CN112724724B - Fuel cell membrane electrode gas diffusion layer and preparation method and application of microporous layer thereof - Google Patents
Fuel cell membrane electrode gas diffusion layer and preparation method and application of microporous layer thereof Download PDFInfo
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- B05D3/00—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials
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Abstract
The invention discloses a fuel cell membrane electrode gas diffusion layer and a preparation method and application of a microporous layer thereof, belonging to the field of fuel cells. The gas diffusion layer comprises a support layer and a microporous layer; the preparation method of the microporous layer comprises the following steps: dissolving organic siloxane, an active monomer, a photoinitiator, a coupling agent and a carbon material in an organic solvent according to a predetermined proportion, and stirring and dispersing to form uniformly mixed slurry; coating the slurry on one side of the support layer subjected to hydrophobic treatment until the loading amount of the carbon material is 0.5-3.0mg/cm2Obtaining a supporting layer with slurry; and placing the support layer with the slurry in an ultraviolet curing box for curing, and forming a microporous layer on the support layer. The invention prepares uniform slurry by organic siloxane, active monomer, photoinitiator, coupling agent and carbon material, and adopts ultraviolet light curing technology to rapidly cure and prepare the microporous layer of the gas diffusion layer, the process is simple and rapid, the energy is saved, and the production is convenient.
Description
Technical Field
The invention belongs to the field of fuel cells (H01M), and particularly relates to a fuel cell membrane electrode gas diffusion layer, a preparation method of a microporous layer of the fuel cell membrane electrode gas diffusion layer and application of the microporous layer.
Background
Gas Diffusion Layers (GDLs) are important components of Membrane Electrode Assemblies (MEAs) for fuel cells, and generally comprise a Support Layer (SL) and a Microporous Layer (MPL). The conventional microporous layer generally adopts a carbon material and Polytetrafluoroethylene (PTFE), the hydrophobicity, the conductivity and the air permeability of the microporous layer are adjusted by adjusting the proportion of the PTFE and the carbon material in the microporous layer, and the preparation method mostly adopts a high-temperature baking process, so that the energy consumption is high, the experimental process is complex, the fluoropolymer is excessively depended on, and the preparation cost is also high.
Disclosure of Invention
In order to overcome the technical defects, the invention provides a fuel cell membrane electrode gas diffusion layer, a preparation method of a microporous layer of the fuel cell membrane electrode gas diffusion layer and application of the microporous layer, so as to solve the problems related to the background technology.
The present invention includes three aspects. In a first aspect, the present invention provides a method of preparing a microporous layer of a gas diffusion layer of a fuel cell membrane electrode, the gas diffusion layer comprising a support layer and a microporous layer; the method comprises the following steps:
dissolving organic siloxane, an active monomer, a photoinitiator, a coupling agent and a carbon material in an organic solvent according to a predetermined proportion, and stirring and dispersing to form uniformly mixed slurry;
coating the slurry on one side of the support layer subjected to hydrophobic treatment until the loading amount of the carbon material is 0.5-3.0mg/cm2Obtaining a supporting layer with slurry;
and placing the support layer with the slurry in an ultraviolet curing box for curing, and forming a microporous layer on the support layer.
Preferably or alternatively, the slurry comprises the following components: 10 to 40 weight percent of organic siloxane, 1 to 2 weight percent of active monomer, 0.1 to 1 weight percent of photoinitiator, 0.5 to 2.5 weight percent of coupling agent, 5 to 20 weight percent of carbon material and the balance of solvent.
Preferably or optionally, the curing conditions for placing the support layer with the slurry in an ultraviolet curing box are as follows: the temperature is 0-25 ℃, the ultraviolet wavelength is 365-2And the curing time is 1-5 min.
Preferably or alternatively, the organosiloxane comprises at least one of polydimethylsiloxane, polymethylsiloxane, alpha, omega-dihydroxypolysiloxane.
Preferably or alternatively, the reactive monomer comprises at least one of butyl acrylate, 1, 6-hexanediol diacrylate, methoxy or ethoxylated acrylate.
