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Multilayer fluorine-contained crosslinking doping ionic membrane with reinforced microporous membrane and preparation method thereof

A technology of microporous membrane and ionic membrane, which is applied in the field of multi-layer fluorine-containing cross-linked doped ionic membrane and its preparation, and can solve the problems such as the decrease of perfluoropolymer equivalent value and the decrease of membrane strength

Active Publication Date: 2010-03-17
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

Generally speaking, when the ion exchange capacity increases, the equivalent value of perfluoropolymer decreases (equivalent value EW value decreases, ion exchange capacity IEC=1000 / EW) and the strength of the membrane also decreases

Method used

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  • Multilayer fluorine-contained crosslinking doping ionic membrane with reinforced microporous membrane and preparation method thereof
  • Multilayer fluorine-contained crosslinking doping ionic membrane with reinforced microporous membrane and preparation method thereof
  • Multilayer fluorine-contained crosslinking doping ionic membrane with reinforced microporous membrane and preparation method thereof

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0083] Example 1: The repeating unit is

[0084]

[0085] 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 the heat treatment, the membrane was sequentially treated with NaOH solution and sulfuric acid solution to obtain each single-layer perfluorosulfonic acid cross-linked as (I) doped ion membrane (single-layer membrane ...

Embodiment 2

[0086] Example 2: The repeating unit is

[0087]

[0088] Polymer with EW=800 and particle size 0.03 μm SiO 2 (SiO 2 The mass ratio with perfluorosulfonic acid resin is 5:100), extruded to obtain a film with a thickness of 30 μm, and then passed through a 12 μm silica-modified porous hexafluoropropylene membrane (porosity 90%) under vacuum at 310 ° C. Press together, then soak in NH in a vacuum oven at 150°C 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 an ion-exchange membrane with a cross-linked structure (II) (single-layer membrane 2#).

[0089] Convert the repeating unit to

[0090]

[0091] A polymer with EW=1200 and tetraphenyltin was extruded into a 50 μm film with a twin-screw extruder, and then the film was heated to 230° C. for 10 hours to obtain a film with a cros...

Embodiment 3

[0092] Embodiment 3: the repeating unit is

[0093]

[0094] Polymer with EW=1100 and H 3PW 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. (single layer film 4#)

[0095] Convert the repeating unit to

[0096]

[0097] Polymer with EW=940 and H 3 PW 12 o 40 by polymer with H 3 PW 12 o 40 A 30% DMSO solution was prepared at a mass ratio of 100:20, and a 10 μm film (monolayer film 5#) was prepared by casting at 170° C. for 60 minutes.

[0098] Stack single-layer membranes 2#, 4, and 5# perfluorosulfonic acid ion membranes for hot pressing, and then hot-press with multilayer membrane 102# to obtain a 60 μm microporous membrane reinforced three-layer cross-linked doped ion membrane (multila...

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Abstract

The invention relates to a multilayer fluorine-contained crosslinking doping ionic membrane with a reinforced microporous membrane and a preparation method thereof. Two to forty layers of membranes are formed by the fluorine-contained ion exchange resin with the EW value of 600-1300; the total thickness is 10-300 mu m; at least one layer of membrane is in a crosslinking net structure; at least onelayer of membrane is added with inorganic dopants with water retention function or proton exchange function; and at least one layer of membrane is reinforced porous membrane with the microporous membrane as a reinforcer. The multilayer fluorine-contained crosslinking doping ionic membrane with the reinforced microporous membrane in the invention improves the mechanical strength of the ionic membrane, improves the stability of the membrane in the directions of length, width, thickness and the like, has high ionic exchange capability and high electrical conductivity, and is used for producing fuel cells.

Description

[0001] This application is a divisional application of the 200810138429.1 patent application. technical field [0002] The invention belongs to the field of functional polymer composite materials, and relates to a microporous membrane-reinforced multi-layer fluorine-containing cross-linked doped ion membrane and a preparation method thereof. Background technique [0003] 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). [0004] 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...

Claims

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Application Information

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IPC IPC(8): B01D71/32B01D67/00B01D69/12C08J5/22H01M4/94H01M8/10H01M8/1023
CPCY02E60/523Y02E60/50Y02P70/50
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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