CN111900418A - Preparation method of carbon paper precursor for gas diffusion layer of fuel cell - Google Patents

Preparation method of carbon paper precursor for gas diffusion layer of fuel cell Download PDF

Info

Publication number
CN111900418A
CN111900418A CN202010760099.0A CN202010760099A CN111900418A CN 111900418 A CN111900418 A CN 111900418A CN 202010760099 A CN202010760099 A CN 202010760099A CN 111900418 A CN111900418 A CN 111900418A
Authority
CN
China
Prior art keywords
carbon fiber
paper
carbon
fuel cell
cellulose
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
CN202010760099.0A
Other languages
Chinese (zh)
Other versions
CN111900418B (en
Inventor
韩文佳
李鸿冰
孔凡功
赵传山
丁其军
李霞
姜亦飞
赵轩
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Qilu University of Technology
Original Assignee
Qilu University of Technology
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Qilu University of Technology filed Critical Qilu University of Technology
Priority to CN202010760099.0A priority Critical patent/CN111900418B/en
Publication of CN111900418A publication Critical patent/CN111900418A/en
Application granted granted Critical
Publication of CN111900418B publication Critical patent/CN111900418B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/88—Processes of manufacture
    • H01M4/8803—Supports for the deposition of the catalytic active composition
    • H01M4/8807—Gas diffusion layers
    • 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
    • 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
    • H01M8/10—Fuel cells with solid electrolytes
    • H01M8/1004—Fuel cells with solid electrolytes characterised by membrane-electrode assemblies [MEA]
    • 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
    • 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
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

Landscapes

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

Abstract

The invention provides a preparation method of a carbon paper precursor for a gas diffusion layer of a fuel cell, belonging to the technical field of fuel cell preparation. The preparation method comprises the steps of mixing and dispersing carbon fibers with different lengths with nano-cellulose, adding a retention aid to improve the retention rate of fine fibers, then obtaining a carbon fiber paper wet paper web by a wet forming technology, then soaking resin into carbon paper by a vacuum negative pressure suction process, and obtaining a carbon paper precursor after vacuum drying. According to the invention, a small amount of nano-cellulose is added, so that the dispersibility of the carbon fiber can be obviously improved, and the carbon paper with a uniform structure can be prepared; the nano-cellulose can form hydrogen bond combination between carbon fibers, so that the carbon paper has excellent mechanical strength and structural stability; the nano-cellulose does not damage the porous structure of the carbon paper, so that the carbon paper has high air permeability, thereby having good practical application value.

