CN111509251A - Bipolar plate for hydrogen fuel cell and preparation method thereof - Google Patents
Bipolar plate for hydrogen fuel cell and preparation method thereof Download PDFInfo
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- CN111509251A CN111509251A CN202010353412.9A CN202010353412A CN111509251A CN 111509251 A CN111509251 A CN 111509251A CN 202010353412 A CN202010353412 A CN 202010353412A CN 111509251 A CN111509251 A CN 111509251A
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- bipolar plate
- hydrogen fuel
- fuel cell
- defoaming agent
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/02—Details
- H01M8/0202—Collectors; Separators, e.g. bipolar separators; Interconnectors
- H01M8/0204—Non-porous and characterised by the material
- H01M8/0213—Gas-impermeable carbon-containing materials
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/02—Details
- H01M8/0202—Collectors; Separators, e.g. bipolar separators; Interconnectors
- H01M8/0258—Collectors; Separators, e.g. bipolar separators; Interconnectors characterised by the configuration of channels, e.g. by the flow field of the reactant or coolant
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
Abstract
The invention discloses a bipolar plate for a hydrogen fuel cell and a preparation method thereof, belonging to the field of fuel cells. The preparation method comprises the following steps: (1) pulping, (2) casting to form a film, drying, (3) vacuum film rolling and densification, roller pressing to form a groove, and (4) cutting, shaping and punching; (5) sintering and densifying again. The invention applies the tape casting film forming technology to the preparation of the bipolar plate of the hydrogen fuel cell for the first time, the preparation method can replace the backward machining forming or compression molding forming mode, the ultrathin bipolar plate can be produced in batch, and the prepared bipolar plate has excellent compactness, corrosion resistance, toughness, conductivity and strength performance.
Description
Technical Field
The invention belongs to the field of fuel cells, and particularly relates to a bipolar plate for a hydrogen fuel cell and a preparation method thereof.
Background
The bipolar plates commonly used in hydrogen fuel cells mainly comprise graphite carbon plates, metal bipolar plates and composite bipolar plates, and the graphite bipolar plates are the mainstream of domestic application at present. Most of the graphite bipolar plates adopt a mechanical processing or compression molding mode, and foreign manufacturers directly adopt a compression molding or expansion graphite extrusion molding mode, so that the processing mode is single.
Disclosure of Invention
In order to solve the technical problem, the invention provides a preparation method of a bipolar plate for a hydrogen fuel cell. The method is a novel manufacturing method of the bipolar plate with the film formed by the tape casting, can replace the backward mechanical processing forming mode or the compression molding forming mode, and can produce the bipolar plate with the ultrathin thickness of 0.1 mm-1 mm in batch.
In order to achieve the purpose, the invention adopts the following technical scheme:
a preparation method of bipolar plates for hydrogen fuel cells comprises the following steps:
(1) pulping: adding graphite powder and a certain proportion of dispersing agent into a solvent (water-based or organic solvent), opening particle agglomeration through ball milling or ultrasonic oscillation, ensuring that the solvent wets the graphite powder, adding a certain proportion of binder and plasticizer, performing secondary ball milling, and adding a defoaming agent to perform vacuum defoaming, thus obtaining stable and uniform slurry;
(2) casting film forming and drying: conveying the slurry into a casting machine container, reasonably setting three parameters of the liquid level height of the slurry, the knife edge height of a casting scraper and the tape travelling speed of the casting machine, obtaining the thickness of a required film, translating the statically stable film through a steel belt, and drying the film through a plurality of drying temperature regions;
(3) vacuum film rolling densification (vacuum degree between 0.1pa and 1000 pa), roller pressing groove: guiding a film with certain strength into a double roller of a film rolling machine, setting the film rolling machine to be in a vacuum state, arranging a plurality of groups of rollers with different intervals on the film rolling machine, gradually reducing the intervals, increasing the density and shaping, wherein the last group of rollers are shaping grooved rollers which are shaping die rollers designed according to the hydrogen diffusion requirement of a bipolar plate, and forming airflow fields of hydrogen, oxygen, water and the like through rolling;
(4) cutting, shaping and punching: designing a cold pressing film according to the design size requirement, punching and forming the bipolar plate, deburring after punching, dulling and polishing edges and corners, and punching;
(5) sintering and densifying again: under the protection of inert gas, the graphite bipolar plate is subjected to high-temperature treatment, and liquid-phase substances such as asphalt and the like are utilized to bond solid particles, so that the effect of densification is achieved again.
