CN115692742A - Gas diffusion layer for proton exchange membrane fuel cell and preparation method thereof - Google Patents
Gas diffusion layer for proton exchange membrane fuel cell and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a gas diffusion layer for a proton exchange membrane fuel cell, which relates to the field of proton exchange membrane fuel cells and comprises a substrate layer and a microporous layer; the preparation material of the substrate layer comprises modified polytetrafluoroethylene emulsion and a carbon bottom layer; the preparation material of the microporous layer comprises microporous layer slurry, and the preparation material of the microporous layer slurry comprises modified epoxy resin, acetone, water repellent emulsion and a conductive carbon material; the preparation material of the modified polytetrafluoroethylene emulsion comprises polytetrafluoroethylene, ethanol, graphene, nano copper oxide, a silane coupling agent, water, perfluoro ammonium caprylate and potassium persulfate; the preparation material of the modified epoxy resin comprises nano montmorillonite, nano alumina, a silane coupling agent, ethanol, cyclohexanone, polydimethylsiloxane, benzyl dimethylamine and epoxy resin. The gas diffusion layer obtained by the invention has high porosity and good air permeability, and the single cell prepared by using the gas diffusion layer has excellent battery performance.
Description
Technical Field
The invention relates to the field of proton exchange membrane fuel cells, in particular to a gas diffusion layer for a proton exchange membrane fuel cell and a preparation method thereof.
Background
The fuel cell is a novel and environment-friendly power generation device, can directly convert chemical energy stored in fuel into electric energy, and is an effective method for solving the current energy crisis by using the fuel cell because the fuel cell does not generate electricity and is not fiercely combusted and the conversion process is green and environment-friendly. Among various fuel cells, the pem fuel cell is considered to be one of the most promising power sources because of its advantages such as high power density, high energy conversion efficiency, low temperature start-up, no pollution, light weight, etc. Fuel cells produce a large amount of water during operation, and if the water cannot be discharged in time, the water flooding phenomenon of the catalyst layer can be caused, so that the whole cell channel is blocked, and the gas transmission is blocked. It is therefore important to have a channel that is both effective in transporting the gas and managing the water produced by the reaction.
The stability and reliability of proton exchange membrane fuel cells depends largely on the water management of the gas diffusion layers. Water management is the effective regulation and control of water in the proton exchange membrane fuel cell. An ideal gas diffusion layer should have less mass transfer resistance, good water drainage properties, and lower electrical resistance. The porosity increases the transmission channel, so that reactants and products can pass through the transmission channel more easily, but the internal resistance of the battery is increased along with the increase of the internal resistance of the battery. The low porosity means that the channels are narrow, which can block the reactants and products, and the low porosity of the diffusion layer can degrade the transmission quality, but the internal resistance of the cell is also reduced.
In summary, after the applicant's mass search, there is at least a problem in the art that it is not guaranteed that the gas diffusion layer has a large porosity, a high air permeability and excellent conductivity, resulting in poor performance of the prepared cell, and therefore, it is necessary to develop or improve a gas diffusion layer for a proton exchange membrane fuel cell and a preparation method thereof.
Disclosure of Invention
Based on the above, in order to solve the problem that the gas diffusion layer cannot be ensured to have high porosity, high air permeability and excellent conductivity at the same time, so that the prepared battery has poor performance, the invention provides a gas diffusion layer for a proton exchange membrane fuel cell and a preparation method thereof, and the specific technical scheme is as follows:
a gas diffusion layer for a proton exchange membrane fuel cell, comprising a substrate layer and a microporous layer;
the preparation material of the substrate layer comprises modified polytetrafluoroethylene emulsion and a carbon substrate layer;
the preparation material of the microporous layer comprises microporous layer slurry, and the preparation material of the microporous layer slurry comprises modified epoxy resin, acetone, water repellent emulsion and a conductive carbon material;
the preparation material of the modified polytetrafluoroethylene emulsion comprises polytetrafluoroethylene, ethanol, graphene, nano copper oxide, a silane coupling agent, water, perfluorooctanoic acid amine and potassium persulfate;
the preparation material of the modified epoxy resin comprises nano montmorillonite, nano alumina, a silane coupling agent, ethanol, cyclohexanone, polydimethylsiloxane, benzyl dimethylamine and epoxy resin.
Further, the conductive carbon material is at least one of acetylene black, carbon nanotubes, super P, vulcan XC-72 and graphene.
Further, the carbon bottom layer comprises one of a carbon fiber layer, a carbon fiber woven cloth and carbon black paper.