Description

Preparation method of carbon paper precursor for gas diffusion layer of fuel cell
Technical Field
The invention belongs to the technical field of fuel cell preparation, and particularly relates to a preparation method of a carbon paper precursor for a gas diffusion layer of a fuel cell.
Background
The information in this background section is only for enhancement of understanding of the general background of the invention and is not necessarily to be construed as an admission or any form of suggestion that this information forms the prior art that is already known to a person of ordinary skill in the art.
Proton exchange membrane fuel cell is a clean, high-efficient, simple green energy device, use renewable resources such as hydrogen, methyl alcohol, ethanol to replace conventional fossil fuel, be regarded as the most promising environmental protection energy, input fuel through the external world continuously, through electrochemical reaction, directly convert the chemical energy of fuel into the electric energy, and then constantly to supplying power outward, can alleviate the situation that the electric power construction supply is nervous, the dilemma that the solution energy exhausts, the while has reduced problems such as environmental pollution, fuel cell technique can be applied to fields such as aerospace, automobile engine, portable power source.
Gas diffusion layers are important components in proton exchange membrane fuel cells, serve to support the catalyst layer and provide channels for reactant gases and product water, while also having good electrical conductivity and corrosion resistance under electrochemical reactions. The carbon fiber material has both high conductivity and high anti-corrosion performance and low cost, and is widely applied to the gas diffusion layer of the fuel cell. At present, carbon fiber materials for the gas diffusion layer are mainly divided into carbon fiber woven cloth, carbon fiber non-woven cloth and carbon fiber paper.
The carbon fiber woven cloth is formed by twisting and weaving carbon fiber yarns serving as raw materials through a spinning process. Chinese patent CN101024910A proposes a woven carbon cloth gas diffusion layer for fuel cells. Due to the adoption of the weaving structure, uniform macro pores exist between the warps and the wefts, and the porosity can be adjusted by controlling the thickness of the woven cloth. The carbon fiber woven cloth has high strength and bending flexibility. The fiber monofilament has a certain elongation at break coefficient, has certain elasticity in the plane direction, and can bear certain pressure. However, the inventors have found that the woven structure is also easily stretchable in the planar direction, and has a problem of large deformation. In addition, the surface flatness of the carbon fiber fabric is poor, and the catalyst is not uniformly attached, so that the stability of the fuel cell is affected. Therefore, woven carbon fiber cloth is not an ideal diffusion layer material.
The carbon fiber non-woven fabric is formed by directionally or randomly distributing chopped fibers or filaments, forming a uniform net structure together with an organic polymer and then reinforcing by adopting a mechanical or chemical method and the like. To achieve more excellent performance, carbon fillers may be added to reduce their resistivity or hydrophobic materials may be added to enhance water drainage. Japanese dongli corporation discloses in patent CN105829593A a carbon fiber nonwoven fabric for a gas diffusion electrode, which makes up for the disadvantages of the carbon fiber paper that it is highly brittle and the carbon fiber woven fabric is easily deformed, and the porosity can be controlled from the raw material stage as required. However, the inventors have found that the process is complicated, the strength is poor, the fuel cell is prone to crack in the right-angle direction, and the durability of the fuel cell is difficult to achieve.
The carbon fiber paper is prepared by preparing a precursor material with a porous three-dimensional net structure through a wet papermaking process, and then forming the carbon paper for the gas diffusion layer through thermal processing processes such as carbonization and graphitization. Since the carbon fibers lack active groups on the surface and cannot form strength between fibers after molding, it is necessary to add binder fibers or binders to improve the mechanical strength of the carbon paper precursor during the paper making process. Chinese patent CN101047253A proposes a carbon fiber paper for a gas diffusion layer of a fuel cell, which is made by introducing acrylic fibers as binder fibers in the paper making process and mixing with a carbon fiber dispersion. In order to ensure the strength of the carbon paper precursor, a large amount of thermal bonding fibers are added in the papermaking process. However, the inventors found that thermal bonding fibers with insulating properties seriously impair the electrical conductivity of the carbon paper. In addition, the thermal bonding fibers shrink and deform during the subsequent heat treatment process, thereby damaging the structure of the carbon fiber paper. Chinese patent CN1986961A proposes a preparation process of carbon nanotube/acrylonitrile-based carbon fiber composite carbon paper. The invention takes acrylonitrile-based carbon fiber as a main body and carbon nano tubes as functional filler, the acrylonitrile-based carbon fiber and the carbon nano tubes are fully mixed by pulping, then polyacrylamide and other high molecular adhesives are added in the dispersion process, and the composite carbon fiber paper is prepared by a wet papermaking process. Although the addition of the binder provides some physical strength to the carbon paper precursor, the inventors have found that it reduces both the air permeability and the carbon content of the carbon fiber paper.
Disclosure of Invention
Aiming at the defects in the prior art, the invention provides a preparation method of a carbon paper precursor for a gas diffusion layer of a fuel cell, and a small amount of nano-cellulose is added in the preparation process, so that the dispersibility of carbon fibers can be obviously improved, and carbon paper with a uniform structure can be prepared; the nano-cellulose can form hydrogen bond combination between carbon fibers, so that the carbon paper has excellent mechanical strength and structural stability; the nano-cellulose can not damage the porous structure of the carbon paper, so that the carbon paper has high air permeability, and the carbon fiber paper with high purity, high porosity, good conductivity and high structural stability is finally prepared, thereby having good practical application value.
Specifically, the invention relates to the following technical scheme:
in a first aspect of the present invention, there is provided a method of preparing a carbon paper precursor for a gas diffusion layer of a fuel cell, the method comprising:
s1, preparation of carbon fiber dispersion liquid: mixing short carbon fibers and long carbon fibers with different fiber lengths with nano-cellulose, adding a retention aid for defibering and dispersing to obtain a carbon fiber dispersion solution;
s2, forming of carbon fiber paper: placing the carbon fiber dispersion liquid in the step S1 in a forming device by adopting a wet forming process, and performing vacuum dehydration to enable the carbon fiber dispersion liquid to pass through a filter screen, thereby forming a carbon fiber wet paper web on the surface of the filter screen;
