CN111063910A - Microporous layer, gas diffusion layer, preparation method and application thereof - Google Patents

Microporous layer, gas diffusion layer, preparation method and application thereof Download PDF

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Publication number
CN111063910A
CN111063910A CN201911150252.1A CN201911150252A CN111063910A CN 111063910 A CN111063910 A CN 111063910A CN 201911150252 A CN201911150252 A CN 201911150252A CN 111063910 A CN111063910 A CN 111063910A
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China
Prior art keywords
layer
gas diffusion
microporous layer
diffusion layer
microporous
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CN201911150252.1A
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Inventor
马千里
曹婷婷
米新艳
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FAW Jiefang Automotive Co Ltd
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FAW Jiefang Automotive Co Ltd
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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
    • H01M8/023—Porous and characterised by the material
    • H01M8/0241—Composites
    • 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
    • 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
    • H01M8/023—Porous and characterised by the material
    • H01M8/0234—Carbonaceous material
    • 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
    • H01M8/023—Porous and characterised by the material
    • H01M8/0239—Organic resins; Organic polymers
    • 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

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  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Sustainable Development (AREA)
  • Sustainable Energy (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Composite Materials (AREA)
  • Fuel Cell (AREA)
  • Inert Electrodes (AREA)

Abstract

The invention provides a microporous layer, a gas diffusion layer, a preparation method and an application thereof; the preparation raw materials of the microporous layer comprise organic siloxane, carbon nano material and organic solvent; the microporous layer comprises organic siloxane and a carbon nanomaterial, the polymethylsiloxane is decomposed into substances with smaller molecular weight under the heat treatment condition, so that the surface tension of the microporous layer is reduced, and the polymethylsiloxane and carbon black form a micro-nano structure; the gas diffusion layer used for the proton exchange membrane fuel cell can improve the electrochemical performance of the fuel cell, so that the gas diffusion layer can be used as a power source for automobiles.