Further, the preparation method of the modified polytetrafluoroethylene emulsion comprises the following steps:
adding 3~7 parts of graphene, 1~3 parts of nano copper oxide and 2~5 parts of a silane coupling agent into 6-10 parts of ethanol in parts by mass, and performing ultrasonic treatment for 2-3h to obtain a modified polytetrafluoroethylene emulsion prefabricated liquid;
adding 25 to 35 parts of polytetrafluoroethylene, 38 to 45 parts of water, 5~8 parts of perfluorooctanoic acid amine and 2~5 parts of potassium persulfate into a reactor in parts by mass, stirring at the speed of 600 to 700r/min for 5 to 8min, then adding the modified polytetrafluoroethylene emulsion prefabricated liquid, and stirring at the speed of 1000 to 1100r/min for 25 to 28min to obtain the modified polytetrafluoroethylene emulsion.
Further, the preparation method of the modified epoxy resin comprises the following steps:
dissolving 0.5 to 2 parts by mass of a silane coupling agent in 18 to 22 parts by mass of ethanol, adding 5~7 parts by mass of nano montmorillonite and 6~8 parts by mass of nano alumina, stirring at 55 to 58 ℃ for 3 to 5 hours, carrying out suction filtration and drying, adding 29 to 35 parts by mass of cyclohexanone and 29 to 35 parts by mass of epoxy resin, stirring at 850 to 900r/min for 50 to 55min, adding 0.5 to 2 parts by mass of polydimethylsiloxane and 0.5 to 2 parts by mass of benzyldimethylamine, and uniformly stirring to obtain the modified epoxy resin.
Further, the silane coupling agent includes at least one of gamma-aminopropyltriethoxysilane, gamma- (2,3-glycidoxy) propyltrimethoxysilane, and gamma-methacryloxypropyltrimethoxysilane.
Further, the preparation method of the substrate layer comprises the following steps:
and (3) dipping the carbon bottom layer in the modified polytetrafluoroethylene emulsion for 3-8min, then sintering at 370-390 ℃ for 1.1-1.3h, and repeating the dipping and sintering steps for 2~5 times until the loading amount of the polytetrafluoroethylene is 0.5-2% of the mass of the carbon bottom layer to obtain the substrate layer.
Further, the preparation method of the microporous layer slurry comprises the following steps:
adding 35 to 41 parts by mass of conductive carbon material into 39 to 45 parts by mass of acetone, carrying out ultrasonic treatment for 1.8 to 2.2h, then adding 12 to 18 parts by mass of modified epoxy resin, stirring at the speed of 750 to 800r/min for 38 to 42min, then adding 3~8 parts by mass of water repellent emulsion, and uniformly stirring to obtain the microporous layer slurry;
the mass percent of the water repellent emulsion is 8-10wt%.
Further, the particle size of the nano montmorillonite is 10 to 40nm;
the particle size of the nano alumina is 10 to 30nm;
the particle size of the nano copper oxide is 15 to 45nm;
the water repellent emulsion comprises at least one of polytetrafluoroethylene emulsion, polyvinylidene fluoride emulsion, copolymer emulsion of tetrafluoroethylene and hexafluoropropylene and polychlorotrifluoroethylene suspension.
The technical scheme also provides a preparation method of the gas diffusion layer, which comprises the following steps:
uniformly coating the microporous layer slurry on a substrate layer, baking for 0.6 to 0.8h at the temperature of 350 to 380 ℃, hot-pressing for 0.6 to 0.8h at the temperature of 360 to 410 ℃ and under the pressure of 0.8 to 2.2MPa, repeating the steps of uniformly coating, baking and hot-pressing for 3~5 times until the gas diffusion layer is obtainedThe loading capacity of the medium conductive carbon material is 2.2 to 2.8mg/cm 2 And obtaining the gas diffusion layer.
According to the technical scheme, the specific modified polytetrafluoroethylene emulsion is adopted as the preparation material of the substrate layer, the specific modified epoxy resin is adopted for preparing the microporous layer, the sintering step is adopted in the preparation process of the substrate layer, the roasting and hot-pressing laminating steps are adopted in the preparation process of the gas diffusion layer, the obtained gas diffusion layer is high in porosity and good in air permeability, and the single cell prepared by using the gas diffusion layer is excellent in battery performance. Specifically, the graphene has good conductivity and toughness, and the modified polytetrafluoroethylene emulsion is subjected to modification of nano copper oxide and graphene and repeated impregnation and sintering steps in the preparation process of the substrate layer, so that the obtained gas diffusion layer has high porosity and air permeability and the conductivity can be enhanced. The modified epoxy resin is modified by the nano montmorillonite and the nano alumina, and after the microporous layer slurry prepared by the modified epoxy resin is roasted, the microporous layer has higher porosity, higher air permeability and excellent conductivity. The repetition of the steps of uniform coating, baking and hot pressing enables the porosity, air permeability and electrical conductivity of the entire gas diffusion layer to be maintained during the preparation of the gas diffusion layer.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is further described in detail below with reference to embodiments thereof. It should be understood that the detailed description and specific examples, while indicating the scope of the invention, are intended for purposes of illustration only and are not intended to limit the scope of the invention.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used herein in the description of the invention is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. As used herein, the term "and/or" includes any and all combinations of one or more of the associated listed items.