s3, impregnating resin: applying resin on one side of the carbon fiber wet paper web, and simultaneously sucking on the other side of the carbon fiber paper by adopting vacuum negative pressure to ensure that the resin is soaked in the carbon fiber paper; vacuum drying to obtain the final product.
In a second aspect of the present invention, there is provided a carbon fiber paper precursor obtained by the above-described production method.
In a third aspect of the present invention, a carbon fiber paper is provided, which is obtained by carbonizing and graphitizing the carbon fiber paper precursor. The carbon fiber paper finally prepared by the preparation method has high evenness, high air permeability, excellent conductivity, stable porous structure and high carbon content, and can effectively meet the performance requirements of the gas diffusion layer of the fuel cell.
In a fourth aspect of the invention, a fuel cell gas diffusion layer is provided, comprising the carbon fiber paper described above.
In a fifth aspect of the present invention, there is provided a fuel cell comprising the above fuel cell gas diffusion layer and/or the above carbon fiber paper.
The beneficial technical effects of one or more technical schemes are as follows:
1. the prepared carbon fiber paper precursor contains carbon fibers with different lengths, the carbon fibers are mutually overlapped to form an excellent conductive system, and the carbon fiber paper precursor also has uniformly distributed pores, so that the defects of the carbon paper for the traditional gas diffusion layer in the aspects of resistivity, porosity, uniformity and the like are overcome.
2. The dispersibility of the carbon fiber can be obviously improved by adding a small amount of nano-cellulose, so that the carbon paper with a uniform structure is prepared; the nano-cellulose can form hydrogen bond combination between carbon fibers, so that the carbon paper has excellent mechanical strength and structural stability; the nano-cellulose can not damage the porous structure of the carbon paper, so that the carbon paper has high air permeability.
3. The retention aid is added in the preparation process, so that the retention rate of the fine fibers can be effectively improved, the addition amount of the nano-cellulose is reduced, and the purity and the carbon content of the carbon paper are further improved. Therefore, it has good practical application value.
Detailed Description
It should be noted that the following detailed description is exemplary and is intended to provide further explanation of the disclosure. 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 application belongs.
It is noted that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of example embodiments according to the present application. As used herein, the singular forms "a", "an" and "the" are intended to include the plural forms as well, and it should be understood that when the terms "comprises" and/or "comprising" are used in this specification, they specify the presence of stated features, steps, operations, devices, components, and/or combinations thereof, unless the context clearly indicates otherwise.
The present invention is further illustrated by reference to specific examples, which are intended to be illustrative only and not limiting. If the experimental conditions not specified in the examples are specified, they are generally according to the conventional conditions, or according to the conditions recommended by the sales companies; materials, reagents and the like used in examples were commercially available unless otherwise specified.
As described above, a gas diffusion layer is an important component in a proton exchange membrane fuel cell, and at present, carbon fiber materials used for the gas diffusion layer are mainly classified into three types, namely carbon fiber woven cloth, carbon fiber non-woven cloth, and carbon fiber paper, but various problems of complicated preparation process, low strength, poor conductivity and air permeability, low carbon content, and the like generally exist, so that it is an urgent problem to solve to develop a carbon fiber paper precursor having high uniformity, high air permeability, excellent conductivity, stable porous structure, and high carbon content.
In view of the above, one embodiment of the present invention provides a method for preparing a carbon paper precursor for a gas diffusion layer of a fuel cell, the method comprising:
s1, preparation of carbon fiber dispersion liquid: mixing short carbon fibers and long carbon fibers with different fiber lengths with nano-cellulose, adding a retention aid for defibering and dispersing to obtain a carbon fiber dispersion solution;
s2, forming of carbon fiber paper: placing the carbon fiber dispersion liquid in the step S1 in a forming device by adopting a wet forming process, and performing vacuum dehydration to enable the carbon fiber dispersion liquid to pass through a filter screen, thereby forming a carbon fiber wet paper web on the surface of the filter screen;
s3, impregnating resin: applying resin on one side of the carbon fiber wet paper web, and simultaneously sucking on the other side of the carbon fiber paper by adopting vacuum negative pressure to ensure that the resin is soaked in the carbon fiber paper; vacuum drying to obtain the final product.
In another embodiment of the present invention, in step S1, the concentration of the system is controlled to be 0.1-0.15% after the retention aid is added;
the length of the short carbon fiber is 0.5-2 mm; the length of the long carbon fiber is 3-6 mm;
the diameter of the nano-cellulose is 20-500 nm, and the length-diameter ratio is 50-200;
more preferably, the nanocellulose has a diameter of-50 nm and an aspect ratio of 150;
the mass ratio of the short carbon fiber to the long carbon fiber to the nano-cellulose is 5-15: 80-90: 1-3.
The preparation process and the raw materials of the nano-cellulose are not particularly limited, and the nano-cellulose can be prepared by one or more processes of a mechanical method, a chemical method and a biological method, and the raw materials of the nano-cellulose are plant fibers or bacterial cellulose.
The retention aid is one or more of cationic starch, cationic polyacrylamide and carboxymethyl cellulose.
The defibering and dispersing treatment can be carried out in a defibering machine; specifically, the rotating speed is controlled to be 200-400 revolutions per minute, and the fluffing and dispersing time is 1-2 minutes;
in another embodiment of the present invention, in step S2,
controlling the concentration of the fiber dispersion liquid to be 0.005-0.01%;
the filter screen can be a stainless steel filter screen, and the mesh number of the filter screen is 80-100 meshes;
in another embodiment of the present invention, in step S3,
the resin can be applied by spraying; the resin may be any one or more of a phenol resin, an epoxy resin and an acrylonitrile resin.
The vacuum drying conditions are as follows: treating at 80-100 ℃ for 10-20 minutes.
In still another embodiment of the present invention, there is provided a carbon fiber paper precursor obtained by the above-described production method.
