CN111169030B - Method for preparing carbon paper for gas diffusion layer of fuel cell by calendering and carbon paper - Google Patents
Method for preparing carbon paper for gas diffusion layer of fuel cell by calendering and carbon paper Download PDFInfo
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- CN111169030B CN111169030B CN202010129887.XA CN202010129887A CN111169030B CN 111169030 B CN111169030 B CN 111169030B CN 202010129887 A CN202010129887 A CN 202010129887A CN 111169030 B CN111169030 B CN 111169030B
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
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- B29C69/00—Combinations of shaping techniques not provided for in a single one of main groups B29C39/00 - B29C67/00, e.g. associations of moulding and joining techniques; Apparatus therefore
- B29C69/02—Combinations of shaping techniques not provided for in a single one of main groups B29C39/00 - B29C67/00, e.g. associations of moulding and joining techniques; Apparatus therefore of moulding techniques only
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C43/00—Compression moulding, i.e. applying external pressure to flow the moulding material; Apparatus therefor
- B29C43/22—Compression moulding, i.e. applying external pressure to flow the moulding material; Apparatus therefor of articles of indefinite length
- B29C43/24—Calendering
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B29C59/00—Surface shaping of articles, e.g. embossing; Apparatus therefor
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- B29C59/04—Surface shaping of articles, e.g. embossing; Apparatus therefor by mechanical means, e.g. pressing using rollers or endless belts
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
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- B29C71/00—After-treatment of articles without altering their shape; Apparatus therefor
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- 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
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- H01M4/8807—Gas diffusion layers
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- H—ELECTRICITY
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- 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]
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
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- B29C71/00—After-treatment of articles without altering their shape; Apparatus therefor
- B29C71/0009—After-treatment of articles without altering their shape; Apparatus therefor using liquids, e.g. solvents, swelling agents
- B29C2071/0045—Washing using non-reactive liquids
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- 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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- 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
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Abstract
The invention provides a method for preparing carbon paper of a gas diffusion layer of a fuel cell by calendering and carbon paper, wherein the carbon paper of the gas diffusion layer is prepared by uniformly dispersing microporous conductive carbon fully soaked with saturated salt solution, soluble salt particles, hot-melt polymers and fiber materials, mixing, calendering and stretching, processing by a needle roller to obtain a sheet, continuously passing the sheet through a guide roller in a solvent pool, leading out and drying, then leading into a clean water pool, and finally leading out and drying, cutting edges and coiling. According to the method provided by the invention, the conductive carbon material with the gaps pre-occupied by the soluble salt and the soluble salt particles are dispersed in the polymer and then subjected to hot calendaring and forming, after the salt is eluted, the small gaps of the carbon particles and the large gaps of the dissolved soluble salt particles coexist, and finally, the carbon paper with high porosity is obtained through needling treatment, soaking in a solvent pool and cold stretching.
Description
Technical Field
The invention relates to the technical field of fuel cell gas diffusion layers, in particular to a method for preparing carbon paper of a fuel cell gas diffusion layer by calendering and carbon paper.
Background
The proton exchange membrane fuel cell has the characteristics of high energy efficiency, cleanness, no pollution and the like, and becomes a hot spot for research and development of various countries in recent years. The membrane electrode three-in-one (MEA) which is a core component is usually prepared by a gas diffusion layer, a catalyst layer and a proton exchange membrane through a hot pressing process. The gas diffusion layer is made of conductive porous materials, plays multiple roles of supporting the catalyst layer, collecting current, conducting gas, discharging water and the like, realizes redistribution of reaction gas and product water between the flow field and the catalyst layer, and is one of key components influencing the performance of the electrode.
The gas diffusion layer generally includes a substrate layer and a microporous layer, the substrate layer generally uses porous carbon paper or carbon cloth, and the gas diffusion layer has a plurality of functions of supporting a catalyst, distributing and diffusing gas, and conducting electricity and transporting water, so the carbon paper is required to have comprehensive properties of conductivity, porosity, hydrophobicity and strength.