The gas diffusion layer for the proton exchange membrane fuel cell in one embodiment of the invention comprises a substrate layer and a microporous layer;
the preparation material of the substrate layer comprises modified polytetrafluoroethylene emulsion and a carbon bottom layer;
the preparation material of the microporous layer comprises microporous layer slurry, and the preparation material of the microporous layer slurry comprises modified epoxy resin, acetone, water repellent emulsion and a conductive carbon material;
the preparation material of the modified polytetrafluoroethylene emulsion comprises polytetrafluoroethylene, ethanol, graphene, nano copper oxide, a silane coupling agent, water, perfluorooctanoic acid amine and potassium persulfate;
the preparation material of the modified epoxy resin comprises nano montmorillonite, nano alumina, a silane coupling agent, ethanol, cyclohexanone, polydimethylsiloxane, benzyl dimethylamine and epoxy resin.
In one embodiment, the conductive carbon material is at least one of acetylene black, carbon nanotubes, super P, vulcan XC-72, and graphene.
In one embodiment, the carbon substrate includes one of a carbon fiber layer, a carbon fiber woven cloth, and a carbon black paper.
In one embodiment, the preparation method of the modified polytetrafluoroethylene emulsion comprises the following steps:
adding 3~7 parts of graphene, 1~3 parts of nano copper oxide and 2~5 parts of silane coupling agent into 6-10 parts of ethanol in parts by mass, and performing ultrasonic treatment for 2-3 hours to obtain a modified polytetrafluoroethylene emulsion prefabricated liquid;
adding 25 to 35 parts of polytetrafluoroethylene, 38 to 45 parts of water, 5~8 parts of perfluorooctanoic acid amine and 2~5 parts of potassium persulfate into a reactor in parts by mass, stirring at the speed of 600 to 700r/min for 5 to 8min, then adding the modified polytetrafluoroethylene emulsion prefabricated liquid, and stirring at the speed of 1000 to 1100r/min for 25 to 28min to obtain the modified polytetrafluoroethylene emulsion.
In one embodiment, the preparation method of the modified epoxy resin comprises the following steps:
dissolving 0.5 to 2 parts by mass of a silane coupling agent in 18 to 22 parts by mass of ethanol, adding 5~7 parts by mass of nano montmorillonite and 6~8 parts by mass of nano alumina, stirring at 55 to 58 ℃ for 3 to 5 hours, carrying out suction filtration and drying, adding 29 to 35 parts by mass of cyclohexanone and 29 to 35 parts by mass of epoxy resin, stirring at 850 to 900r/min for 50 to 55min, adding 0.5 to 2 parts by mass of polydimethylsiloxane and 0.5 to 2 parts by mass of benzyldimethylamine, and uniformly stirring to obtain the modified epoxy resin.
In one embodiment, the silane coupling agent comprises at least one of gamma-aminopropyltriethoxysilane, gamma- (2,3-glycidoxy) propyltrimethoxysilane and gamma-methacryloxypropyltrimethoxysilane.
In one embodiment, the method for preparing the substrate layer comprises the following steps:
and (3) dipping the carbon bottom layer in the modified polytetrafluoroethylene emulsion for 3-8min, then sintering at 370-390 ℃ for 1.1-1.3h, and repeating the dipping and sintering steps for 2~5 times until the loading amount of the polytetrafluoroethylene is 0.5-2% of the mass of the carbon bottom layer to obtain the substrate layer.
In one embodiment, the method for preparing the microporous layer slurry comprises the following steps:
adding 35 to 41 parts by mass of conductive carbon material into 39 to 45 parts by mass of acetone, carrying out ultrasonic treatment for 1.8 to 2.2h, then adding 12 to 18 parts by mass of modified epoxy resin, stirring at the speed of 750 to 800r/min for 38 to 42min, then adding 3~8 parts by mass of water repellent emulsion, and uniformly stirring to obtain the microporous layer slurry;
the mass percent of the water repellent emulsion is 8-10wt%.
In one embodiment, the particle size of the nano montmorillonite is 10 to 40nm;
the particle size of the nano alumina is 10 to 30nm;
the particle size of the nano copper oxide is 15 to 45nm;
the water repellent emulsion comprises at least one of polytetrafluoroethylene emulsion, polyvinylidene fluoride emulsion, copolymer emulsion of tetrafluoroethylene and hexafluoropropylene and polychlorotrifluoroethylene suspension.