The invention can adopt 100-plus 500-mesh artificial graphite as a raw material, and the following components are added according to the mass percentage of graphite powder: 10-25% of a dispersant, wherein the dispersant is one or more of dimethylthiamine, carboxymethyl cellulose, sodium polyacrylate, sodium dodecyl benzene sulfonate and sodium dodecyl sulfate; 10-25% of a solvent, wherein the solvent is ethanol; 10-20% of a binder, wherein the binder is vinyl resin or bisphenol; 5-20% of a plasticizer, wherein the plasticizer is dibutyl phthalate or polyethylene glycol; 0.1-1.5% of defoaming agent, wherein the defoaming agent is polyether defoaming agent, glycol or n-butyl alcohol; the secondary ball milling time is 2-20 hours.
The invention can also adopt 100-plus 500-mesh artificial graphite powder coated with 5-10% by mass of 100-plus 150 ℃ asphalt as a raw material, and the following components are added according to the mass percent of the graphite powder coated with the asphalt: 15-30% of a dispersant, wherein the dispersant is one or more of dimethylthiamine, carboxymethyl cellulose, sodium polyacrylate, sodium dodecyl benzene sulfonate and sodium dodecyl sulfate; 10-25% of a solvent, wherein the solvent is ethanol; 5-10% of a binder, wherein the binder is vinyl resin or bisphenol; 5-20% of a plasticizer, wherein the plasticizer is dibutyl phthalate or polyethylene glycol; 0.1-1.5% of defoaming agent, wherein the defoaming agent is polyether defoaming agent, glycol or n-butyl alcohol; the secondary ball milling time is 2-20 hours.
Further, the drying temperature in the step (2) is 200-500 ℃, the sintering temperature in the step (5) is 900-1300 ℃, and the sintering time is 0.5-3 hours.
The invention can also adopt 100-mesh 500-mesh artificial graphite powder coated with metal nickel with the mass percent of 2-5% as a raw material, and the following components are added according to the mass percent of the graphite powder coated with the metal nickel: 15-30% of a dispersant, wherein the dispersant is one or more of dimethylthiamine, carboxymethyl cellulose, sodium polyacrylate, sodium dodecyl benzene sulfonate and sodium dodecyl sulfate; 10-25% of a solvent, wherein the solvent is ethanol; 5-10% of a binder, wherein the binder is vinyl resin or bisphenol; 5-20% of a plasticizer, wherein the plasticizer is dibutyl phthalate or polyethylene glycol; 0.1-1.5% of defoaming agent, wherein the defoaming agent is polyether defoaming agent, glycol or n-butyl alcohol; the secondary ball milling time is 2-20 hours.
Further, the drying temperature in the step (2) is 200-500 ℃, the sintering temperature in the step (5) is 900-1300 ℃, and the sintering time is 0.5-3 hours.
The invention also provides a bipolar plate of the hydrogen fuel cell prepared by the method.
The graphite bipolar plate for the hydrogen fuel cell, which has the thickness of 0.1-1mm, high compactness, high strength, good toughness, good electrical conductivity and corrosion resistance, can be obtained by the method.
Compared with the prior art, the invention has the following beneficial effects:
the invention applies the tape casting film forming technology to the preparation of the bipolar plate of the hydrogen fuel cell for the first time, the preparation method can replace the backward machining forming mode or the compression molding forming mode, and can produce the ultrathin bipolar plate in batches, and the prepared electrode plate has excellent compactness, corrosion resistance, toughness, conductivity and strength performance.