The carbon paper selected at present is mainly imported products such as Dongli (Japan), Balard (Jia), SGL (German), and the like, and the carbon paper is high in price and difficult to supply in batches due to the adoption of carbon fibers. In addition, the conventional carbon paper has high brittleness, and needs to be subjected to flexibility treatment such as coating resin, and the porosity and the conductivity are adversely affected. The conductive carbon material is supported by the flexible polymer, so that the film-shaped carbon paper can be conveniently formed, and a technical support is provided for large-scale preparation of the flexible carbon paper. However, in practice, since the thermoplastic molding is not carbonized again, the carbon particles are tightly coated with the polymer, the porosity thereof is low, and the conductivity is affected. Therefore, researches for improving the porosity and conductivity of the carbon paper of the gas diffusion layer are considered by researchers.
The Chinese patent application No. 201310504496.1 discloses a high-performance carbon paper special for a fuel cell gas diffusion layer and a preparation method thereof, wherein the carbon paper is prepared by taking short carbon fibers, plant fibers, thermal bonding fibers and carbon black as raw materials, defibering, pulping, preparing pulp, papermaking by a wet papermaking process, and then coating by waterproof paint. Chinese invention patent application No. 200910010385.9 discloses a carbon fiber paper for a gas diffusion layer of a fuel cell electrode, which is characterized in that: cutting short carbon fibers, wherein the length of the cut short carbon fibers is between 0.5 and 5.0mm, and the average length of the cut short carbon fibers is between 1.0 and 3.0 mm; dispersing the short carbon fibers in an aqueous phase by using a dispersing agent with the content of less than 1% to form a slurry raw material, wherein the content of the carbon fibers is between 97.1 and 99.1 weight percent; the carbon fiber paper material is prepared by a wet papermaking forming method.
In order to solve the problem of low porosity of the existing carbon paper for the gas diffusion layer of the fuel cell, especially the polymer carbon paper, it is necessary to provide a preparation method of a novel carbon paper for the gas diffusion layer, so that the porosity of the carbon paper for the gas diffusion layer of the fuel cell is improved, and the conductivity is improved.
Disclosure of Invention
Aiming at the problem of low porosity of the carbon paper for the gas diffusion layer of the fuel cell prepared by large-scale thermoplastic forming at present, the invention provides a method for preparing the carbon paper for the gas diffusion layer of the fuel cell by calendering and the carbon paper, so that the porosity of the carbon paper for the gas diffusion layer is effectively improved, and the gas diffusion performance is improved.
In order to solve the problems, the invention adopts the following technical scheme:
a method for preparing gas diffusion layer carbon paper prepared by rolling comprises the following steps of uniformly dispersing microporous conductive carbon fully soaked with saturated salt solution, soluble salt particles, hot-melt polymer and fiber material, mixing, rolling, stretching and needling to obtain a sheet, continuously passing the sheet through a guide roller in a solvent pool, guiding the sheet into a clean water pool after being dried, and finally guiding the sheet out for drying, edge cutting and coiling, wherein the specific preparation method comprises the following steps:
(1) immersing the microporous conductive carbon into a saturated salt solution for 1-2h to enable the microporous conductive carbon to fully adsorb salt liquid, then filtering out redundant liquid salt liquid, and drying to enable salt to occupy gaps of the microporous conductive carbon to obtain pretreated microporous conductive carbon;
(2) uniformly dispersing pretreated microporous conductive carbon, soluble salt particles, hot-melt polymer and fiber material, adding the mixture into a mixing roll for hot mixing, calendering by a calender, carrying out unidirectional stretching, and finally carrying out needling roller treatment to obtain a sheet which penetrates through micropores and has the thickness of 0.2-0.3 mm;
(3) the method comprises the steps of firstly, guiding a sheet into a solvent pool to continuously pass through a guide roller, applying 30-50N traction tension to enable the sheet to be kept in the solvent to be soaked for 1-5min to form a microporous and loose sheet, drying the sheet at 80-100 ℃ for 60-90min after the sheet is led out of the solvent pool to enable the soaked solvent to be fully volatilized, then guiding the sheet into a cleaning pool for 20-30min, eluting salt, leading out, further drying, cutting edges and coiling to obtain the carbon paper of the gas diffusion layer of the fuel cell.