In one embodiment, the present disclosure provides a method for preparing a gas diffusion layer, including the following steps:
uniformly coating the microporous layer slurry on a substrate layer, baking for 0.6 to 0.8h at the temperature of 350 to 380 ℃, hot-pressing for 0.6 to 0.8h at the temperature of 360 to 410 ℃ and under the pressure of 0.8 to 2.2MPa, repeating the steps of uniformly coating, baking and hot-pressing for 3~5 times until the loading capacity of the conductive carbon material in the gas diffusion layer is 2.2 to 2.8mg/cm 2 And obtaining the gas diffusion layer.
Embodiments of the present invention will be described in detail below with reference to specific examples.
Example 1:
preparing modified polytetrafluoroethylene emulsion: adding 5 parts of graphene, 2 parts of nano copper oxide with the particle size of 30nm and 3 parts of gamma-aminopropyltriethoxysilane in 8 parts of ethanol by mass, and carrying out ultrasonic treatment for 2.5 hours to obtain a modified polytetrafluoroethylene emulsion prefabricated liquid; according to the mass parts, 30 parts of polytetrafluoroethylene, 42 parts of water, 6 parts of perfluorooctanoic acid amine and 3 parts of potassium persulfate are added into a reactor, stirred at the speed of 650r/min for 6min, then the modified polytetrafluoroethylene emulsion prefabricated liquid is added, and stirred at the speed of 1050r/min for 26min, so that the modified polytetrafluoroethylene emulsion is obtained.
Preparation of modified epoxy resin: dissolving 1 part of gamma-aminopropyltriethoxysilane in 20 parts of ethanol by mass, adding 6 parts of nano-montmorillonite with the particle size of 25nm and 7 parts of nano-alumina with the particle size of 20nm, stirring at 56 ℃ for 4 hours, performing suction filtration and drying, adding 32 parts of cyclohexanone and 32 parts of epoxy resin, stirring at 870r/min for 52min, adding 1 part of polydimethylsiloxane and 1 part of benzyldimethylamine, and uniformly stirring to obtain the modified epoxy resin.
Preparation of microporous layer slurry: adding 38 parts by mass of acetylene black into 42 parts by mass of acetone, carrying out ultrasonic treatment for 2.0h, then adding 15 parts by mass of modified epoxy resin, stirring at a speed of 770r/min for 40min, then adding 5 parts by mass of 9wt% of polytetrafluoroethylene emulsion, and uniformly stirring to obtain microporous layer slurry.
Preparation of the base layer: and (3) dipping the carbon black paper in the modified polytetrafluoroethylene emulsion for 5min, then sintering at 380 ℃ for 1.2h, and repeating the dipping and sintering steps for 3 times until the loading of the polytetrafluoroethylene is 1.2% of the mass of the carbon black paper, thus obtaining the substrate layer.
Preparation of gas diffusion layer: uniformly coating the microporous layer slurry on a substrate layer, roasting for 0.7h at 360 ℃, hot-pressing and attaching for 0.7h at 380 ℃ and 1.5MPa, and repeating the steps of uniformly coating, roasting and hot-pressing for 4 times until the loading amount of acetylene black in the gas diffusion layer is 2.5mg/cm 2 And obtaining the gas diffusion layer.
Example 2:
the other portions were the same as in example 1 except that acetylene black was replaced with carbon nanotubes.
Example 3:
the other portions are the same as in example 1 except that carbon black paper is replaced with a carbon fiber layer.
Example 4:
the other portions were the same as in example 1 except that nano copper oxide having a particle size of 30nm was replaced with nano copper oxide having a particle size of 15 nm.
Example 5:
the other portions were the same as in example 1 except that nano copper oxide having a particle size of 30nm was replaced with nano copper oxide having a particle size of 45 nm.
Example 6:
the other part was the same as in example 1 except that nano-montmorillonite having a particle size of 25nm was replaced with nano-montmorillonite having a particle size of 10 nm.
Example 7:
the other part was the same as in example 1 except that nano-montmorillonite having a particle size of 25nm was replaced with nano-montmorillonite having a particle size of 40 nm.
Example 8:
the other portions are the same as example 1 except that nano alumina having a particle size of 20nm is replaced with nano alumina having a particle size of 10 nm.
Example 9:
the other portions were the same as in example 1 except that nano alumina having a particle size of 20nm was replaced with nano alumina having a particle size of 30 nm.
Comparative example 1:
preparation of polytetrafluoroethylene emulsion for substrate layer: 30 parts by mass of polytetrafluoroethylene and 42 parts by mass of water were stirred at 1050r/min for 26min to obtain a polytetrafluoroethylene emulsion for a base layer.