Description

Microporous layer, gas diffusion layer, preparation method and application thereof
Technical Field
The invention belongs to the field of fuel cells, and relates to a microporous layer, a gas diffusion layer, and preparation methods and applications thereof.
Background
A Proton Exchange Membrane Fuel Cell (PEMFC) is a low temperature fuel cell that uses a proton exchange membrane as an electrolyte, Pt/C as a catalyst, hydrogen as a fuel, and air or pure oxygen as an oxidant. Considering that environmental pollution and energy problems are now serious, PEMFC has the advantages of higher power density and environmental friendliness, making it promising to replace fossil fuels as an energy resource applied to automatic, stationary and portable devices. A Membrane Electrode Assembly (MEA) is a vital part of a proton exchange membrane fuel cell system and includes a proton exchange membrane, a catalytic layer, and a Gas Diffusion Layer (GDL).
Application No. 200480027044.8 discloses a fuel cell gas diffusion layer comprising a hydrophilic surface layer having a thickness of no more than 1 micron and underlying a hydrophobic second layer having a thickness of at least 5 microns. In addition, the invention also provides a method for preparing the gas diffusion layer of the fuel cell, which comprises the following steps: a) providing a carbon fiber structure; b) coating at least the upper surface of the carbon fiber structure with a composition comprising a fluoropolymer; and c) exposing the upper surface to at least one plasma, such as a silane plasma, to produce a hydrophilic surface layer having a thickness of no greater than 1 micron. The invention also provides a method which additionally comprises partial coating of the upper surface with a mask with windows according to a pattern, whereby a hydrophilic surface layer is applied according to the pattern. The present invention also provides a method wherein the carbon fiber structure is provided in roll-good form, and the step of exposing the upper surface to at least one plasma in a continuous roll-to-roll manner; but the hydrophobicity of the resulting gas diffusion layer still remains to be improved.
The patent application No. 200610068168.1 discloses a gas diffusion layer for a proton exchange membrane fuel cell and a method of making the same. The gas diffusion layer comprises a porous supporting layer and a microporous layer, wherein the porous supporting layer is of a net-shaped and porous structure. The microporous layer is compounded on the surface of the porous support layer close to one side of the catalytic layer. The microporous layer uniformly covers the surfaces of the macropores and the fiber-dense region of the porous support layer and does not penetrate into the interior of the porous support layer. The invention adopts dry method to prepare gas diffusion layer for proton exchange membrane fuel cell, the used fluorine-containing polymer 1 and fluorine-containing polymer 2 can be the same polymer or different polymers. The hydrophilic/hydrophobic degrees of the porous support layer and the microporous layer of the gas diffusion layer are respectively adjustable. The hydrophobicity of the gas diffusion layer of the invention remains to be improved.
Therefore, it is very necessary to provide a gas diffusion layer having excellent hydrophobic properties.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide a microporous layer, a gas diffusion layer, and a preparation method and application thereof; the microporous layer comprises organic siloxane and a carbon nanomaterial, the polymethylsiloxane is decomposed into substances with smaller molecular weight under the heat treatment condition, so that the surface tension of the microporous layer is reduced, and the polymethylsiloxane and carbon black form a micro-nano structure; the gas diffusion layer used for the proton exchange membrane fuel cell can improve the electrochemical performance of the fuel cell, so that the gas diffusion layer can be used as a power source for automobiles.
An object of the present invention is to provide a microporous layer, which is prepared from raw materials including an organosiloxane, a carbon nanomaterial, and an organic solvent.
In the invention, the microporous layer comprises organic siloxane and carbon nanomaterials, the polymethylsiloxane is decomposed into substances with smaller molecular weight under the heat treatment condition, so that the surface tension of the microporous layer is reduced, and the polymethylsiloxane and carbon black form a micro-nano structure.
In the present invention, the raw material for preparing the microporous layer includes 2 to 35 mass% (e.g., 2%, 5%, 7%, 10%, 12%, 15%, 17%, 20%, 22%, 25%, 27%, 30%, 32%, 35%, etc.) of an organosiloxane, 2 to 50 mass% (e.g., 2%, 5%, 7%, 10%, 12%, 15%, 17%, 20%, 22%, 25%, 27%, 30%, 32%, 35%, 37%, 40%, 42%, 45%, 47%, 50%, etc.) of a carbon nanomaterial, and 15 to 96 mass% (e.g., 15%, 20%, 25%, 30%, 35%, 40%, 45%, 50%, 55%, 60%, 65%, 70%, 75%, 80%, 85%, 90%, 96%, etc.) of an organic solvent.
In the present invention, the raw material for preparing the microporous layer includes 2 to 10 mass% (e.g., 2%, 3%, 4%, 5%, 6%, 7%, 8%, 9%, 10%, etc.) of an organosiloxane, 3 to 15 mass% (e.g., 3%, 4%, 5%, 6%, 7%, 8%, 9%, 10%, 11%, 12%, 13%, 14%, 15%, etc.) of a carbon nanomaterial, and 75 to 95 mass% (e.g., 75%, 77%, 80%, 82%, 85%, 87%, 90%, 92%, 95%, etc.) of an organic solvent.
In the present invention, the organosiloxane is polymethylsiloxane.
In the present invention, the carbon nanomaterial is carbon black.
In the present invention, the organic solvent is tetrahydrofuran.
