Fiber reinforced composite multi-layer total fluoride crosslinking ionic membrane and preparation method thereof

A fiber composite, perfluorinated ion technology, applied in chemical instruments and methods, membrane technology, semi-permeable membrane separation, etc., can solve the problems of low mechanical strength, decreased equivalent value, and increased gas permeability.

Active Publication Date: 2011-04-06
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 Gas permeability also increases, which will have a very serious impact on the fuel cell

Method used

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  • Fiber reinforced composite multi-layer total fluoride crosslinking ionic membrane and preparation method thereof
  • Fiber reinforced composite multi-layer total fluoride crosslinking ionic membrane and preparation method thereof
  • Fiber reinforced composite multi-layer total fluoride crosslinking ionic membrane and preparation method thereof

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0091] Convert the repeating unit to

[0092]

[0093] , EW=1000 polymer resin and cerium carbonate (accounting for 0.01% of resin quality) are dispersed in propanol-water, and the total mass concentration that makes is 5% propanol-water solution, then adding mass concentration is 5% peroxide Perfluoromalonyl DMF solution, add surface 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 is peeled off to obtain a single-layer fluorine-containing sulfonic acid ion membrane (single-layer membrane 1#) whose crosslinking bridge is (I). Two layers of the above-mentioned single-layer perfluorinated cross-linked ionic membranes were stacked and hot-pressed to obtain a double-layer fiber-reinforced perfluorinated cross-linked ionic membrane (multilayer membrane 1#)...

Embodiment 2

[0095] Convert the repeating unit to

[0096]

[0097] , EW=800 polymer resin and surface phosphorylated alkali-free glass fiber (diameter is 0.05 μm, length is 5 μm, the mass ratio of perfluorosulfonic acid resin is 1:40) is mixed, then extruded to obtain a thickness of 30 μm The film was heated in a vacuum oven at 150°C for 1 hour, and then soaked in NH 4 Cl in DMF solution for 5 hours, and then place the soaked membrane 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 with a cross-linked bridge structure (II) (single-layer membrane 2#).

[0098] Convert the repeating unit to

[0099]

[0100] , polymer resin with EW=1200 and tetraphenyl tin were extruded into a film with a thickness of 20 μm by a twin-screw extruder, and then the film was heated to 230° C. for 10 hours to obtain a film with a cross-linked bridge structur...

Embodiment 3

[0102] Convert the repeating unit to

[0103]

[0104] , the polymer resin of EW=1100, lanthanum acetate (lanthanum acetate accounts for 0.001% of resin quality) is mixed, is dissolved in the solvent, makes the polymer resin solution that total mass concentration is 3%, then casts into film, and then The membrane was cross-linked by 50KGy radiation to obtain an ionic membrane (single-layer membrane 4#) with a thickness of 10 μm and a cross-linked bridge structure of (I).

[0105] Convert the repeating unit to

[0106]

[0107] , the polymer resin of EW=940, Ce (III)-DMSO complex compound (accounting for 0.1% of resin quality) makes the DMSO solution that total mass concentration is 30%, adds 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 170 ° C for 60 minutes by casting to obtain a 10 μm thick Membrane (single layer membrane 5#).

[0108] The sing...

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Abstract

The invention relates to a fiber composite multi-layer total fluoride crosslinking ionic membrane and a preparation method thereof, which belongs to the field of functional polymer composite materials. The fluorine-containing ion exchange membrane is in a double-net structure with chemical bonding crosslinking and physical bonding crosslinking of a high valent metallic compound and an acidic exchange group and simultaneously contains reinforced fiber. The prepared ion exchange membrane has higher dimensional stability and good mechanical strength.

Description

technical field [0001] The invention belongs to the field of functional polymer composite materials, and relates to a fiber-reinforced multi-layer perfluorinated cross-linked ion membrane. 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 membrane an...

Claims

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Application Information

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Patent Type & Authority Patents(China)
IPC IPC(8): B01D71/32H01M8/02H01M2/16C08L27/18C08K7/14C08L27/12C08L27/20C08K7/04C08K3/28C08K3/30C08K3/32C08K5/098C08L5/16C08J5/22H01M8/1041H01M8/1069H01M50/411H01M50/414H01M50/44H01M50/457H01M50/491H01M50/497
CPCY02E60/50Y02E60/12
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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