Preparation of modified epoxy resin: dissolving 1 part of gamma-aminopropyltriethoxysilane in 20 parts of ethanol by mass, adding 6 parts of nano-montmorillonite with the particle size of 25nm and 7 parts of nano-alumina with the particle size of 20nm, stirring at 56 ℃ for 4 hours, performing suction filtration and drying, adding 32 parts of cyclohexanone and 32 parts of epoxy resin, stirring at 870r/min for 52min, adding 1 part of polydimethylsiloxane and 1 part of benzyldimethylamine, and uniformly stirring to obtain the modified epoxy resin.
Preparation of microporous layer slurry: adding 38 parts by mass of acetylene black into 42 parts by mass of acetone, carrying out ultrasonic treatment for 2.0h, then adding 15 parts by mass of modified epoxy resin, stirring at a speed of 770r/min for 40min, then adding 5 parts by mass of 9wt% of polytetrafluoroethylene emulsion, and uniformly stirring to obtain microporous layer slurry.
Preparation of the base layer: and (3) dipping the carbon black paper into the substrate layer, sintering for 5min by using polytetrafluoroethylene emulsion at 380 ℃, repeating the dipping and sintering steps for 3 times until the loading amount of the polytetrafluoroethylene is 1.2% of the mass of the carbon black paper, and obtaining the substrate layer.
Preparation of gas diffusion layer: uniformly coating the microporous layer slurry on a substrate layer, roasting for 0.7h at 360 ℃, hot-pressing and attaching for 0.7h at 380 ℃ and 1.5MPa, and repeating the steps of uniformly coating, roasting and hot-pressing for 4 times until the loading amount of acetylene black in the gas diffusion layer is 2.5mg/cm 2 And obtaining the gas diffusion layer.
Comparative example 2:
preparing modified polytetrafluoroethylene emulsion: adding 5 parts of graphene, 2 parts of nano copper oxide with the particle size of 30nm and 3 parts of gamma-aminopropyltriethoxysilane in 8 parts of ethanol by mass, and carrying out ultrasonic treatment for 2.5 hours to obtain a modified polytetrafluoroethylene emulsion prefabricated liquid; according to the mass parts, 30 parts of polytetrafluoroethylene, 42 parts of water, 6 parts of perfluorooctanoic acid amine and 3 parts of potassium persulfate are added into a reactor, stirred at the speed of 650r/min for 6min, then the modified polytetrafluoroethylene emulsion prefabricated liquid is added, and stirred at the speed of 1050r/min for 26min, so that the modified polytetrafluoroethylene emulsion is obtained.
Preparation of microporous layer slurry: adding 38 parts by mass of acetylene black into 42 parts by mass of acetone, carrying out ultrasonic treatment for 2.0h, then adding 15 parts by mass of epoxy resin, stirring at a speed of 770r/min for 40min, then adding 5 parts by mass of 9wt% of polytetrafluoroethylene emulsion, and uniformly stirring to obtain microporous layer slurry.
Preparation of the base layer: and (3) dipping the carbon black paper in the modified polytetrafluoroethylene emulsion for 5min, then sintering at 380 ℃ for 1.2h, and repeating the dipping and sintering steps for 3 times until the loading of the polytetrafluoroethylene is 1.2% of the mass of the carbon black paper, thus obtaining the substrate layer.
Preparation of gas diffusion layer: uniformly coating the microporous layer slurry on a substrate layer, roasting at 360 ℃ for 0.7h, hot-pressing and attaching at 380 ℃ and 1.5MPa for 0.7h, and repeating the steps of uniformly coating, roasting and hot-pressing for 4 times until the loading amount of acetylene black in the gas diffusion layer is 2.5mg/cm 2 And obtaining the gas diffusion layer.
Comparative example 3:
preparing modified polytetrafluoroethylene emulsion: adding 5 parts by mass of graphene, 2 parts by mass of nano copper oxide with the particle size of 30nm and 3 parts by mass of gamma-aminopropyltriethoxysilane into 8 parts by mass of ethanol, and carrying out ultrasonic treatment for 2.5 hours to obtain a modified polytetrafluoroethylene emulsion prefabricated liquid; according to the mass parts, 30 parts of polytetrafluoroethylene, 42 parts of water, 6 parts of perfluorooctanoic acid amine and 3 parts of potassium persulfate are added into a reactor, stirred at the speed of 650r/min for 6min, then the modified polytetrafluoroethylene emulsion prefabricated liquid is added, and stirred at the speed of 1050r/min for 26min, so that the modified polytetrafluoroethylene emulsion is obtained.