Preferably or alternatively, the photoinitiator comprises at least one of 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-phenyl-1-propanone, 2-methyl-2- (4-morpholinyl) -1- [4- (methylthio) phenyl ] -1-propanone, 2-hydroxy-2-methyl-1- [4- (2-hydroxyethoxy) phenyl ] -1-propanone, diphenyltrimethyl benzoyl phosphine oxide, ethyl 4-dimethylaminobenzoate, triarylsulfonium salts, and diaryliodonium salts.
Preferably or alternatively, the coupling agent is a silane coupling agent having the general formula Y-Si-X3Wherein Y is vinyl, methacryloxy, epoxy, amino; x is methoxyl, ethoxyl and chloro.
Preferably or optionally, the carbon material comprises at least one of carbon black, acetylene black, graphite, carbon nanotubes, carbon fibers, graphene.
In a second aspect, the present invention provides a gas diffusion layer obtained by the above method for preparing a microporous layer of a gas diffusion layer of a membrane electrode for a fuel cell.
In a third aspect, the invention provides a fuel cell membrane electrode prepared by a gas diffusion layer, and an application of the fuel cell membrane electrode prepared by the gas diffusion layer as the fuel cell membrane electrode or as a component of the fuel cell membrane electrode in the field of fuel cells.
The invention relates to a fuel cell membrane electrode gas diffusion layer, a preparation method and application of a microporous layer thereof, compared with the prior art, the fuel cell membrane electrode gas diffusion layer has the following beneficial effects:
1. according to the invention, the active monomer is used as a curing agent, the active monomer forms an organic polymer under the action of a photoinitiator, and the organic siloxane and the carbon material are uniformly cured on the outer surface of the supporting layer; on the other hand, compared with the binding force of high-temperature baking, the organic polymer has higher mechanical strength and toughness, small expansion coefficient and no residual stress after curing.
2. According to the invention, the silane coupling agent is adopted, the organic polymer, the supporting layer, the organic polymer and the carbon material are connected through chemical bonds, and the bonding force is stronger than that of high-temperature baking.
3. The invention adopts the ultraviolet curing technology, can be quickly cured to form the microporous layer, saves energy and reduces resource waste; and the formed microporous layer has better hydrophobicity and a proper pore structure, so that the performance of the battery is effectively improved.
4. The invention adopts the organic siloxane as the hydrophobic agent, effectively reduces the surface tension, ensures the hydrophobicity of the microporous layer of the gas diffusion layer, reduces the use of the fluorine-containing polymer, is beneficial to reducing the production cost and reducing the fluorine pollution.
5. Because the high temperature condition can lead the organic siloxane to be decomposed into substances with smaller molecular weight, and the ultraviolet curing technology adopted by the invention does not relate to the high temperature treatment process, and has relatively smaller influence on the molecular weight of the organic siloxane, the organic siloxane oligomer is adopted as the hydrophobic material, has good compatibility, can more effectively reduce the surface tension of the microporous layer, and can realize accurate regulation and control on the hydrophobicity of the microporous layer by adjusting the molecular weight of the organic siloxane.
6. The organic siloxane has very low surface tension, can reduce the surface tension of the microporous layer, and forms a micro-nano material with a carbon material to increase the roughness of the micro-nano material, so that the super-hydrophobicity of the microporous layer is realized; therefore, the present invention adjusts the hydrophobicity, conductivity and gas permeability of the microporous layer by adjusting the ratio of the organosiloxane and the carbon material in the microporous layer and the loading amount of the carbon material.
In conclusion, the invention prepares uniform slurry by using the organic siloxane, the active monomer, the photoinitiator, the coupling agent and the carbon material, and adopts the ultraviolet curing technology to rapidly cure and prepare the microporous layer of the gas diffusion layer, so that the process is simple and rapid, the reaction condition is mild, and the production is convenient.
Detailed Description
In the following description, numerous specific details are set forth in order to provide a more thorough understanding of the present invention. It will be apparent, however, to one skilled in the art, that the present invention may be practiced without one or more of these specific details. In other instances, well-known features have not been described in order to avoid obscuring the invention.