Detailed Description
Example 1
In this embodiment, the preparation of the graphite bipolar plate for the hydrogen fuel cell by using 100-mesh and 500-mesh artificial graphite as a raw material comprises the following steps:
(1) pulping: adding a dispersing agent dimethylthiamine according to the mass percentage of 10-25% of graphite powder, adding a solvent ethanol according to the mass percentage of 10-25%, adding a plasticizer dibutyl phthalate according to the mass percentage of 5-20%, opening particle agglomeration through ball milling or ultrasonic oscillation, ensuring that the solvent wets the graphite powder, adding a binder vinyl resin (P104-02) according to the mass percentage of 10-20% of graphite powder, performing secondary ball milling for 2-20 hours, adding a defoaming agent ethylene glycol according to the mass percentage of 0.3%, and performing vacuum defoaming to obtain stable and uniform slurry;
(2) casting film forming and drying: conveying the slurry into a casting machine container, reasonably setting three parameters of slurry liquid level height, blade height of a casting scraper and tape travelling speed of the casting machine to obtain the thickness of a required film, and performing steel tape translation on the film which is stable in standing and drying through a plurality of drying temperature areas, wherein the drying temperature is 200 ℃;
(3) vacuum film rolling densification and groove rolling: guiding a film with certain strength into a double roller of a film rolling machine, setting the film rolling machine to be in a vacuum state, arranging a plurality of groups of rollers with different intervals on the film rolling machine, gradually reducing the intervals, increasing the density and shaping, wherein the last group of rollers are shaping grooved rollers which are shaping die rollers designed according to the hydrogen diffusion requirement of a bipolar plate, and forming airflow fields of hydrogen, oxygen, water and the like through rolling;
(4) cutting and shaping: designing a cold pressing film according to the design size requirement, punching and forming the bipolar plate, deburring after punching, and blunting and polishing edges and corners;
(5) sintering and densifying again: under the protection of inert gas, the graphite bipolar plate is sintered at the high temperature of 900 ℃ for 2 hours, and the liquid phase substance is utilized to bond solid particles, so that the effect of densification is achieved again.
The performance parameters of the graphite bipolar plate for the hydrogen fuel cell prepared by the method are shown in table 1, and the thickness of the graphite bipolar plate is 0.3 mm.
TABLE 1
As can be seen from the above table, the bipolar plate prepared in this example is excellent in compactness, strength, conductivity, corrosion resistance, etc.
Example 2
In the embodiment, the graphite bipolar plate for the hydrogen fuel cell is prepared by using asphalt-coated 100-mesh 500-mesh artificial graphite powder with the mass percentage of 5-10% and the temperature of 120 ℃ as a raw material, and the steps are as follows:
(1) pulping: adding a dispersing agent carboxymethyl cellulose (CMC) according to the mass percent of 15-30% of graphite powder coated with asphalt, adding a solvent ethanol in 10-25%, adding a plasticizer polyethylene glycol (with the polymerization degree of 8-100) in 5-20%, opening particle agglomeration through ball milling or ultrasonic oscillation, ensuring that the solvent wets the graphite powder, adding a binder bisphenol in 5-10%, carrying out secondary ball milling for 2-20 hours, adding n-butyl alcohol serving as a defoaming agent in 0.2%, and carrying out vacuum defoaming to obtain stable and uniform slurry;
(2) casting film forming and drying: conveying the slurry into a casting machine container, reasonably setting three parameters of slurry liquid level height, blade height of a casting scraper and tape travelling speed of the casting machine to obtain the thickness of a required film, and performing steel tape translation on the film which is stable in standing and drying through a plurality of drying temperature areas, wherein the drying temperature is 500 ℃;
(3) vacuum film rolling densification and groove rolling: guiding a film with certain strength into a double roller of a film rolling machine, setting the film rolling machine to be in a vacuum state, arranging a plurality of groups of rollers with different intervals on the film rolling machine, gradually reducing the intervals, increasing the density and shaping, wherein the last group of rollers are shaping grooved rollers which are shaping die rollers designed according to the hydrogen diffusion requirement of a bipolar plate, and forming airflow fields of hydrogen, oxygen, water and the like through rolling;
(4) cutting and shaping: and designing a cold pressing film according to the design size requirement, punching and forming the bipolar plate, deburring after punching, and blunting and polishing edges and corners.
(5) Sintering and densifying again: under the protection of inert gas, the graphite bipolar plate is sintered for 3 hours at 1100 ℃, and solid particles are bonded by using a liquid phase substance to play a role in densification again.
The graphite bipolar plate for the hydrogen fuel cell, which has the thickness of 0.1-1mm, high compactness, high strength, good toughness, good electrical conductivity and corrosion resistance, can be obtained by the method.
