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Microporous-film-reinforced fluorine-containing cross-linking doping ion-exchange membrane and preparation method thereof

An ion-exchange membrane and ion-doping technology, applied in the field of microporous membrane reinforced fluorine-containing cross-linked doped ion-exchange membrane and its preparation, which can solve the problems of alkali instability, strength reduction and the like

Active Publication Date: 2010-06-23
SHANDONG DONGYUE WEILAI HYDROGEN ENERGY MATERIAL CO LTD
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

For example, US20070031715 describes the cross-linking method of sulfonyl chloride cross-linking to generate sulfonyl anhydride. The sulfonyl anhydride cross-linking structure formed in this method can effectively improve the mechanical strength of the membrane, but the cross-linking structure has obvious disadvantages: The anhydride unit is unstable to bases
However, the addition of inorganic water-retaining agents tends to reduce the strength of the membrane

Method used

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  • Microporous-film-reinforced fluorine-containing cross-linking doping ion-exchange membrane and preparation method thereof
  • Microporous-film-reinforced fluorine-containing cross-linking doping ion-exchange membrane and preparation method thereof
  • Microporous-film-reinforced fluorine-containing cross-linking doping ion-exchange membrane and preparation method thereof

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0066] Example 1: The repeating unit is

[0067]

[0068] Polymer with EW=1000 and Zr(HPO 4 ) 2 (Zr(HPO 4 ) 2 The mass ratio with the resin is 3: 100) to make 5wt% propanol aqueous solution, then configure in the perfluoromalonyl peroxide DMF solution with a concentration of 5%, the expanded polytetrafluoroethylene film (pore) with a thickness of 30 μm rate of 70%) was placed in the above solution and soaked for about 1 hour, then the soaked film was dried on a heating plate, and the film was rolled with a rubber roller. Then cast the above solution into a polytetrafluoroethylene mold placed horizontally, and after vacuum drying at 80°C for 12 hours, the film was peeled off. 2 SO 4 The solution was boiled for 1 hour and washed with deionized water. After heat treatment, the membrane was treated with NaOH solution and sulfuric acid solution in sequence to obtain a single-layer perfluorosulfonic acid cross-linked doped ion membrane (1#) of type (I).

Embodiment 2

[0069] Example 2: The repeating unit is

[0070]

[0071] Polymers with EW=800 and the repeating unit as

[0072]

[0073] The polymer with EW=1200 is mixed at a mass ratio of 2:3, and then mixed with SiO with a particle size of 0.03 μm 2 (SiO 2 The mass ratio of perfluorosulfonic acid resin is 5: 100) and tetraphenyltin mixed extrusion to obtain a film thickness of 30 μm and then with 30 μm silicon dioxide modified porous hexafluoropropylene membrane (porosity 94%) passed through at 260 ℃ hot pressing together under vacuum state, then soak in NH in 150℃ vacuum oven for 1 hour 4 Cl in DMF for 5 hours. The soaked membrane was then placed in triethylamine at 200°C for 2 hours to obtain a crosslinked membrane. The membrane was sequentially treated with KOH solution and hydrochloric acid solution to obtain ion-exchange membranes (2#) with cross-linked structures (II) and (V).

Embodiment 3

[0074] Embodiment 3: the repeating unit is

[0075]

[0076] Polymer with EW=1100 and H 3 PW 12 o 40 A 3% polymer solution was prepared at a ratio of 100:1, and the porous Al 2 o 3 Thin film (50% porosity) is immersed in the above-mentioned solution, after 30 minutes, film is taken out and dried, then this film obtains 20 μm cross-linked structure is the ionic membrane of (I) through 50KGy radiation cross-linking. (3#)

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Abstract

The invention relates to a microporous film reinforced fluoric cross-linked doped ion-exchange film and a preparation method thereof, pertaining to the field of functional macromolecular composite materials. The ion-exchange film takes microposous film as reinforce, containing inorganic adulterant and uses fluoric ion-exchange resin to form a cross-linked film with a mesh structure. The ion-exchange film prepared by the method has the advantages of relatively high high-temperature electric conductivity and dimensional stability and as well as sound mechanical strength.

Description

technical field [0001] The invention belongs to the field of functional polymer composite materials, and relates to a microporous membrane reinforced fluorine-containing cross-linked doped ion exchange membrane and a preparation method thereof. Background technique [0002] Proton exchange membrane fuel cell is a power generation device that directly converts chemical energy into electrical energy by electrochemical means, and is considered to be the preferred clean and efficient power generation technology in the 21st century. Proton exchange membrane (proton exchange membrane, PEM) is the key material of proton exchange membrane fuel cell (proton exchange membrane fuel cell, PEMFC). [0003] Although the current perfluorosulfonic acid proton exchange membrane has been used for many years, there are still some shortcomings that cannot meet the requirements of commercialization, such as low proton conductivity at high temperature, poor dimensional stability, and low mechanic...

Claims

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Application Information

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Patent Type & Authority Patents(China)
IPC IPC(8): H01M8/02H01M2/16C08J5/22C08L27/12C08J3/24C08J3/28H01M8/102H01M8/1069H01M50/414
CPCY02E60/50
Inventor 张永明王军唐军柯王汉利
Owner SHANDONG DONGYUE WEILAI HYDROGEN ENERGY MATERIAL CO LTD
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