The invention provides a preparation method of a microporous layer of a gas diffusion layer of a membrane electrode of a fuel cell, which comprises the following steps:
dissolving organic siloxane, an active monomer, a photoinitiator, a coupling agent and a carbon material in an organic solvent according to a predetermined proportion, and stirring and dispersing to form uniformly mixed slurry;
coating the slurry on one side of the support layer subjected to hydrophobic treatment until the loading amount of the carbon material is 0.5-3.0mg/cm2Obtaining a supporting layer with slurry;
and placing the support layer with the slurry in an ultraviolet curing box for curing, and forming a microporous layer on the support layer.
In a further embodiment, the slurry comprises the following components: 10 to 40 weight percent of organic siloxane, 1 to 2 weight percent of active monomer, 0.1 to 1 weight percent of photoinitiator, 0.5 to 2.5 weight percent of coupling agent, 5 to 20 weight percent of carbon material and the balance of solvent.
Wherein the organosiloxane serves as a hydrophobic agent for reducing the surface tension of the microporous layer; the active monomer is used as a curing agent, organic polymer is formed under the action of a photoinitiator, and organic siloxane and a carbon material are cured on the supporting layer; the silane coupling agent connects the organic polymer with the supporting layer, the organic polymer and the carbon material through chemical bonds, so that the organic polymer has stronger mechanical strength; a carbon material is used as the conductive material for maintaining the conductivity of the microporous layer, but it is preferable that the amount of the carbon material is 0.5 to 3.0mg/cm2(ii) a When the loading amount of the carbon material is less than 0.5mg/cm2The carbon materials are isolated from each other and cannot form a passage, andresulting in a sudden drop in conductivity of the microporous layer; when the carbon material is higher than 3.0mg/cm2When the organic siloxane is used, the orientation of the organic siloxane is influenced, and the hydrophobicity is reduced.
In a further embodiment, the curing conditions for placing the support layer with the slurry in an ultraviolet curing oven are as follows: the temperature is room temperature (0-25 ℃), the ultraviolet wavelength is 365-2And the curing time is 1-5 min.
In a further embodiment, the coating method is knife coating, spraying or screen printing. Other selection conditions are within the scope of the present invention for those skilled in the art, and are not repeated herein to avoid unnecessary repetition.
In a further embodiment, the organosiloxane comprises at least one of polydimethylsiloxane, polymethylsiloxane, alpha, omega-dihydroxypolysiloxane. Preferably, the polydimethylsiloxane, the polymethylsiloxane, and the alpha, omega-dihydroxypolysiloxane are all oligomers having a molecular weight of 500-4000 g/mol.
Because the high temperature condition can lead the organic siloxane to be decomposed into substances with smaller molecular weight, and the ultraviolet curing technology adopted by the invention does not relate to the high temperature treatment process, and has relatively smaller influence on the molecular weight of the organic siloxane, the organic siloxane oligomer is adopted as the hydrophobic material, the oligomer has good compatibility, the surface tension of the microporous layer can be more effectively reduced, and in the specific implementation process, the hydrophobic property of the microporous layer can be accurately regulated and controlled by adjusting the molecular weight of the organic siloxane.
In a further embodiment, the reactive monomer comprises at least one of butyl acrylate, 1, 6-hexanediol diacrylate, methoxy or ethoxylated acrylates. Preferably, the active monomer is 1, 6-hexanediol diacrylate, and the 1, 6-hexanediol diacrylate is a bifunctional functional monomer with the characteristics of low skin irritation, low shrinkage and high activity.
In a further embodiment, the photoinitiator comprises at least one of 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-phenyl-1-propanone, 2-methyl-2- (4-morpholinyl) -1- [4- (methylthio) phenyl ] -1-propanone, 2-hydroxy-2-methyl-1- [4- (2-hydroxyethoxy) phenyl ] -1-propanone, diphenyltrimethyl benzoyl phosphine oxide, ethyl 4-dimethylaminobenzoate, triarylsulfonium salts, and diaryliodonium salts.
In a further embodiment, the coupling agent is a silane coupling agent having the general formula Y-Si-X3Wherein Y is vinyl, methacryloxy, epoxy, amino; x is methoxyl, ethoxyl and chloro.