Example 3
In the embodiment, the graphite bipolar plate for the hydrogen fuel cell is prepared by using the artificial graphite powder with the particle size of 100 meshes coated with 2-5% of metallic nickel in percentage by mass as a raw material, and the preparation method comprises the following steps:
(1) pulping: adding a dispersing agent sodium dodecyl benzene sulfonate according to the mass percentage of 15-30% of graphite powder coated with metallic nickel, adding a solvent ethanol according to the mass percentage of 10-25%, adding a plasticizer dibutyl phthalate according to the mass percentage of 5-20%, opening particle agglomeration through ball milling or ultrasonic oscillation, ensuring that the solvent wets graphite powder, adding a binder bisphenol according to the mass percentage of 5-10%, adding a defoaming agent ethylene glycol according to the mass percentage of 0.1-1.5%, carrying out vacuum defoaming, and carrying out ball milling for 2-20 hours to obtain stable and uniform slurry;
(2) casting film forming and drying: the method comprises the steps of conveying the slurry into a casting machine container, reasonably setting three parameters of slurry liquid level height, knife edge height of a casting scraper and tape travelling speed of the casting machine to obtain the thickness of a required film, enabling the film which is stable in standing to be translated through a steel belt, and drying through a plurality of drying temperature zones, wherein the drying temperature is 300 ℃.
(3) Vacuum film rolling densification and groove rolling: guiding a film with certain strength into a double roller of a film rolling machine, setting the film rolling machine to be in a vacuum state, arranging a plurality of groups of rollers with different intervals on the film rolling machine, gradually reducing the intervals, increasing the density and shaping, wherein the last group of rollers are shaping grooved rollers which are shaping die rollers designed according to the hydrogen diffusion requirement of a bipolar plate, and forming airflow fields of hydrogen, oxygen, water and the like through rolling;
(4) cutting and shaping: designing a cold pressing film according to the design size requirement, punching and forming the bipolar plate, deburring after punching, and blunting and polishing edges and corners;
(5) sintering and densifying again: under the protection of inert gas, the graphite bipolar plate is sintered for 0.5 hour at 1300 ℃, and solid particles are bonded by liquid phase substances, so that the effect of densification is achieved again.
The graphite bipolar plate for the hydrogen fuel cell, which has the thickness of 0.1-1mm, high compactness, high strength, good toughness, good electrical conductivity and corrosion resistance, can be obtained by the method.
The above-described embodiments are merely illustrative of the preferred embodiments of the present invention, and do not limit the scope of the present invention, and various modifications and improvements of the technical solutions of the present invention can be made by those skilled in the art without departing from the spirit of the present invention, and the technical solutions of the present invention are within the scope of the present invention defined by the claims.
Claims (10)
1. A preparation method of bipolar plates for hydrogen fuel cells is characterized by comprising the following steps:
(1) pulping: adding graphite powder and a dispersant in a certain proportion into a solvent, uniformly mixing, adding a binder and a plasticizer in a certain proportion, performing secondary ball milling, and adding a defoaming agent to perform vacuum defoaming, thus obtaining stable and uniform slurry;
(2) casting to form a film and drying;
(3) vacuum film rolling densification and groove rolling;
(4) cutting, shaping and punching;
(5) sintering and densifying again.
2. The method for preparing a bipolar plate for a hydrogen fuel cell as claimed in claim 1, wherein the graphite powder is prepared from 100-500 mesh artificial graphite.
3. The method for manufacturing a bipolar plate for a hydrogen fuel cell according to claim 2, wherein 5 to 10 mass% of asphalt at 100 ℃ to 150 ℃ is added to the artificial stone toner, and then the artificial stone toner is coated with the asphalt and added to the solvent together with the dispersant.
4. The method of manufacturing a bipolar plate for a hydrogen fuel cell according to claim 2, wherein the artificial graphite powder is graphite powder coated with metal nickel in an amount of 2 to 5% by mass on the surface thereof, and the graphite powder is added to a solvent together with a dispersant.
5. The method for producing a bipolar plate for a hydrogen fuel cell according to claim 1 or 2, wherein the following components are added in percentage by mass of graphite powder: 10-25% of a dispersant, wherein the dispersant is one or more of dimethylthiamine, carboxymethyl cellulose, sodium polyacrylate, sodium dodecyl benzene sulfonate and sodium dodecyl sulfate; 10-25% of a solvent, wherein the solvent is ethanol; 10-20% of a binder, wherein the binder is vinyl resin or bisphenol; 5-20% of a plasticizer, wherein the plasticizer is dibutyl phthalate or polyethylene glycol; 0.1-1.5% of defoaming agent, wherein the defoaming agent is polyether defoaming agent, glycol or n-butyl alcohol; the secondary ball milling time is 2-20 hours.