In another embodiment of the present invention, a carbon fiber paper is provided, which is obtained by carbonizing and graphitizing the carbon fiber paper precursor. The carbon fiber paper finally prepared by the preparation method has high evenness, high air permeability, excellent conductivity, stable porous structure and high carbon content, and can effectively meet the performance requirements of the gas diffusion layer of the fuel cell.
In yet another embodiment of the present invention, a fuel cell gas diffusion layer is provided comprising the carbon fiber paper described above.
In yet another embodiment of the present invention, a fuel cell is provided comprising the above-described fuel cell gas diffusion layer and/or the above-described carbon fiber paper.
The invention is further illustrated by the following examples, which are not to be construed as limiting the invention thereto. It should be understood that these examples are for illustrative purposes only and are not intended to limit the scope of the present invention.
Example 1
A preparation method of a carbon paper precursor for a gas diffusion layer of a fuel cell comprises the following steps:
(1) preparation of carbon fiber dispersion: short carbon fiber with the fiber length of 0.5mm, long carbon fiber with the fiber length of 3mm and nano-cellulose (the diameter of the nano-cellulose is 50nm, the length-diameter ratio is 150) are mixed according to the mass ratio of 9:90:1 and added into a defiberizer. Then 0.2% of carboxymethyl cellulose retention aid is added, the concentration of the system is adjusted to be 0.1%, and the mixture is dispersed for 2 minutes under the high-speed stirring of 200 revolutions per minute.
(2) Forming carbon fiber paper: and (2) adopting a wet forming process, adding water into the carbon fiber dispersion liquid prepared in the step (1) to adjust the concentration to be 0.005%, then adding the carbon fiber dispersion liquid into a former, and performing vacuum dehydration to enable the dispersion liquid to pass through a stainless steel filter screen of 80 meshes to form a wet paper web on the surface of the filter screen.
(3) Impregnating resin: spraying phenolic resin on one side of the carbon fiber wet paper web, and simultaneously sucking on the other side of the carbon fiber paper by adopting vacuum negative pressure so as to immerse the phenolic resin into the carbon fiber paper. After completion, the mixture was dried under vacuum at 100 ℃ for 10 minutes.
Example 2
A preparation method of a carbon paper precursor for a gas diffusion layer of a fuel cell comprises the following steps:
(1) preparation of carbon fiber dispersion: short carbon fiber with the fiber length of 1mm, long carbon fiber with the fiber length of 4mm and nano-cellulose (the diameter of the nano-cellulose is 50nm, the length-diameter ratio is 150) are mixed and added into a defiberizing machine according to the mass ratio of 4:95: 1. Then 0.25% of carboxymethyl cellulose retention aid is added, the concentration of the system is adjusted to be 0.12%, and the mixture is dispersed for 1.5 minutes under the high-speed stirring of 300 revolutions per minute.
(2) Forming carbon fiber paper: and (2) adopting a wet forming process, adding water into the carbon fiber dispersion liquid prepared in the step (1) to adjust the concentration to be 0.007%, then adding the carbon fiber dispersion liquid into a former, and performing vacuum dehydration to enable the dispersion liquid to pass through a 90-mesh stainless steel filter screen to form a wet paper web on the surface of the filter screen.
(3) Impregnating resin: spraying phenolic resin on one side of the carbon fiber wet paper web, and simultaneously sucking on the other side of the carbon fiber paper by adopting vacuum negative pressure so as to immerse the phenolic resin into the carbon fiber paper. After completion, the mixture was dried under vacuum at 95 ℃ for 12 minutes.
Example 3
A preparation method of a carbon paper precursor for a gas diffusion layer of a fuel cell comprises the following steps:
(1) preparation of carbon fiber dispersion: short carbon fiber with the fiber length of 2mm, long carbon fiber with the fiber length of 5mm and nano-cellulose (the diameter of the nano-cellulose is 50nm, the length-diameter ratio is 150) are mixed according to the mass ratio of 13:85:2 and added into a defibrator. Then 0.3% of carboxymethyl cellulose retention aid is added, the concentration of the system is adjusted to be 0.15%, and the mixture is dispersed for 1 minute under the high-speed stirring of 400 revolutions per minute.
(2) Forming carbon fiber paper: and (2) adopting a wet forming process, adding water into the carbon fiber dispersion liquid prepared in the step (1) to adjust the concentration to be 0.01%, then adding the carbon fiber dispersion liquid into a former, and performing vacuum dehydration to enable the dispersion liquid to pass through a stainless steel filter screen of 100 meshes to form a wet paper web on the surface of the filter screen.
(3) Impregnating resin: spraying phenolic resin on one side of the carbon fiber wet paper web, and simultaneously sucking on the other side of the carbon fiber paper by adopting vacuum negative pressure so as to immerse the phenolic resin into the carbon fiber paper. After completion, it was dried under vacuum at 90 ℃ for 15 minutes.
Comparative example 1
The preparation method of the carbon paper without adding the nano-cellulose comprises the following steps:
(1) preparation of carbon fiber dispersion: short carbon fiber with the fiber length of 0.5mm and long carbon fiber with the fiber length of 3mm are mixed and added into a fiber fluffer according to the mass ratio of 1: 90. Then 0.2% of carboxymethyl cellulose retention agent is added, the concentration of the system is adjusted to be 0.1%, and the mixture is dispersed for 2 minutes under the high-speed stirring of 200 revolutions per minute.
(2) Forming carbon fiber paper: and (2) adopting a wet forming process, adding water into the carbon fiber dispersion liquid prepared in the step (1) to adjust the concentration to be 0.005%, then adding the carbon fiber dispersion liquid into a former, and performing vacuum dehydration to enable the dispersion liquid to pass through a stainless steel filter screen of 80 meshes to form a wet paper web on the surface of the filter screen.
(3) Impregnating resin: spraying phenolic resin on one side of the carbon fiber wet paper web, and simultaneously sucking on the other side of the carbon fiber paper by adopting vacuum negative pressure so as to immerse the phenolic resin into the carbon fiber paper. After completion, the mixture was dried under vacuum at 100 ℃ for 10 minutes.
The test results of the carbon fiber paper for a gas diffusion layer of a fuel cell prepared in each example and comparative example are shown in table 1.
TABLE 1
Figure BDA0002612831610000071
As can be seen from Table 1, the method provided by the invention can significantly improve the performance of the carbon paper precursor, and effectively improve the overall stability of the carbon paper in the application of the gas diffusion layer of the fuel cell.
Finally, it should be noted that: although the present invention has been described in detail with reference to the foregoing embodiments, it will be apparent to those skilled in the art that changes may be made in the embodiments and/or equivalents thereof without departing from the spirit and scope of the invention. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.