In a further embodiment, the carbon material comprises at least one of carbon black, acetylene black, graphite, carbon nanotubes, carbon fibers, graphene.
In a further embodiment, the organic solvent comprises at least one of toluene, xylene, butyl acetate, ethyl acetate, and butanone.
The invention will now be further described with reference to the following examples, which are intended to be illustrative of the invention and are not to be construed as limiting the invention.
Example 1
1. 1g of polydimethylsiloxane (organosiloxane, concentration of 10 wt%), 0.1g of 1, 6-hexanediol diacrylate (active monomer), 0.01g of diphenyltrimethylbenzoylphosphine oxide (photoinitiator), 0.05g of gamma-methacryloxypropyltrimethoxysilane (coupling agent) and 0.5g of carbon black (carbon material) were dissolved in 8.3g of xylene (organic solvent), and the mixture was stirred and dispersed to form a uniformly mixed slurry.
2. Coating the slurry obtained in the step 1 on one side of the support layer subjected to hydrophobic treatment by means of blade coating, spraying or screen printing and the like until the loading amount of the carbon material is 1.0mg/cm2。
3. Placing the sample in an ultraviolet curing box for curing, wherein the curing conditions are as follows: room temperature, ultraviolet wavelength of 365nm and curing energy of 1600mJ/cm2And curing for 1min to obtain the microporous layer of the gas diffusion layer.
Example 2
1. 1g of polydimethylsiloxane (organosiloxane, concentration of 10 wt%), 0.1g of 1, 6-hexanediol diacrylate (active monomer), 0.01g of diphenyltrimethylbenzoylphosphine oxide (photoinitiator), 0.05g of gamma-methacryloxypropyltrimethoxysilane (coupling agent) and 1g of carbon black (carbon material) were dissolved in 7.8g of xylene (organic solvent), and the mixture was stirred and dispersed to form a slurry which was uniformly mixed.
2. Coating the slurry obtained in the step 1 on one side of the support layer subjected to hydrophobic treatment by means of blade coating, spraying or screen printing and the like until the loading amount of the carbon material is 1.0mg/cm2。
3. Placing the sample in an ultraviolet curing box for curing, wherein the curing conditions are as follows: room temperature, ultraviolet wavelength of 365nm and curing energy of 1600mJ/cm2And curing for 1min to obtain the microporous layer of the gas diffusion layer.
Example 3
1. 2g of polydimethylsiloxane (organosiloxane, concentration of 10 wt%), 0.2g of 1, 6-hexanediol diacrylate (active monomer), 0.02g of diphenyltrimethylbenzoylphosphine oxide (photoinitiator), 0.1g of gamma-methacryloxypropyltrimethoxysilane (coupling agent) and 3g of carbon black (carbon material) were dissolved in 14.7g of xylene (organic solvent), and the mixture was stirred and dispersed to form a slurry which was uniformly mixed.
2. Coating the slurry obtained in the step 1 on one side of the support layer subjected to hydrophobic treatment by means of blade coating, spraying or screen printing and the like until the loading amount of the carbon material is 1.0mg/cm2。
3. Placing the sample in an ultraviolet curing box for curing, wherein the curing conditions are as follows: room temperature, ultraviolet wavelength of 365nm and curing energy of 1600mJ/cm2And curing for 1min to obtain the microporous layer of the gas diffusion layer.
Example 4
1. 1g of polydimethylsiloxane (organosiloxane, concentration of 10 wt%), 0.1g of 1, 6-hexanediol diacrylate (active monomer), 0.01g of diphenyltrimethylbenzoylphosphine oxide (photoinitiator), 0.05g of gamma-methacryloxypropyltrimethoxysilane (coupling agent) and 0.5g of acetylene black (carbon material) were dissolved in 8.3g of xylene (organic solvent), and the mixture was stirred and dispersed to form a slurry which was uniformly mixed.
2. Coating the slurry obtained in the step 1 on one side of the support layer subjected to hydrophobic treatment by means of blade coating, spraying or screen printing and the like until the loading amount of the carbon material is 1.0mg/cm2。
3. Placing the sample in an ultraviolet curing box for curing, wherein the curing conditions are as follows: room temperature, ultraviolet wavelength of 365nm and curing energy of 1600mJ/cm2And curing for 1min to obtain the microporous layer of the gas diffusion layer.