Another object of the present invention is to provide a method for preparing a microporous layer, the method comprising: and mixing the organic siloxane, the carbon nano material and the organic solvent, and curing to obtain the microporous layer.
The preparation method of the microporous layer is simple, the raw materials are easy to obtain, the price is low, the realization is easy, and the industrial large-scale production and application are facilitated.
In the present invention, the mixing manner is ultrasonic mixing.
In the present invention, the curing temperature is 120-.
In the present invention, the curing time is 10-70min, such as 10min, 20min, 30min, 40min, 50min, 60min, 70min, etc.
Another object of the present invention is to provide a gas diffusion layer including a substrate layer and a microporous layer on one side surface of the substrate layer, the microporous layer being one of the objects.
In the present invention, the support layer is a carbon paper layer.
The fourth object of the present invention is to provide a method for preparing a gas diffusion layer, comprising: and coating a mixed solution of organic siloxane, a carbon nano material and an organic solvent on the surface of one side of the supporting layer, and curing to obtain the gas diffusion layer.
In the invention, the coating mode is knife coating or spraying.
In the present invention, the curing temperature is 120-.
In the present invention, the curing time is 10-70min, such as 10min, 20min, 30min, 40min, 50min, 60min, 70min, etc.
The fifth object of the present invention is to provide a proton exchange membrane fuel cell, which comprises a proton exchange layer, a catalyst layer and a gas diffusion layer laminated together, wherein the gas diffusion layer is the gas diffusion layer of the third object.
The sixth purpose of the invention is to provide an application of the proton exchange membrane fuel cell as the fifth purpose in the early automobile as power energy.
Compared with the prior art, the invention has the following beneficial effects:
the microporous layer comprises organic siloxane and a carbon nanomaterial, the polymethylsiloxane is decomposed into substances with smaller molecular weight under the heat treatment condition, so that the surface tension of the microporous layer is reduced, and the microporous layer and carbon black form a micro-nano structure; the gas diffusion layer used for the proton exchange membrane fuel cell can improve the electrochemical performance of the fuel cell, so that the gas diffusion layer can be used as a power source for automobiles.
Detailed Description
The technical solution of the present invention is further explained by the following embodiments. It should be understood by those skilled in the art that the examples are only for the understanding of the present invention and should not be construed as the specific limitations of the present invention.
Example 1
The present embodiment provides a method for preparing a gas diffusion layer, including: adding 4g of polymethylsiloxane into 92g of tetrahydrofuran, mechanically stirring, ultrasonically forming uniform suspension, and then coating the suspension on one side surface of the hydrophobic carbon paper until the loading amount of carbon black is up toIs 1mg/cm2And naturally drying, placing in a drying oven, and sintering at 150 ℃ for 10min to obtain the gas diffusion layer.
The gas diffusion layer obtained in example 1 was subjected to a contact angle test, and the contact angle was 153 ℃.
Example 2
The present embodiment provides a method for preparing a gas diffusion layer, including: adding 2g of polymethylsiloxane and 3g of carbon black into 95g of tetrahydrofuran, mechanically stirring, ultrasonically forming uniform suspension, and then coating the suspension on one side surface of the hydrophobic carbon paper until the loading amount of the carbon black is 1mg/cm2And naturally drying, placing in a drying oven, and sintering at 150 ℃ for 30min to obtain the gas diffusion layer.
The gas diffusion layer obtained in example 2 was subjected to the same test method as in example 1, and the contact angle was 149 ℃.
Example 3
The present embodiment provides a method for preparing a gas diffusion layer, including: adding 3g of polymethylsiloxane and 3g of carbon black into 94g of tetrahydrofuran, mechanically stirring, ultrasonically forming uniform suspension, and then coating the suspension on one side surface of the hydrophobic carbon paper until the loading amount of the carbon black is 1mg/cm2And naturally drying, placing in a drying oven, and sintering at 150 ℃ for 30min to obtain the gas diffusion layer.
The gas diffusion layer obtained in example 3 was subjected to the same test method as in example 1, and the contact angle was 151 ℃.
Example 4
The present embodiment provides a method for preparing a gas diffusion layer, including: adding 10g of polymethylsiloxane and 15g of carbon black into 75g of tetrahydrofuran, mechanically stirring, ultrasonically forming uniform suspension, and then coating the suspension on one side surface of the hydrophobic carbon paper until the loading amount of the carbon black is 6mg/cm2And naturally drying, placing in a drying oven, and sintering at 120 ℃ for 70min to obtain the gas diffusion layer.
The gas diffusion layer obtained in example 4 was subjected to the same test method as in example 1, and the contact angle was 148 ℃.
The applicant declares that the above description is only a specific embodiment of the present invention, but the scope of the present invention is not limited thereto, and it should be understood by those skilled in the art that any changes or substitutions that can be easily conceived by those skilled in the art within the technical scope of the present invention are within the scope and disclosure of the present invention.

