High temperature resistant proton exchange membrane based on sulfonated graphene and preparation method therefor

A technology of sulfonated graphene and proton exchange membrane, which is applied in the field of high temperature resistant proton exchange membrane based on sulfonated graphene and its preparation, can solve the problems of high price, low working temperature, high methanol permeability and the like, and achieves low cost , good oxidation resistance, simple preparation process

Active Publication Date: 2015-09-23
SUZHOU GRAPHENE NEW MATERIAL TECH
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

But the high price (800$/m 2 ), low operating temperature (<100°C), high methanol permeability, a

Method used

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Examples

Experimental program
Comparison scheme
Effect test

Example Embodiment

[0020] Example 1 Add fuming sulfuric acid and chlorosulfonic acid with a mass ratio of 3:4 into a multi-tube membrane reactor, and then add graphene (with a radial size of 500nm-50μm and a thickness of 1-20nm) and mix them evenly. The graphene content in the reactant reaches 2wt%, and the reaction is carried out at 80°C for 1 hour. After the reaction is completed, the mixed reactant is distilled at 165°C, and the residue is washed with water to obtain sulfonated graphene.

[0021] Dissolve the sulfonated graphene and partially quaternized polytrifluorostyrene sulfonated resin (see CN1346707A) and perfluorosulfonic acid resin with a mass ratio of 1:65:34 in dimethyl sulfoxide, and then The film is cast at room temperature and then dried in hot air at 80°C to form a proton exchange membrane. The thickness of the proton exchange membrane is 100μm and the average surface resistance is about 5.65×10 6 Ω, the proton conductivity at 100°C is 0.21S.cm-1, and the highest temperature resist...

Example Embodiment

[0022] Example 2 Put fuming sulfuric acid and chlorosulfonic acid into a multi-tube membrane reactor at a mass ratio of 4:4, and then add graphene (500nm-50μm in radial size, 1-20nm in thickness) and mix uniformly to make the mixing reaction The graphene content in the material reached 1% (wt), and the reaction was carried out at 80°C for 1 hour. After the reaction was completed, the mixed reactant was distilled at 165°C, and the residue was washed with water to obtain sulfonated graphene.

[0023] Dissolve the sulfonated graphene and partially quaternized polytrifluorostyrene sulfonated resin (refer to CN1346707A) and perfluorosulfonic acid resin with a mass ratio of 0.5:65:34.5 in dimethyl sulfoxide, and then The film is cast at room temperature and then dried in hot air at 80°C to form a proton exchange membrane. The thickness of the proton exchange membrane is 100μm and the average surface resistance is about 3.80×10 6 Ω, 100℃ proton conductivity is 0.25S.cm -1 , And the highe...

Example Embodiment

[0024] Example 3 Add oleum and chlorosulfonic acid into a multi-tube membrane reactor at a mass ratio of 3:5, and then add graphene (with a radial size of 500nm-50μm and a thickness of 1-20nm) and mix uniformly to make the mixed reactants The content of the graphene in the resin reaches 3% (wt), and the reaction is carried out at 80°C for 1 hour. After the reaction is completed, the mixed reactant is distilled at 165°C, and the residue is washed with water to obtain sulfonated graphene.

[0025] Dissolve the sulfonated graphene and partially quaternized polytrifluorostyrene sulfonated resin (refer to CN1346707A) and perfluorosulfonic acid resin with a mass ratio of 2:65:33 in dimethyl sulfoxide, and then The film is cast at room temperature and then dried at 80°C with hot air to form a proton exchange membrane. The thickness of the proton exchange membrane is 100μm and the average surface resistance is about 5.90×10 6 Ω, the proton conductivity of 100℃ is 0.20S.cm-1, and the highe...

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Abstract

The invention discloses a high temperature resistant proton exchange membrane based on sulfonated graphene and a preparation method therefor. The proton exchange membrane comprises the following components in percentage by weight: 20wt% to 70wt% of partially quaternized polytrifluorostyrene sulfonated resin, 10wt% to 50wt% of perfluorinated sulfonic acid resin and 0.01wt% to 2wt% of sulfonated graphene, wherein the radial dimension of the sulfonated graphene is 500 nm to 50 [mu]m, the thickness of the sulfonated graphene is 1-20 nm, and the mole ratio of C to S in the sulfonated graphene is 12: 1 to 6: 1. The preparation method of the proton exchange membrane comprises the following steps: dissolving the sulfonated graphene, the partially quaternized polytrifluorostyrene sulfonated resin and the perfluorinated sulfonic acid resin in an organic solvent, then adopting a casting or tape casting method for film formation, and then drying to obtain the proton exchange membrane. The surface resistance of the proton exchange membrane disclosed by the invention is 106-107 omega in the order of magnitudes, the proton exchange membrane can be used at the temperature of more than 200 DEG C, the proton conductivity at the temperature of 100 DEG C is greater than 0.2 S/cm, the proton exchange membrane has good oxidative resistance, the service life exceeds 5000 hours, and the proton exchange membrane is simple in preparation technology, low in cost, safe and environment-friendly and can be widely used in the fuel cell industry, flow cell industry and chlorine alkali industry.

Description

technical field [0001] The invention relates to a proton exchange membrane and a preparation method thereof, in particular to a high temperature resistant proton exchange membrane based on sulfonated graphene and a preparation method thereof. Background technique [0002] Proton exchange membranes are widely used in the field of fuel cells and have a very important impact on the performance of fuel cells. At present, the perfluorosulfonic acid Nafion membrane produced by DuPont of the United States is widely used. This type of perfluorosulfonic acid membrane has the advantages of good proton conductivity, strong corrosion resistance, and long service life. But the high price (800$ / m 2 ), low operating temperature (<100°C), high methanol permeability, and environmental problems caused by fluorine-containing materials limit its commercial application. Therefore, it is an important research direction to find new proton exchange membrane materials that are cheap, have high ...

Claims

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Application Information

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IPC IPC(8): C08L25/18C08L101/04C08K9/04C08K3/04C08J5/22H01M8/10
CPCY02E60/50
Inventor 蒋永华郝建东栗建民
Owner SUZHOU GRAPHENE NEW MATERIAL TECH
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