Preferably, the saturated salt solution is a saturated solution of sodium chloride or a mixture of sodium sulfate and ammonium sulfate or ammonium phosphate.
Preferably, the microporous conductive carbon is one or a combination of more than two of conductive carbon black, graphene aerogel and carbon fiber balls with micropores, the particle size of the conductive carbon is 50-100 μm, and the pore diameter of the micropores is 1-5 μm.
Preferably, the soluble salt particles are one of sodium chloride particles and sodium sulfate particles, and the particle diameter of the particles is 10-20 μm.
Furthermore, the microporous conductive carbon is fully soaked in a saturated soluble salt solution, so that the micro-gaps of the microporous conductive carbon pre-occupy soluble salt, and the pretreated microporous conductive carbon is dispersed into a polymer to be thermally calendered into a film. In the hot calendering process, micropores of the microporous conductive carbon cannot be occupied by the thermoplastic polymer, and micropores of 1-5 microns of the carbon can be better reserved after subsequent washing and desalting; meanwhile, soluble salt particles with the particle size of 10-20 mu m are added during hot rolling, so that 10-20 mu m gaps are formed after subsequent washing and desalting. The method enables small gaps of the microporous conductive carbon particles and large gaps of the soluble salt particles after dissolution to exist cooperatively, and further greatly improves the porosity of the carbon paper.
Preferably, the hot-melt polymer is one or a combination of two or more of polyimide, polytetrafluoroethylene and polypropylene.
Preferably, the fiber material is one or a combination of more than two of chopped carbon fiber and softwood pulp fiber.
Further preferably, the carbon fiber is one or a combination of two or more of polyacrylonitrile-based carbon fiber, pitch-based carbon fiber, viscose-based carbon fiber and phenolic-based carbon fiber.
Preferably, in the step (2), the mass ratio of the hot-melt polymer, the pretreated microporous conductive carbon, the soluble salt particles and the fiber material is 100:10-20:8-13: 20-26.
Preferably, the mixing roll in the step (2) is one of a screw extruder and an internal mixer, the thermal mixing temperature is 180-.
Preferably, the roll temperature of the calender in the step (2) is 150 ℃ and 180 ℃, and the roll speed is 25-35 m/min.
Preferably, the temperature of the unidirectional stretching in the step (2) is 40-60 ℃, and the stretching ratio is 1.5-2.
Preferably, the diameter of the needle processed by the needle roller in the step (2) is 0.03-0.05mm, and the arrangement interval of the needles is 50 meshes.
Preferably, the solvent in the solvent pool is one of N-methyl pyrrolidone, dimethyl sulfoxide and N, N-dimethylformamide.
The microporous conductive carbon selected by the invention has a large number of small gaps, has the characteristics of high porosity, large pore volume, excellent conductivity and stability and the like, and is a good conductive carbon material for preparing the carbon paper of the gas diffusion layer.
Furthermore, in the process of obtaining the sheet by calendaring molding, the hot-melt polymer tightly coats the carbon particles and the soluble salt particles to form a protective film, which can cause the difficulty in salt elution, but the invention creatively uses a needling roller to process the obtained sheet to form through micropores, then continuously passes through a guide roller in a solvent pool, and uses infiltration and cold stretching to dissolve part of the polymer and loosen the sheet, thereby being more beneficial to the rapid and complete dissolution of the soluble salt, further forming good gaps and obtaining the carbon paper with high porosity.