Claims (10)

1. A method of making a carbon paper precursor for a gas diffusion layer of a fuel cell, the method comprising:
s1, preparation of carbon fiber dispersion liquid: mixing short carbon fibers and long carbon fibers with different fiber lengths with nano-cellulose, adding a retention aid for defibering and dispersing to obtain a carbon fiber dispersion solution;
s2, forming of carbon fiber paper: placing the carbon fiber dispersion liquid in the step S1 in a forming device by adopting a wet forming process, and performing vacuum dehydration to enable the carbon fiber dispersion liquid to pass through a filter screen, thereby forming a carbon fiber wet paper web on the surface of the filter screen;
s3, impregnating resin: applying resin on one side of the carbon fiber wet paper web, and simultaneously sucking on the other side of the carbon fiber paper by adopting vacuum negative pressure to ensure that the resin is soaked in the carbon fiber paper; vacuum drying to obtain the final product.
2. The process of claim 1, wherein in step S1, the concentration of the retention aid is controlled to be 0.1-0.15%.
3. The method of claim 1, wherein in step S1, the short carbon fibers have a length of 0.5 to 2 mm; the length of the long carbon fiber is 3-6 mm;
the diameter of the nano-cellulose is 20-500 nm, and the length-diameter ratio is 50-200;
preferably, the nanocellulose has a diameter of 50nm and an aspect ratio of 150;
the mass ratio of the short carbon fiber to the long carbon fiber to the nano-cellulose is 5-15: 80-90: 1-3;
the retention aid is one or more of cationic starch, cationic polyacrylamide and carboxymethyl cellulose;
defibering and dispersing treatment is carried out in a defibering machine; preferably, the rotation speed is controlled to be 200-400 rpm, and the fluffing and dispersing time is 1-2 minutes.
4. The method of claim 1, wherein in step S2,
the concentration of the fiber dispersion is controlled to be 0.005-0.01%.
5. The method of claim 1, wherein in step S2,
the mesh number of the filter screen is 80-100 meshes.
6. The method according to claim 1, wherein in step S3,
applying resin and treating in a spraying mode; the resin is any one or more of phenolic resin, epoxy resin and acrylonitrile resin;
the vacuum drying conditions are as follows: treating at 80-100 ℃ for 10-20 minutes.
7. A carbon fiber paper precursor obtained by the production method according to any one of claims 1 to 6.
8. A carbon fiber paper, characterized in that, the carbon fiber paper is obtained by carbonizing and graphitizing the carbon fiber paper precursor according to claim 7.
9. A fuel cell gas diffusion layer comprising the carbon fiber paper of claim 8.
10. A fuel cell, characterized in that the fuel cell comprises a fuel cell gas diffusion layer according to claim 9 and/or a carbon fiber paper according to claim 8.
CN202010760099.0A 2020-07-31 2020-07-31 Preparation method of carbon paper precursor for gas diffusion layer of fuel cell Active CN111900418B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202010760099.0A CN111900418B (en) 2020-07-31 2020-07-31 Preparation method of carbon paper precursor for gas diffusion layer of fuel cell