Example 5
1. 1g of polydimethylsiloxane (organosiloxane, concentration of 10 wt%), 0.1g of 1, 6-hexanediol diacrylate (active monomer), 0.01g of diphenyltrimethylbenzoylphosphine oxide (photoinitiator), 0.05g of gamma-methacryloxypropyltrimethoxysilane (coupling agent) and 0.5g of carbon black (carbon material) were dissolved in 8.3g of xylene (organic solvent), and the mixture was stirred and dispersed to form a uniformly mixed slurry.
2. Coating the slurry obtained in the step 1 on one side of the support layer subjected to hydrophobic treatment by means of blade coating, spraying or screen printing and the like until the loading amount of the carbon material is 0.5mg/cm2。
3. Placing the sample in an ultraviolet curing box for curing, wherein the curing conditions are as follows: room temperature, ultraviolet wavelength of 365nm and curing energy of 1600mJ/cm2And curing for 1min to obtain the microporous layer of the gas diffusion layer.
Example 6
1. 1g of polydimethylsiloxane (organosiloxane, concentration of 10 wt%), 0.1g of 1, 6-hexanediol diacrylate (active monomer), 0.01g of diphenyltrimethylbenzoylphosphine oxide (photoinitiator), 0.05g of gamma-methacryloxypropyltrimethoxysilane (coupling agent) and 0.5g of carbon black (carbon material) were dissolved in 8.3g of xylene (organic solvent), and the mixture was stirred and dispersed to form a uniformly mixed slurry.
2. Coating the slurry obtained in the step 1 on one side of the support layer subjected to hydrophobic treatment by means of blade coating, spraying or screen printing and the like until the loading amount of the carbon material is 1.0mg/cm2。
3. Placing the sample in an ultraviolet curing box for curing, wherein the curing conditions are as follows: room temperature, ultraviolet wavelength of 365nm and curing energy of 1000mJ/cm2And curing for 5min to obtain the microporous layer of the gas diffusion layer.
Comparative example 1
This comparative example differs from any of examples 1 to 6 in that: the microporous layer of the gas diffusion layer is prepared by adopting a traditional high-temperature curing process.
1. 1g of polydimethylsiloxane (organosiloxane, concentration: 10 wt%) and 0.5g of carbon black (carbon material) were dissolved in 8.5g of xylene (organic solvent), and the resulting solution was stirred and dispersed to form a slurry which was uniformly mixed.
2. Coating the slurry obtained in the step 1 on one side of the support layer subjected to hydrophobic treatment by means of blade coating, spraying or screen printing and the like until the loading amount of the carbon material is 1.0mg/cm2。
3. And placing the sample in a drying box, and sintering at 160 ℃ for 10min to obtain the microporous layer of the gas diffusion layer.
Comparative example 2
This comparative example differs from any of examples 1 to 6 in that: the microporous layer of the gas diffusion layer is prepared by adopting the traditional polytetrafluoroethylene as a hydrophobic agent.
1. 1g of polytetrafluoroethylene (PTFE, concentration of 10 wt%), 0.1g of 1, 6-hexanediol diacrylate (active monomer), 0.01g of diphenyltrimethylbenzoylphosphine oxide (photoinitiator), 0.05g of gamma-methacryloxypropyltrimethoxysilane (coupling agent) and 0.5g of carbon black (carbon material) were dissolved in 8.3g of xylene (organic solvent), and the mixture was stirred and dispersed to form a slurry which was uniformly mixed.
2. Coating the slurry obtained in the step 1 on one side of the support layer subjected to hydrophobic treatment by means of blade coating, spraying or screen printing and the like until the loading amount of the carbon material is 1.0mg/cm2。
3. Placing the sample in an ultraviolet curing box for curing, wherein the curing conditions are as follows: room temperature, ultraviolet wavelength of 365nm and curing energy of 1600mJ/cm2And curing for 1min to obtain the microporous layer of the gas diffusion layer.