Preparation of modified epoxy resin: dissolving 1 part of gamma-aminopropyltriethoxysilane in 20 parts of ethanol by mass, adding 6 parts of nano-montmorillonite with the particle size of 25nm and 7 parts of nano-alumina with the particle size of 20nm, stirring at 56 ℃ for 4 hours, performing suction filtration and drying, adding 32 parts of cyclohexanone and 32 parts of epoxy resin, stirring at 870r/min for 52min, adding 1 part of polydimethylsiloxane and 1 part of benzyldimethylamine, and uniformly stirring to obtain the modified epoxy resin.
Preparation of microporous layer slurry: adding 38 parts by mass of acetylene black into 42 parts by mass of acetone, carrying out ultrasonic treatment for 2.0h, then adding 15 parts by mass of modified epoxy resin, stirring at a speed of 770r/min for 40min, then adding 5 parts by mass of 9wt% of polytetrafluoroethylene emulsion, and uniformly stirring to obtain microporous layer slurry.
Preparation of the base layer: and (3) dipping the carbon black paper in the modified polytetrafluoroethylene emulsion for 5min, then drying, and repeating the steps of dipping and drying until the loading amount of the polytetrafluoroethylene is 1.2% of the mass of the carbon black paper, so as to obtain the substrate layer.
Preparation of gas diffusion layer: uniformly coating the microporous layer slurry on a substrate layer, roasting for 0.7h at 360 ℃, hot-pressing and attaching for 0.7h at 380 ℃ and 1.5MPa, and repeating the steps of uniformly coating, roasting and hot-pressing for 4 times until the loading amount of acetylene black in the gas diffusion layer is 2.5mg/cm 2 And obtaining the gas diffusion layer.
Comparative example 4:
preparing modified polytetrafluoroethylene emulsion: adding 5 parts of graphene, 2 parts of nano copper oxide with the particle size of 30nm and 3 parts of gamma-aminopropyltriethoxysilane in 8 parts of ethanol by mass, and carrying out ultrasonic treatment for 2.5 hours to obtain a modified polytetrafluoroethylene emulsion prefabricated liquid; according to the mass parts, 30 parts of polytetrafluoroethylene, 42 parts of water, 6 parts of perfluorooctanoic acid amine and 3 parts of potassium persulfate are added into a reactor, stirred at the speed of 650r/min for 6min, then the modified polytetrafluoroethylene emulsion prefabricated liquid is added, and stirred at the speed of 1050r/min for 26min, so that the modified polytetrafluoroethylene emulsion is obtained.
Preparation of modified epoxy resin: dissolving 1 part of gamma-aminopropyltriethoxysilane in 20 parts of ethanol by mass, adding 6 parts of nano-montmorillonite with the particle size of 25nm and 7 parts of nano-alumina with the particle size of 20nm, stirring at 56 ℃ for 4 hours, filtering, drying, adding 32 parts of cyclohexanone and 32 parts of epoxy resin, stirring at 870r/min for 52 minutes, adding 1 part of polydimethylsiloxane and 1 part of benzyldimethylamine, and uniformly stirring to obtain the modified epoxy resin.
Preparation of microporous layer slurry: adding 38 parts by mass of acetylene black into 42 parts by mass of acetone, carrying out ultrasonic treatment for 2.0h, then adding 15 parts by mass of modified epoxy resin, stirring at a speed of 770r/min for 40min, then adding 5 parts by mass of 9wt% of polytetrafluoroethylene emulsion, and uniformly stirring to obtain microporous layer slurry.
Preparation of the base layer: and (3) dipping the carbon black paper in the modified polytetrafluoroethylene emulsion for 5min, then sintering at 380 ℃ for 1.2h, and repeating the dipping and sintering steps for 3 times until the loading amount of the polytetrafluoroethylene is 1.2% of the mass of the carbon black paper, so as to obtain the substrate layer.
Preparation of gas diffusion layer: uniformly coating the microporous layer slurry on a substrate layer, drying, hot-pressing and laminating for 0.7h at 380 ℃ and under 1.5MPa, and repeating the steps of uniformly coating, drying and hot-pressing until the loading amount of acetylene black in the gas diffusion layer is 2.5mg/cm 2 And obtaining the gas diffusion layer.
Comparative example 5:
preparing modified polytetrafluoroethylene emulsion: adding 5 parts of graphene, 2 parts of nano copper oxide with the particle size of 30nm and 3 parts of gamma-aminopropyltriethoxysilane in 8 parts of ethanol by mass, and carrying out ultrasonic treatment for 2.5 hours to obtain a modified polytetrafluoroethylene emulsion prefabricated liquid; according to the mass parts, 30 parts of polytetrafluoroethylene, 42 parts of water, 6 parts of perfluorooctanoic acid amine and 3 parts of potassium persulfate are added into a reactor, stirred at the speed of 650r/min for 6min, then the modified polytetrafluoroethylene emulsion prefabricated liquid is added, and stirred at the speed of 1050r/min for 26min, so that the modified polytetrafluoroethylene emulsion is obtained.
