Fiber composite and multi-layer perfluorinated cross-linked doped ion-exchange membrane

A technology of doping ions and fiber composites, which is applied in the field of functional polymer composite materials, and can solve problems such as alkali instability, increased gas permeability, and poor chemical stability.

Active Publication Date: 2010-06-16
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

However, they also have many defects: such as poor dimensional stability, low mechanical strength, poor chemical stability, etc.
[0012] 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: sulfonyl chloride Anhydride units are unstable to bases
Generally speaking, when the ion exchange capacity increases, the equivalent value of the perfluoropolymer decreases (the equivalent value EW value decreases, the ion exchange capacity IEC=1000 / EW), and the strength of the membrane also decreases, and the membrane strength The gas permeability also increases, which will have a very serious impact on the fuel cell

Method used

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  • Fiber composite and multi-layer perfluorinated cross-linked doped ion-exchange membrane
  • Fiber composite and multi-layer perfluorinated cross-linked doped ion-exchange membrane
  • Fiber composite and multi-layer perfluorinated cross-linked doped ion-exchange membrane

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0101] Convert the repeating unit to

[0102]

[0103] , polymer with EW=1000 and vanadium carbonate (accounting for 0.01% of resin mass), Zr(HPO with a particle size of 0.005 μm) 4 ) 2 (Zr(HPO 4 ) 2 The mass ratio with resin is 3: 100) is dispersed in propanol-water, makes total mass concentration and is 5% propanol-water solution, then adding mass concentration is the perfluoromalonyl peroxide DMF solution of 5%, to Add H to the above solution 3 PO 4 -SiO 2 Modified polytetrafluoroethylene fibers (1 μm in diameter, 50 μm in length, 7:100 mass ratio to polymer resin) were then cast into a horizontally placed polytetrafluoroethylene mold and vacuum-dried at 80°C for 12 hours. The membrane was peeled off to obtain a single-layer perfluorosulfonic acid cross-linked bridge (I) doped ion membrane (single-layer membrane 1#). Then, the above two single-layer perfluorinated cross-linked ion-doped membranes were stacked and hot-pressed to prepare a vanadium ion-bonded double...

Embodiment 2

[0105] Convert the repeating unit to

[0106]

[0107] , EW = 800 polymer resin, SiO with a particle size of 0.03 μm 2 (SiO 2 The mass ratio with perfluorosulfonic acid resin is 5:100), and the surface phosphorylated alkali-free glass fiber (diameter is 0.05 μm, length is 5 μm, without mass ratio with perfluorosulfonic acid resin is 1:40) is fully Mixed, then extruded to obtain a film with a thickness of 30 μm, and then the film was soaked in NH 4 Cl in DMF for 5 hours. The soaked membrane was then placed in triethylamine at 200°C for 2 hours to obtain a cross-linked membrane. The membrane was sequentially treated with KOH solution and hydrochloric acid solution to obtain an ion exchange membrane (single-layer membrane 2#) with a cross-linked bridge structure (II).

[0108] Convert the repeating unit to

[0109]

[0110] , polymer resin with EW=1200 and tetraphenyl tin are extruded into a film with a thickness of 20 μm by a twin-screw extruder, and then the film is ...

Embodiment 3

[0112] Convert the repeating unit to

[0113]

[0114] , the polymer resin of EW=1100, lanthanum acetate (lanthanum acetate accounts for 0.001% of resin mass) and H 3 PW 12 o 40 (resin and H 3 PW 12 o40 The mass ratio is 100:1) in the solvent to make a polymer solution with a total mass concentration of 3%, cast into a film, and then this film is cross-linked through 50KGy radiation to obtain a cross-linked bridge structure with a thickness of 10 μm as (I ) ion membrane (monolayer membrane 4#).

[0115] Convert the repeating unit to

[0116]

[0117] , polymer resin of EW=940, Ru-DMSO complex (accounting for 0.1% of resin quality) and H 3 PW 12 o 40 (Polymer and H 3 PW 12 o 40 mass ratio of 100:20) was dispersed in DMSO to obtain a DMSO solution with a total mass concentration of 30%, adding sulfuric acid-ZrO 2 Modified polytetrafluoroethylene fibers (0.2 μm in diameter, 80 μm in length, and a weight ratio of 7:100 to the polymer resin) were then treated at 1...

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Abstract

The invention relates to a fiber-reinforced multi-layer cross-linked doped perfluorinated ion-exchange membrane and a preparation method thereof, belonging to the field of functional polymer composite materials. The perfluorinated ion-exchange membrane comprises a multi-layer structure and is simultaneously doped with reinforcing fibers and auxiliary proton conducting substances, and the cross-linking reaction is carried out under certain conditions, thereby forming the ion-exchange membrane with the dual-network structure formed by chemical bonding and cross-linking and physical bonding and cross-linking between high valent metal compounds and acidic exchange groups. The prepared ion-exchange membrane has high proton conductivity and high dimensional stability.

Description

technical field [0001] The invention belongs to the field of functional polymer composite materials, and relates to a multi-layer perfluorinated cross-linked doped ion membrane composed of fibers. 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] The currently used perfluorosulfonic acid proton exchange membrane has good proton conductivity and chemical stability at lower temperature (80°C) and higher humidity. However, they also have many defects: such as poor dimensional stability, low mechanical strength, and poor chemical stability. The water absorption rate of the mem...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): B01D71/32H01M8/02H01M2/16C08J5/22C08L27/18C08J3/24H01M8/102H01M50/411H01M50/44H01M50/446H01M50/457H01M50/489
CPCY02E60/12Y02E60/50
Inventor 张永明唐军柯刘萍张恒王军
Owner SHANDONG DONGYUE WEILAI HYDROGEN ENERGY MATERIAL CO LTD
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