Example of detection
The microporous layers of the gas diffusion layers prepared in examples 1 to 6 and comparative examples 1 to 2 were combined with CCM (cathode Pt loading 0.4 mg/cm)2Anode Pt loading 0.07mg/cm2) The frame and the sealing element are assembled into a single cell (the effective area is 7cm by 4 cm), and the test conditions are as follows: the cell temperature was 45 ℃, open cathode, hydrogen pressure 50kPa, hydrogen flow rate 2.77slpm, ambient humidity 50%. The test results are given in the following table:
as can be seen from the above table, the voltage values of examples 1 to 6 are all higher than those of comparative examples 1 to 2, and the better conductivity is shown, especially the effect of the microporous layer of the gas diffusion layer prepared in example 1 is the best, which shows that the preparation process using the organic siloxane as the hydrophobic agent and combining with the ultraviolet light curing technology is simple, and the battery performance is effectively improved.
It should be noted that the various features described in the above embodiments may be combined in any suitable manner without departing from the scope of the invention. The invention is not described in detail in order to avoid unnecessary repetition.
Claims (4)
1. A method of preparing a microporous layer of a gas diffusion layer of a membrane electrode of a fuel cell, the gas diffusion layer comprising a support layer and a microporous layer; the method is characterized by comprising the following steps:
dissolving organic siloxane, an active monomer, a photoinitiator, a coupling agent and a carbon material in an organic solvent according to a predetermined proportion, and stirring and dispersing to form uniformly mixed slurry;
coating the slurry on one side of the support layer subjected to hydrophobic treatment until the loading amount of the carbon material is 0.5-3.0mg/cm2Obtaining a supporting layer with slurry;
placing the support layer with the slurry in an ultraviolet curing box for curing, and forming a microporous layer on the support layer;
the organic siloxane is one of polydimethylsiloxane, polymethylsiloxane and alpha, omega-dihydroxy polysiloxane;
the polydimethylsiloxane, the polymethylsiloxane and the alpha, omega-dihydroxy polysiloxane are all oligomers, and the molecular weight of the oligomers is 500-4000 g/mol;
the slurry comprises the following components: 10 to 40 weight percent of organic siloxane, 1 to 2 weight percent of active monomer, 0.1 to 1 weight percent of photoinitiator, 0.5 to 2.5 weight percent of coupling agent, 5 to 20 weight percent of carbon material and the balance of solvent;
the curing conditions for placing the support layer with the sizing agent in an ultraviolet curing box for curing are as follows: the temperature is 0-25 ℃, the ultraviolet wavelength is 365-2Curing for 1-5 min;
the active monomer is one of butyl acrylate, 1, 6-hexanediol diacrylate, methoxyl or ethoxylated acrylate;
the coupling agent is a silane coupling agent with a general formula of Y-Si-X3Wherein Y is vinyl, methacryloxy, epoxy, amino; x is methoxy, ethoxy, chloro;
the carbon material is one of carbon black, acetylene black, graphite, carbon nanotubes, carbon fibers and graphene.
2. The method of claim 1, wherein the photoinitiator comprises at least one of 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-phenyl-1-propanone, 2-methyl-2- (4-morpholinyl) -1- [4- (methylthio) phenyl ] -1-propanone, 2-hydroxy-2-methyl-1- [4- (2-hydroxyethoxy) phenyl ] -1-propanone, diphenyltrimethylbenzoylphosphine oxide, ethyl 4-dimethylaminobenzoate, triarylsulfonium salts, and diaryliodonium salts.
3. A gas diffusion layer obtained by a method for preparing a microporous layer based on the fuel cell membrane electrode gas diffusion layer of claim 1 or 2.
4. The use of a fuel cell membrane electrode produced on the basis of the gas diffusion layer according to claim 3 as a fuel cell membrane electrode or as a constituent of a fuel cell membrane electrode in the fuel cell field.
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| CN114430050B (en) * | 2022-01-18 | 2023-10-24 | 山东仁丰特种材料股份有限公司 | Gas diffusion layer for high-performance hydrogen fuel cell and preparation method thereof |
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