The existing gas diffusion layer carbon paper is not carbonized again in the process of thermoplastic molding, so that carbon particles are tightly coated by polymers, the carbon paper has the defect of low porosity, and the application of the carbon paper is limited. In view of the above, the invention provides a method for preparing carbon paper for a gas diffusion layer of a fuel cell by calendering and carbon paper, which comprises the steps of immersing microporous conductive carbon in a saturated salt solution to fully adsorb salt solution, filtering out redundant liquid salt solution, and drying to enable salt to occupy gaps of the microporous conductive carbon; uniformly dispersing microporous conductive carbon, soluble salt particles, hot-melt polymer and fiber material, carrying out hot mixing in a mixing roll, and then calendering by a calender, carrying out unidirectional stretching, and carrying out needle roller treatment to obtain a sheet with through micropores; continuously introducing the slices into a solvent pool, continuously passing through a guide roller, keeping the slices soaked in the solvent, and drying the slices after being led out of the solvent pool to volatilize the soaked solvent; and then, introducing the carbon paper into a cleaning tank, quickly permeating water in the cleaning tank into a loose sheet with micropores, eluting salt, further drying, cutting edges, and coiling to obtain the carbon paper of the gas diffusion layer of the fuel cell. According to the method provided by the invention, the conductive carbon material with the gaps pre-occupied by the soluble salt and the soluble salt particles are dispersed in the polymer and then subjected to hot calendaring and forming, after the salt is eluted, the small gaps of the carbon particles and the large gaps of the dissolved soluble salt particles coexist, and finally, the carbon paper with high porosity is obtained through needling treatment, soaking in a solvent pool and cold stretching.
The invention also provides a carbon paper for the gas diffusion layer of the fuel cell prepared by calendering, which is prepared by uniformly dispersing microporous conductive carbon fully soaked with saturated salt solution, soluble salt particles, hot-melt polymer and fiber material, mixing, calendering, stretching and needling to obtain a sheet, continuously passing the sheet through a guide roller in a solvent pool, guiding the sheet into a clean water pool after being guided out and dried, and finally guiding out and drying, cutting edges and coiling.
Compared with the prior art, the invention provides a method for preparing carbon paper of a gas diffusion layer of a fuel cell by calendering and the carbon paper, and the outstanding characteristics and excellent effects are as follows:
1. according to the invention, the microporous conductive carbon is selected, soluble salt is pre-occupied in micro-gaps of the microporous conductive carbon, then the microporous conductive carbon and soluble salt particles are dispersed in a hot-melt polymer together and then subjected to hot-calendering molding, and further salt washing is carried out, so that small gaps of the carbon particles and large gaps after the soluble salt particles are dissolved out coexist, and the porosity of the carbon paper is greatly improved.
2. According to the invention, the sheet obtained by hot calendering is subjected to needle punching to form through micropores, and then is soaked in a solvent pool and subjected to cold stretching to loosen the sheet, so that the soluble salt is dissolved out quickly and completely, and good gaps are formed in the carbon paper.
3. The preparation method has the advantages of simple preparation process, low cost and easy large-scale production.
Drawings
FIG. 1 is a flow chart of the preparation process of the present invention.
Detailed Description
The present invention will be described in further detail with reference to specific embodiments, but it should not be construed that the scope of the present invention is limited to the following examples. Various substitutions and alterations can be made by those skilled in the art and by conventional means without departing from the spirit of the method of the invention described above.