Preparation of modified epoxy resin: dissolving 1 part of gamma-aminopropyltriethoxysilane in 20 parts of ethanol by mass, adding 6 parts of nano-montmorillonite with the particle size of 25nm and 7 parts of nano-alumina with the particle size of 20nm, stirring at 56 ℃ for 4 hours, filtering, drying, adding 32 parts of cyclohexanone and 32 parts of epoxy resin, stirring at 870r/min for 52 minutes, adding 1 part of polydimethylsiloxane and 1 part of benzyldimethylamine, and uniformly stirring to obtain the modified epoxy resin.
Preparation of microporous layer slurry: adding 38 parts by mass of acetylene black into 42 parts by mass of acetone, carrying out ultrasonic treatment for 2.0h, then adding 15 parts by mass of modified epoxy resin, stirring at a speed of 770r/min for 40min, then adding 5 parts by mass of 9wt% of polytetrafluoroethylene emulsion, and uniformly stirring to obtain microporous layer slurry.
Preparation of the base layer: and (3) dipping the carbon black paper in the modified polytetrafluoroethylene emulsion for 5min, then sintering at 380 ℃ for 1.2h, and repeating the dipping and sintering steps for 3 times until the loading amount of the polytetrafluoroethylene is 1.2% of the mass of the carbon black paper, so as to obtain the substrate layer.
Preparation of gas diffusion layer: uniformly coating the microporous layer slurry on a substrate layer, roasting at 360 ℃ for 0.7h, and repeating the steps of uniformly coating and roasting until the loading amount of acetylene black in the gas diffusion layer is 2.5mg/cm 2 And obtaining the gas diffusion layer.
Test method
Testing of gas diffusion layer properties: the porosity and air permeability of the gas diffusion layer were tested.
Performance testing using gas diffusion layer single cells: the gas diffusion layers were assembled into single cells and the maximum power density of the single cells was tested.
Cell performance test conditions
High humidification maximum power density test conditions: the temperature of the cell is 68 ℃, the relative humidity of the anode is 95%, the feeding gas of the anode is hydrogen, the flow rate is 100ml/min, the back pressure of the anode is 0.05MPa, the relative humidity of the cathode is 95%, the feeding gas of the cathode is air, the flow rate is 800ml/min, and the back pressure of the cathode is 0.05MPa.
Low humidification maximum power density test conditions: the temperature of the cell is 68 ℃, the relative humidity of the anode is 35 percent, the feeding gas of the anode is hydrogen, the flow rate is 100ml/min, the back pressure of the anode is 0.05MPa, the relative humidity of the cathode is 35 percent, the feeding gas of the cathode is air, the flow rate is 800ml/min, and the back pressure of the cathode is 0.05MPa.
The results of the tests for example 1~9 and comparative example 1~5 are shown in table 1.
Table 1:
as can be seen from the data of example 1~9 and comparative example 1~5 in Table 1, the present invention employs a specific modified polytetrafluoroethylene emulsion for the material for the base layer, a specific modified epoxy resin for the microporous layer, and a sintering step in combination with the base layer during the gas diffusion layer manufacturing process, a baking stepThe obtained gas diffusion layer has high porosity and good air permeability, and the single cell prepared by using the gas diffusion layer has excellent battery performance, which is specifically shown in that the maximum power density of high humidification reaches 0.95W/cm 2 Above, the maximum power density of low humidification reaches 0.60W/cm 2 The above.
The technical features of the embodiments described above may be arbitrarily combined, and for the sake of brevity, all possible combinations of the technical features in the embodiments described above are not described, but should be considered as being within the scope of the present specification as long as there is no contradiction between the combinations of the technical features.
The above-mentioned embodiments only express several embodiments of the present invention, and the description thereof is more specific and detailed, but not construed as limiting the scope of the invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention. Therefore, the protection scope of the present patent shall be subject to the appended claims.
Claims (10)
1. A gas diffusion layer for a proton exchange membrane fuel cell, comprising a substrate layer and a microporous layer;
the preparation material of the substrate layer comprises modified polytetrafluoroethylene emulsion and a carbon bottom layer;
the preparation material of the microporous layer comprises microporous layer slurry, and the preparation material of the microporous layer slurry comprises modified epoxy resin, acetone, water repellent emulsion and a conductive carbon material;
the preparation material of the modified polytetrafluoroethylene emulsion comprises polytetrafluoroethylene, ethanol, graphene, nano copper oxide, a silane coupling agent, water, perfluoro ammonium caprylate and potassium persulfate;
the preparation material of the modified epoxy resin comprises nano montmorillonite, nano alumina, a silane coupling agent, ethanol, cyclohexanone, polydimethylsiloxane, benzyl dimethylamine and epoxy resin.