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202010760099.0A CN111900418B (en) 2020-07-31 2020-07-31 Preparation method of carbon paper precursor for gas diffusion layer of fuel cell

Publications (2)

Publication Number Publication Date
CN111900418A true CN111900418A (en) 2020-11-06
CN111900418B CN111900418B (en) 2021-11-30

Family

ID=73183847

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202010760099.0A Active CN111900418B (en) 2020-07-31 2020-07-31 Preparation method of carbon paper precursor for gas diffusion layer of fuel cell

Country Status (1)

Country Link
CN (1) CN111900418B (en)

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113066996A (en) * 2021-03-23 2021-07-02 中国科学院化学研究所 PEM fuel cell, gas diffusion layer porous carbon paper and preparation method thereof
CN114538947A (en) * 2022-03-08 2022-05-27 苏州碳创新材料技术开发有限公司 Preparation method for roll-to-roll continuous production of carbon material substrate of gas diffusion layer
CN114808520A (en) * 2022-04-14 2022-07-29 广东氢发新材料科技有限公司 Continuous carbon fiber papermaking process
CN115020645A (en) * 2022-07-26 2022-09-06 山东仁丰特种材料股份有限公司 Composite electrode material, preparation method thereof and solid-state battery
CN115233489A (en) * 2021-04-22 2022-10-25 中国石油化工股份有限公司 Carbon fiber paper and preparation method and application thereof
CN115287941A (en) * 2022-08-10 2022-11-04 浙江科技学院 Preparation method of three-dimensional conductive carbon fiber paper
US11876232B2 (en) 2021-05-31 2024-01-16 Donghua University Gas diffusion layer for proton exchange membrane fuel cell and preparation method thereof