6. The method for preparing a bipolar plate for a hydrogen fuel cell according to claim 3, wherein the following components are added in percentage by mass to the graphite powder coated with the pitch: 15-30% of a dispersant, wherein the dispersant is one or more of dimethylthiamine, carboxymethyl cellulose, sodium polyacrylate, sodium dodecyl benzene sulfonate and sodium dodecyl sulfate; 10-25% of a solvent, wherein the solvent is ethanol; 5-10% of a binder, wherein the binder is vinyl resin or bisphenol; 5-20% of a plasticizer, wherein the plasticizer is dibutyl phthalate or polyethylene glycol; 0.1-1.5% of defoaming agent, wherein the defoaming agent is polyether defoaming agent, glycol or n-butyl alcohol; the secondary ball milling time is 2-20 hours.
7. The method for preparing a bipolar plate for a hydrogen fuel cell according to claim 4, wherein the following components are added in percentage by mass to the graphite powder coated with metallic nickel: 15-30% of a dispersant, wherein the dispersant is one or more of dimethylthiamine, carboxymethyl cellulose, sodium polyacrylate, sodium dodecyl benzene sulfonate and sodium dodecyl sulfate; 10-25% of a solvent, wherein the solvent is ethanol; 5-10% of a binder, wherein the binder is vinyl resin or bisphenol; 5-20% of a plasticizer, wherein the plasticizer is dibutyl phthalate or polyethylene glycol; 0.1-1.5% of defoaming agent, wherein the defoaming agent is polyether defoaming agent, glycol or n-butyl alcohol; the secondary ball milling time is 2-20 hours.
8. The method of manufacturing a bipolar plate for a hydrogen fuel cell according to claim 6, wherein the baking temperature in the step (2) is 200 ℃ to 500 ℃, the sintering temperature in the step (5) is 900 ℃ to 1300 ℃, and the sintering time is 0.5 to 3 hours.
9. The method of manufacturing a bipolar plate for a hydrogen fuel cell according to claim 7, wherein the baking temperature in the step (2) is 200 ℃ to 500 ℃, the sintering temperature in the step (5) is 900 ℃ to 1300 ℃, and the sintering time is 0.5 to 3 hours.
10. A bipolar plate for a hydrogen fuel cell, wherein the bipolar plate for a hydrogen fuel cell is prepared by the preparation method of any one of claims 1 to 4 and 6 to 9.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN114784308A (en) * | 2022-04-14 | 2022-07-22 | 广东氢发新材料科技有限公司 | Preparation method of proton exchange membrane fuel cell bipolar plate |
| DE102022200621A1 (en) | 2022-01-20 | 2023-07-20 | Robert Bosch Gesellschaft mit beschränkter Haftung | Process for manufacturing a contact plate |
| WO2023236234A1 (en) * | 2022-06-08 | 2023-12-14 | 深圳市氢瑞燃料电池科技有限公司 | Fuel cell bipolar plate and manufacturing method therefor |
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| CN1472833A (en) * | 2003-05-22 | 2004-02-04 | 上海交通大学 | High-per formance carbon material preparing method by water-base curtain coating technology |
| CN102074714A (en) * | 2010-12-17 | 2011-05-25 | 湖南大学 | Method for preparing fuel cell bipolar plate by using transition metal-graphite interlayer complex as filler |
| CN104355303A (en) * | 2014-10-22 | 2015-02-18 | 合肥杰事杰新材料股份有限公司 | Carbon film with high conductivity and heat conduction and forming process therefor |
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| CN1472833A (en) * | 2003-05-22 | 2004-02-04 | 上海交通大学 | High-per formance carbon material preparing method by water-base curtain coating technology |
| CN102074714A (en) * | 2010-12-17 | 2011-05-25 | 湖南大学 | Method for preparing fuel cell bipolar plate by using transition metal-graphite interlayer complex as filler |
| CN104355303A (en) * | 2014-10-22 | 2015-02-18 | 合肥杰事杰新材料股份有限公司 | Carbon film with high conductivity and heat conduction and forming process therefor |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE102022200621A1 (en) | 2022-01-20 | 2023-07-20 | Robert Bosch Gesellschaft mit beschränkter Haftung | Process for manufacturing a contact plate |
| CN114784308A (en) * | 2022-04-14 | 2022-07-22 | 广东氢发新材料科技有限公司 | Preparation method of proton exchange membrane fuel cell bipolar plate |
| WO2023236234A1 (en) * | 2022-06-08 | 2023-12-14 | 深圳市氢瑞燃料电池科技有限公司 | Fuel cell bipolar plate and manufacturing method therefor |
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