.88g polysulfone and 750ml chloroform to a 1000ml round bottom flask, stir at room temperature to dissolve the polysulfone, then add 10g paraformaldehyde, 0.8ml tin tetrachloride and 42.5ml trimethylchlorosilane, and the system heats up React at 52°C for 20h. After the reaction is terminated, the product is precipitated in methanol, filtered, the filter cake is washed with methanol, and vacuum-dried at 40°C to obtain the chloromethylated polysulfone product (the production process diagram is shown in figure 1 Shown), its degree of substitution as determined by NMR is 0.55, that is, there are 0.55 chloromethyl groups on each polysulfone repeating unit;

[0037] (2) In a 100ml round bottom flask, add 10g trifluoroethyl methacrylate, 10g trimethylchlorosilane-terminated hydroxyethyl methacrylate, 10g chloromethylated polysulfone obtained in step (1), 10g polysulfone Dipyridine and 50ml N,N-dimethylformamide were mixed, the mixed system was dissolved and argon was...

Embodiment 2

[0045] Same as Example 1, except that 35 g of trifluoroethyl methacrylate and 30 g of trimethylchlorosilane-terminated hydroxyethyl methacrylate were added in the reaction. The phosphorylated polymer composite membrane obtained in this embodiment has a structure as shown in formula (I), wherein m is 19, x is 21, and n is 65.

Embodiment 3

[0047] Same as Example 1, except that 30 g of trifluoroethyl methacrylate and 20 g of trimethylchlorosilane-terminated hydroxyethyl methacrylate were added in the reaction. The phosphorylated polymer composite membrane obtained in this embodiment has a structure as shown in formula (I), wherein m is 13, x is 18, and n is 65.