Citations (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20070218343A1 (en) * 2006-03-17 2007-09-20 Chunxin Ji Gas diffusion media and fuel cell
CN101286565A (en) * 2008-05-23 2008-10-15 黄志达 Production method of electrode material of high performance carbon fibre for fuel cell
US20090068545A1 (en) * 2007-09-11 2009-03-12 Korea Institute Of Energy Research Method of manufacturing cellulose electrode for fuel cells, cellulose electrode manufactured thereby, and use of cellulose fibers as fuel cell electrodes
CN101492895A (en) * 2009-02-18 2009-07-29 程显军 Carbon fibre cloth for gaseous diffusion layer of fuel cell electrode
CN101591868A (en) * 2009-06-23 2009-12-02 东华大学 Be used for the preparation of the carbon fiber paper of gas diffusion layer of proton exchange membrane fuel cell
KR101304489B1 (en) * 2012-07-24 2013-09-05 한국에너지기술연구원 Method for preparing carbon paper by controling specific charge density and viscosity in solution, the carbon paper prepared using the method and fuel cell comprising the carbon paper
CN105113320A (en) * 2015-07-08 2015-12-02 浙江理工大学 Method for improving strength of wastepaper fibers based on nanometer microcrystalline cellulose
CN106149460A (en) * 2016-07-06 2016-11-23 福建农林大学 High intensity high antibiotic property water proof type conductive paper and preparation method thereof
US20170072670A1 (en) * 2015-09-10 2017-03-16 University Of Maine System Board Of Trustees Composite products of paper and cellulose nanofibrils and process of making
CN106560944A (en) * 2015-09-25 2017-04-12 中国科学院大连化学物理研究所 Porous carbon fiber paper electrode material for all-vanadium redox flow battery, and preparation and application thereof
CN107086311A (en) * 2017-04-17 2017-08-22 王敏 The method that fuel cell porous diffusion layer battery lead plate is made using graphene carbon cellulose fiber conductive paper
CN107227651A (en) * 2017-05-12 2017-10-03 北京观澜科技有限公司 A kind of environment-friendly type repeated writing paper and preparation method thereof
CN107815007A (en) * 2017-11-17 2018-03-20 芜湖蓝天工程塑胶有限公司 Breathable polyethylene Film laminated paper and preparation method thereof
CN110512459A (en) * 2019-08-16 2019-11-29 华南理工大学 A kind of high performance carbon paper and the preparation method and application thereof for fuel cell

Patent Citations (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20070218343A1 (en) * 2006-03-17 2007-09-20 Chunxin Ji Gas diffusion media and fuel cell
US20090068545A1 (en) * 2007-09-11 2009-03-12 Korea Institute Of Energy Research Method of manufacturing cellulose electrode for fuel cells, cellulose electrode manufactured thereby, and use of cellulose fibers as fuel cell electrodes
CN101286565A (en) * 2008-05-23 2008-10-15 黄志达 Production method of electrode material of high performance carbon fibre for fuel cell
CN101492895A (en) * 2009-02-18 2009-07-29 程显军 Carbon fibre cloth for gaseous diffusion layer of fuel cell electrode
CN101591868A (en) * 2009-06-23 2009-12-02 东华大学 Be used for the preparation of the carbon fiber paper of gas diffusion layer of proton exchange membrane fuel cell
KR101304489B1 (en) * 2012-07-24 2013-09-05 한국에너지기술연구원 Method for preparing carbon paper by controling specific charge density and viscosity in solution, the carbon paper prepared using the method and fuel cell comprising the carbon paper
CN105113320A (en) * 2015-07-08 2015-12-02 浙江理工大学 Method for improving strength of wastepaper fibers based on nanometer microcrystalline cellulose
US20170072670A1 (en) * 2015-09-10 2017-03-16 University Of Maine System Board Of Trustees Composite products of paper and cellulose nanofibrils and process of making
CN106560944A (en) * 2015-09-25 2017-04-12 中国科学院大连化学物理研究所 Porous carbon fiber paper electrode material for all-vanadium redox flow battery, and preparation and application thereof
CN106149460A (en) * 2016-07-06 2016-11-23 福建农林大学 High intensity high antibiotic property water proof type conductive paper and preparation method thereof
CN107086311A (en) * 2017-04-17 2017-08-22 王敏 The method that fuel cell porous diffusion layer battery lead plate is made using graphene carbon cellulose fiber conductive paper
CN107227651A (en) * 2017-05-12 2017-10-03 北京观澜科技有限公司 A kind of environment-friendly type repeated writing paper and preparation method thereof
CN107815007A (en) * 2017-11-17 2018-03-20 芜湖蓝天工程塑胶有限公司 Breathable polyethylene Film laminated paper and preparation method thereof
CN110512459A (en) * 2019-08-16 2019-11-29 华南理工大学 A kind of high performance carbon paper and the preparation method and application thereof for fuel cell

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
谭思聪: "碳纤维纸基超级电容器电极的制备及性能表征", 《中国优秀硕士学位论文全文数据库 (工程科技Ⅰ辑)》 *

Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113066996A (en) * 2021-03-23 2021-07-02 中国科学院化学研究所 PEM fuel cell, gas diffusion layer porous carbon paper and preparation method thereof
CN115233489A (en) * 2021-04-22 2022-10-25 中国石油化工股份有限公司 Carbon fiber paper and preparation method and application thereof
CN115233489B (en) * 2021-04-22 2024-03-26 中国石油化工股份有限公司 Carbon fiber paper and preparation method and application thereof
US11876232B2 (en) 2021-05-31 2024-01-16 Donghua University Gas diffusion layer for proton exchange membrane fuel cell and preparation method thereof
CN114538947A (en) * 2022-03-08 2022-05-27 苏州碳创新材料技术开发有限公司 Preparation method for roll-to-roll continuous production of carbon material substrate of gas diffusion layer
CN114808520A (en) * 2022-04-14 2022-07-29 广东氢发新材料科技有限公司 Continuous carbon fiber papermaking process
CN115020645A (en) * 2022-07-26 2022-09-06 山东仁丰特种材料股份有限公司 Composite electrode material, preparation method thereof and solid-state battery
CN115020645B (en) * 2022-07-26 2023-12-08 山东仁丰特种材料股份有限公司 Composite electrode material, preparation method thereof and solid-state battery
CN115287941A (en) * 2022-08-10 2022-11-04 浙江科技学院 Preparation method of three-dimensional conductive carbon fiber paper
CN115287941B (en) * 2022-08-10 2023-10-20 浙江科技学院 Preparation method of three-dimensional conductive carbon fiber paper

Also Published As

Publication number Publication date
CN111900418B (en) 2021-11-30

Similar Documents

Publication Publication Date Title
CN111900418B (en) Preparation method of carbon paper precursor for gas diffusion layer of fuel cell
CN110528314A (en) A kind of composite sheet and its preparation method and application of the polyphenylene sulfide superfine fiber containing melt-blown
JP3774439B2 (en) Conductive nonwoven fabric
CN111900416A (en) Preparation method and application of carbon paper impregnating resin for fuel cell gas diffusion layer
EP2669977A1 (en) Porous electrode substrate, method for producing same, precursor sheet, membrane electrode assembly, and solid polymer fuel cell
US11876232B2 (en) Gas diffusion layer for proton exchange membrane fuel cell and preparation method thereof
CN113584940A (en) Preparation method of carbon fiber paper
CN112941965B (en) Carbon fiber filter paper and preparation method thereof
US12054887B2 (en) Preparation method of double-layer carbon-paper base paper with high uniformity and gradient pores
CN113480328B (en) Large-scale graphene heat-conducting roll film and preparation method thereof
CN114855308B (en) Carbon fiber paper and preparation method and application thereof
CN111129555A (en) Carbon paper material for high-toughness high-conductivity proton exchange membrane battery
CN115341407A (en) Carbon fiber paper for gas diffusion layer of fuel cell and preparation method and application thereof
CN111900417A (en) Preparation method of carbon paper for high-carbon-content fuel cell gas diffusion layer
KR100997418B1 (en) Method of preparing gas diffusion layer having carbon nanotube and carbon compound for fuel cell
CN114538947A (en) Preparation method for roll-to-roll continuous production of carbon material substrate of gas diffusion layer
CN115172767A (en) Preparation method of carbon paper for gas diffusion layer of fuel cell
CN116314860A (en) Microporous layer for gas diffusion layer and preparation method thereof
CN109103026A (en) A kind of preparation method of the derivative carbon nanofiber membrane of fluorine, nitrogen co-doped bacteria cellulose
CN111617706B (en) Al (aluminum)2O3-B2O3-SiO2Composite sol, core-shell structure active carbon fiber and preparation method thereof
KR20200040423A (en) Method of desizing carbon fiber and method of manufacturing gas diffusion layer of fuel cell thereby
CN112982027B (en) Modification method of high-performance carbon paper based on supercritical fluid technology
CN107217523B (en) A kind of preparation method of the novel hybride fiber carbon paper for supercapacitor
AU2021104826A4 (en) Method for making wood-converted carbon fiber paper
CN115287941B (en) Preparation method of three-dimensional conductive carbon fiber paper

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant
CP03 Change of name, title or address

Address after: 250353 University Road, Changqing District, Ji'nan, Shandong Province, No. 3501

Patentee after: Qilu University of Technology (Shandong Academy of Sciences)

Country or region after: China

Address before: 250353 University Road, Changqing District, Ji'nan, Shandong Province, No. 3501

Patentee before: Qilu University of Technology

Country or region before: China