CN-121983624-A - Proton exchange membrane capable of efficiently resisting carbon monoxide poisoning and preparation method thereof

CN121983624ACN 121983624 ACN121983624 ACN 121983624ACN-121983624-A

Abstract

The invention relates to the technical field of fuel cells, in particular to a proton exchange membrane capable of efficiently resisting carbon monoxide poisoning and a preparation method thereof. According to the invention, a graphene functionalized anchoring catalyst and gradient catalyst distribution membrane structural design strategy is adopted, so that the dispersibility and the utilization rate of the catalyst in the proton membrane are improved, further, the stack performance attenuation caused by gas impurities is effectively relieved, and the membrane electrode and the stack are guided to optimize and iterate. Compared with the proton exchange membrane without additives, the proton exchange membrane based on the membrane has greatly improved performance, and the carbon monoxide poisoning resistance capability can reach 0.72V@600mA/cm 2 @60ppm CO, so that the durability of the fuel cell is effectively improved.

Inventors

SONG YARU
LIU ZHIQIANG
ZHANG TONGHUA
WU GUOLING
PENG JIAHUI
YANG ZHIHAO

Assignees

山东国创燃料电池技术创新中心有限公司

Dates

Publication Date: 20260505
Application Date: 20260409

Claims (10)

1. The proton exchange membrane is characterized by comprising an additive layer and a fluorine-containing proton exchange membrane; The additive layer is a fluorine-containing resin layer containing graphene oxide and a carbon monoxide poisoning resistant catalyst, wherein the graphene oxide and the carbon monoxide poisoning resistant catalyst exist in a blending mode or a layer-by-layer stacking mode; The additive layers are positioned on two sides of the fluorine-containing proton exchange membrane and contain graphene oxide and carbon monoxide poisoning resistant catalyst in a graded distribution.
2. The proton exchange membrane of claim 1, wherein the carbon monoxide poisoning resistant catalyst is a single metal, an alloy, a supported single metal or a supported alloy comprising a catalytically active component selected from Pt, ru, rh, pd, mo; Or the carrier of the supported single metal and supported alloy is at least one of carbon, silicon oxide, aluminum oxide and titanium oxide.
3. The proton exchange membrane of claim 1, wherein the total thickness of the carbon monoxide poisoning resistant proton exchange membrane is 8 μm to 40 μm; or, the additive layer has a monolayer thickness of 1 μm to 10 μm; or the thickness of the fluorine-containing proton exchange membrane is 6 μm-20 μm.
4. The proton exchange membrane according to claim 1, wherein the mass ratio of the GO-carbon monoxide poisoning resistant catalyst to the fluorine-containing resin in the additive layer is 0.01 to 10; or the mass ratio of the carbon monoxide poisoning resistant catalyst to the GO in the GO-carbon monoxide poisoning resistant catalyst is 0.01-10.0%.
5. The proton exchange membrane according to claim 1, wherein the GO-carbon monoxide poisoning resistant catalyst content gradient distribution in the single-layer additive layer is such that the GO-carbon monoxide poisoning resistant catalyst and the fluorine-containing resin have a mass ratio change of 0.002-0.005 at a thickness interval of 0.2 μm to 0.5 μm, and an increasing trend is shown from the middle to the two sides.
6. The method for preparing a proton exchange membrane according to claim 1, wherein when the graphene oxide and the catalyst for resisting carbon monoxide poisoning in the additive layer are in a blending mode, the method comprises the following steps: the graphene oxide powder and the catalyst for resisting carbon monoxide poisoning are firstly dispersed in an organic solvent, then mixed with a resin dispersion liquid, coated on a fluorine-containing proton exchange membrane, dried and formed.
7. The method of claim 6, wherein the dispersing process is one or more of magnetic stirring, ultrasonic dispersing, ball milling, high pressure homogenization, or microfluidics; or the ultrasonic dispersion power is 100-800W, the ultrasonic time is 10-60 minutes, the intermittent operation is performed, and the operation is 1-10 seconds/pause is 1-10 seconds; Or the organic solvent is one or more of water, alcohols, N-dimethylformamide, N-dimethylacetamide or N-methylpyrrolidone; or, the coating method comprises spraying, spin coating, knife coating or ink-jet printing; Or, the drying and forming are vacuum heating and drying, the vacuum degree is-0.1 MPa, the temperature is controlled to be (40-60) DEG C- (70-100) DEG C- (110-140) DEG C, and each section lasts for 3-15 min.
8. The method for preparing a proton exchange membrane according to claim 1, wherein when graphene oxide and a catalyst for resisting carbon monoxide poisoning in the additive layer are stacked layer by layer, the method comprises the following steps: transferring the graphene film onto a fluorine-containing proton exchange membrane by a wet process, performing oxidation treatment by oxygen plasma, mixing a catalyst dispersion liquid and a resin dispersion liquid for resisting carbon monoxide poisoning, coating the mixture on the proton membrane containing graphene oxide, drying and forming, repeating the operation until the last layer is scraped, and drying and forming.
9. The method of claim 8, wherein the wet process is a polymethyl methacrylate assisted wet chemistry process; Or the oxygen plasma oxidation treatment is carried out at the power of 20-100W for 1-10 minutes, the gas flow is 5-100 sccm, and the gas pressure is 10-100 mTorr; Or the dispersion technology of the catalyst dispersion liquid containing the carbon monoxide poisoning resistance is one or more of magnetic stirring, ultrasonic dispersion, ball milling, high-pressure homogenization or micro-jet; or the ultrasonic dispersion power is 100-800W, the ultrasonic time is 10-60 minutes, the intermittent operation is performed, and the operation is 1-10 seconds/pause is 1-10 seconds; Or, in the catalyst dispersion liquid containing carbon monoxide poisoning resistance, the solvent is one or more of water, alcohols, N-dimethylformamide, N-dimethylacetamide or N-methylpyrrolidone; Or, the drying and forming are vacuum heating and drying, the vacuum degree is-0.1 MPa, the temperature is controlled to be (40-60) DEG C- (70-100) DEG C- (110-140) DEG C, and each section lasts for 3-15 min.
10. A membrane electrode comprising the proton exchange membrane of claim 1.