Claims (10)

1. A microporous layer, characterized in that the microporous layer is prepared from raw materials comprising an organosiloxane, a carbon nanomaterial, and an organic solvent.
2. The microporous layer of claim 1, wherein the raw materials for preparing the microporous layer comprise 2-35 wt% of organic siloxane, 2-50% of carbon nanomaterial, and 15-96% of organic solvent;
preferably, the raw materials for preparing the microporous layer comprise 2-10% of organic siloxane, 3-15% of carbon nano material and 75-95% of organic solvent by mass percentage.
3. The microporous layer of claim 1 or 2, wherein the organosiloxane is a polymethylsiloxane;
preferably, the carbon nanomaterial is carbon black;
preferably, the organic solvent is tetrahydrofuran.
4. The method of preparing a microporous layer according to any of claims 1-3, wherein the method of preparing a microporous layer comprises: and mixing the organic siloxane, the carbon nano material and the organic solvent, and curing to obtain the microporous layer.
5. The method of claim 4, wherein the mixing is performed by ultrasonic mixing;
preferably, the temperature of the curing is 120-210 ℃;
preferably, the curing time is 10-70 min.
6. A gas diffusion layer comprising a substrate layer and a microporous layer on one surface of the substrate layer, wherein the microporous layer is according to any one of claims 1 to 3.
7. Gas diffusion layer according to claim 1 or 2, characterized in that the support layer is a carbon paper layer.
8. The method for producing a gas diffusion layer according to claim 6 or 7, comprising: coating a mixed solution of organic siloxane, a carbon nano material and an organic solvent on the surface of one side of the support layer subjected to hydrophobic treatment, and curing to obtain the gas diffusion layer;
preferably, the coating mode is knife coating or spraying;
preferably, the temperature of the curing is 120-210 ℃;
preferably, the curing time is 10-70 min.
9. A proton exchange membrane fuel cell comprising a proton exchange membrane layer, a catalytic layer, and a gas diffusion layer according to claim 6 or 7, which are laminated together.
10. The pem fuel cell of claim 9 for use in an automobile as a power cell.
CN201911150252.1A 2019-11-21 2019-11-21 Microporous layer, gas diffusion layer, preparation method and application thereof Pending CN111063910A (en)

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113948716A (en) * 2021-10-14 2022-01-18 一汽解放汽车有限公司 Fuel cell gas diffusion layer and preparation method and application thereof
CN113948715A (en) * 2021-10-14 2022-01-18 一汽解放汽车有限公司 Fuel cell gas diffusion layer and preparation method and application thereof
CN114976060A (en) * 2022-07-04 2022-08-30 一汽解放汽车有限公司 Preparation method and application of gas diffusion layer

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1861668A (en) * 2006-06-16 2006-11-15 武汉理工大学 Preparation process of composite proton exchanging member based on hydrophilic porous poly tetrafluoro ethylene matrix
CN1988225A (en) * 2005-12-23 2007-06-27 中国科学院大连化学物理研究所 Gas diffusion layer for proton exchanging film fuel cell and its preparing method
CN104779407A (en) * 2015-04-27 2015-07-15 武汉理工大学 Nitrogen-containing polyphosphonic acid based polysiloxane/Nafion double-layer proton exchange membrane and preparation method thereof
CN109256569A (en) * 2017-07-14 2019-01-22 中国科学院青岛生物能源与过程研究所 A kind of gas diffusion layer of proton exchange membrane fuel cell microporous layers and preparation method thereof

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1988225A (en) * 2005-12-23 2007-06-27 中国科学院大连化学物理研究所 Gas diffusion layer for proton exchanging film fuel cell and its preparing method
CN1861668A (en) * 2006-06-16 2006-11-15 武汉理工大学 Preparation process of composite proton exchanging member based on hydrophilic porous poly tetrafluoro ethylene matrix
CN104779407A (en) * 2015-04-27 2015-07-15 武汉理工大学 Nitrogen-containing polyphosphonic acid based polysiloxane/Nafion double-layer proton exchange membrane and preparation method thereof
CN109256569A (en) * 2017-07-14 2019-01-22 中国科学院青岛生物能源与过程研究所 A kind of gas diffusion layer of proton exchange membrane fuel cell microporous layers and preparation method thereof

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113948716A (en) * 2021-10-14 2022-01-18 一汽解放汽车有限公司 Fuel cell gas diffusion layer and preparation method and application thereof
CN113948715A (en) * 2021-10-14 2022-01-18 一汽解放汽车有限公司 Fuel cell gas diffusion layer and preparation method and application thereof
CN114976060A (en) * 2022-07-04 2022-08-30 一汽解放汽车有限公司 Preparation method and application of gas diffusion layer
CN114976060B (en) * 2022-07-04 2024-05-28 一汽解放汽车有限公司 Preparation method and application of gas diffusion layer

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Application publication date: 20200424