2. The gas diffusion layer of claim 1, wherein the electrically conductive carbon material is at least one of acetylene black, carbon nanotubes, super P, vulcan XC-72, and graphene.
3. The gas diffusion layer of claim 1, wherein the carbon underlayer comprises one of a carbon fiber layer, a woven carbon fiber cloth, and a carbon black paper.
4. The gas diffusion layer of claim 1, wherein the modified polytetrafluoroethylene emulsion is prepared by a method comprising the steps of:
adding 3~7 parts of graphene, 1~3 parts of nano copper oxide and 2~5 parts of silane coupling agent into 6-10 parts of ethanol in parts by mass, and performing ultrasonic treatment for 2-3 hours to obtain a modified polytetrafluoroethylene emulsion prefabricated liquid;
adding 25 to 35 parts of polytetrafluoroethylene, 38 to 45 parts of water, 5~8 parts of perfluorooctanoic acid amine and 2~5 parts of potassium persulfate into a reactor in parts by mass, stirring at the speed of 600 to 700r/min for 5 to 8min, then adding the modified polytetrafluoroethylene emulsion prefabricated liquid, and stirring at the speed of 1000 to 1100r/min for 25 to 28min to obtain the modified polytetrafluoroethylene emulsion.
5. The gas diffusion layer of claim 1, wherein the modified epoxy resin is prepared by a method comprising the steps of:
dissolving 0.5 to 2 parts by mass of a silane coupling agent in 18 to 22 parts by mass of ethanol, adding 5~7 parts by mass of nano montmorillonite and 6~8 parts by mass of nano alumina, stirring at 55 to 58 ℃ for 3 to 5 hours, carrying out suction filtration and drying, adding 29 to 35 parts by mass of cyclohexanone and 29 to 35 parts by mass of epoxy resin, stirring at 850 to 900r/min for 50 to 55min, adding 0.5 to 2 parts by mass of polydimethylsiloxane and 0.5 to 2 parts by mass of benzyldimethylamine, and uniformly stirring to obtain the modified epoxy resin.
6. The gas diffusion layer of claim 1, wherein the silane coupling agent comprises at least one of gamma-aminopropyltriethoxysilane, gamma- (2,3-glycidoxy) propyltrimethoxysilane, and gamma-methacryloxypropyltrimethoxysilane.
7. The gas diffusion layer of claim 1, wherein the substrate layer is prepared by a method comprising the steps of:
and (3) dipping the carbon bottom layer in the modified polytetrafluoroethylene emulsion for 3-8min, then sintering at 370-390 ℃ for 1.1-1.3h, and repeating the dipping and sintering steps for 2~5 times until the loading amount of the polytetrafluoroethylene is 0.5-2% of the mass of the carbon bottom layer to obtain the substrate layer.
8. The gas diffusion layer of claim 1, wherein the microporous layer slurry is prepared by a method comprising the steps of:
adding 35 to 41 parts by mass of conductive carbon material into 39 to 45 parts by mass of acetone, carrying out ultrasonic treatment for 1.8 to 2.2h, then adding 12 to 18 parts by mass of modified epoxy resin, stirring at the speed of 750 to 800r/min for 38 to 42min, then adding 3~8 parts by mass of water repellent emulsion, and uniformly stirring to obtain the microporous layer slurry;
the mass percent of the water repellent emulsion is 8-10wt%.
9. The gas diffusion layer according to claim 1, wherein the nano-montmorillonite has a particle size of 10 to 40nm;
the particle size of the nano alumina is 10 to 30nm;
the particle size of the nano copper oxide is 15 to 45nm;
the water repellent emulsion comprises at least one of polytetrafluoroethylene emulsion, polyvinylidene fluoride emulsion, copolymer emulsion of tetrafluoroethylene and hexafluoropropylene and polychlorotrifluoroethylene suspension.
10. The method of making a gas diffusion layer according to any one of claims 1~9 comprising the steps of:
uniformly coating the microporous layer slurry on a substrate layer, baking for 0.6 to 0.8h at the temperature of 350 to 380 ℃, and baking at 360 DEG CHot-pressing and sticking for 0.6 to 0.8h at the temperature of between 410 and 0.8 to 2.2MPa, repeating the steps of uniform coating, roasting and hot-pressing for 3~5 times until the loading capacity of the conductive carbon material in the gas diffusion layer is between 2.2 and 2.8mg/cm 2 And obtaining the gas diffusion layer.
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