Description

Proton exchange membrane capable of efficiently resisting carbon monoxide poisoning and preparation method thereof Technical Field The invention relates to the technical field of fuel cells, in particular to a proton exchange membrane capable of efficiently resisting carbon monoxide poisoning and a preparation method thereof. Background The fuel cell is an energy conversion device for generating electric energy through electrochemical reaction of hydrogen and oxygen, and the reaction product is only water, so that the fuel cell has no pollution and zero emission in the true sense. However, gaseous impurities such as carbon monoxide, etc., which may be present in the raw gas, may poison the catalyst, hinder the adsorption of hydrogen and the subsequent electrochemical oxidation process, so that the battery performance is severely degraded. In view of this problem, the prior art research mainly focuses on the design and preparation of a catalyst for resisting carbon monoxide poisoning, for example, doping Ru, mo, W, sn elements in the catalyst to reduce the influence of CO. However, in the prior art, the dispersibility of the gas impurities such as carbon monoxide in the proton exchange membrane is not concerned too much, and the gas impurities such as carbon monoxide enter the proton exchange membrane to cause the performance attenuation of the galvanic pile, so that the performance of the battery is seriously reduced. Disclosure of Invention In view of the above, the invention provides a proton exchange membrane with high efficiency and carbon monoxide poisoning resistance and a preparation method thereof, the invention adopts gradient distribution membrane structural design and graphene functional anchoring catalyst, the dispersion uniformity of the catalyst for resisting carbon monoxide poisoning in the proton exchange membrane is improved, the capability of the proton exchange membrane for resisting gas impurity poisoning is improved, and a foundation is laid for optimization iteration of the membrane electrode and the galvanic pile. In order to achieve the above object, the present invention is realized by the following technical scheme: in a first aspect, the invention provides a proton exchange membrane with high efficiency and carbon monoxide poisoning resistance, wherein the proton exchange membrane consists of an additive layer and a fluorine-containing proton exchange membrane; The additive layer is a fluorine-containing resin layer containing graphene oxide and a carbon monoxide poisoning resistant catalyst (GO-M), wherein the graphene oxide and the carbon monoxide poisoning resistant catalyst exist in a blending mode or a layer-by-layer stacking mode; The additive layers are positioned at two sides of the fluorine-containing proton exchange membrane, and the graphene oxide and the carbon monoxide poisoning resistant catalyst are distributed in a content gradient way. Further, the Graphene Oxide (GO) is prepared from graphene oxide powder directly prepared by a Hummers method or a graphene film prepared by a chemical vapor deposition method (CVD) and then is obtained by oxidation treatment. Graphene oxide carries an anchor group such as an epoxy group (C-O-C), a hydroxyl group (-OH), a carboxyl group (-COOH), a carbonyl group (c=o), and the like. The oxygen-containing functional group of the graphene oxide improves the dispersibility and stability of the catalyst through an anchoring effect (coordination, hydrogen bond or electrostatic effect and the like), and relieves CO poisoning through an electronic effect and an interfacial synergistic effect. The oxygen-containing functional group can be used as an anchoring site of the metal nano-particles, and is combined with the active components (such as Pt, ru and the like) of the catalyst through chemical bonds (such as coordination bonds and hydrogen bonds) or electrostatic action to inhibit the agglomeration of the metal particles, so that the highly uniform dispersion is realized. The uniformly dispersed catalyst active sites are exposed more, so that the utilization rate of the reactive surfaces can be improved, and the catalytic efficiency of CO oxidation and hydrogen oxidation can be enhanced. The strong interaction of the functional groups with the metal particles prevents migration or shedding of the catalyst during operation, especially maintaining long-term stability under dynamic fuel cell conditions. The anchoring effect can reduce the sintering phenomenon of metal particles at high temperature or high potential and maintain the nano-scale active structure of the catalyst. Oxygen-containing functional groups (such as carboxyl and hydroxyl) have strong electron withdrawing property, can adjust the electron state of the supported metal, and weaken the adsorption strength of CO on the Pt surface (the adsorption energy of CO is reduced), thereby reducing CO poisoning. For the Pt/Ru alloy catalyst, the electronic effect of GO can cooperate wi