Example 1
(1) Immersing the microporous conductive carbon into a saturated salt solution for 1.5h to enable the microporous conductive carbon to fully adsorb salt liquid, then filtering out redundant liquid salt liquid, and drying to enable salt to occupy gaps of the microporous conductive carbon to obtain pretreated microporous conductive carbon; the microporous conductive carbon is conductive carbon black with micropores; the saturated salt solution is a saturated solution compounded by sodium chloride and ammonium sulfate;
(2) uniformly dispersing pretreated microporous conductive carbon, soluble salt particles, hot-melt polymer and fiber material, adding the mixture into a mixing roll for hot mixing, calendering by a calender, carrying out unidirectional stretching, and finally carrying out needling roller treatment to obtain a sheet which penetrates through micropores and has an average thickness of 0.26 mm; the soluble salt particles are sodium chloride particles; the hot-melt polymer is polyimide; the fiber material is short-cut polyacrylonitrile-based carbon fiber; in the mixed material, the mass ratio of the hot-melt polymer, the pretreated microporous conductive carbon, the soluble salt particles and the fiber material is 100:16:11: 23; the mixing roll adopts a screw extruder, the temperature of hot mixing is 190 ℃, the rotating speed is 130rpm, and the mixing time is 28 min; the temperature of the roller for calendering by the calender is 170 ℃, and the roller speed is 28 m/min; the temperature of the unidirectional stretching is 48 ℃, and the stretching ratio is 1.7; the diameter of the felting needles processed by the felting roller is 0.04mm, and the arrangement interval of the felting needles is 50 meshes;
(3) guiding the thin sheet into a solvent pool to continuously pass through a guide roller, applying 45N traction tension to enable the thin sheet to be kept in the solvent for soaking for 3min to form a microporous and loose thin sheet, guiding the thin sheet out of the solvent pool, drying at 88 ℃ for 70min to enable the soaked solvent to be fully volatilized, guiding the thin sheet into a cleaning pool for 26min, eluting salt, guiding out, and further drying, cutting edges and coiling to obtain the carbon paper of the gas diffusion layer of the fuel cell; the solvent in the solvent pool is N-methyl pyrrolidone.
The test method comprises the following steps:
the porosity of the carbon paper of the gas diffusion layer prepared in this example was measured with an autopore iv series mercury porosimeter, and the results are shown in table 1.
Example 2
(1) Immersing the microporous conductive carbon into a saturated salt solution for 1h to enable the microporous conductive carbon to fully adsorb a salt solution, then filtering out redundant liquid salt solution, and drying to enable salt to occupy gaps of the microporous conductive carbon to obtain pretreated microporous conductive carbon; the microporous conductive carbon is graphene aerogel with micropores; the saturated salt solution is a saturated solution compounded by sodium chloride and ammonium phosphate;
(2) uniformly dispersing pretreated microporous conductive carbon, soluble salt particles, hot-melt polymer and fiber material, adding the mixture into a mixing roll for hot mixing, calendering by a calender, carrying out unidirectional stretching, and finally carrying out needling roller treatment to obtain a sheet which penetrates through micropores and has an average thickness of 0.2 mm; the soluble salt particles are sodium sulfate particles; the hot-melt polymer is polytetrafluoroethylene; the fiber material is short-cut pitch-based carbon fiber; in the mixed material, the mass ratio of the hot-melt polymer, the pretreated microporous conductive carbon, the soluble salt particles and the fiber material is 100:10:8: 20; the mixing roll adopts an internal mixer, the temperature of hot mixing is 180 ℃, the rotating speed is 100rpm, and the mixing time is 40 min; the temperature of the roller for calendering by the calender is 150 ℃, and the roller speed is 25 m/min; the temperature of the unidirectional stretching is 40 ℃, and the stretching ratio is 1.5; the diameter of the felting needles processed by the felting roller is 0.03mm, and the arrangement interval of the felting needles is 50 meshes;
(3) guiding the thin sheet into a solvent pool to continuously pass through a guide roller, applying 30N traction tension to enable the thin sheet to be kept in the solvent for soaking for 1min to form a microporous and loose thin sheet, guiding the thin sheet out of the solvent pool, drying the thin sheet for 90min at 80 ℃ to enable the soaked solvent to be fully volatilized, then guiding the thin sheet into a cleaning pool for 20min, eluting salt, guiding the thin sheet out, and further drying, cutting edges and coiling to obtain the carbon paper of the gas diffusion layer of the fuel cell; the solvent in the solvent pool is dimethyl sulfoxide.
The test was carried out by the method of example 1, and the test results are shown in Table 1.
Example 3
(1) Immersing the microporous conductive carbon into a saturated salt solution for 2 hours to enable the microporous conductive carbon to fully adsorb a salt solution, then filtering out redundant liquid salt solution, and drying to enable salt to occupy gaps of the microporous conductive carbon to obtain pretreated microporous conductive carbon; the microporous conductive carbon is a carbon fiber ball with micropores; the saturated salt solution is a saturated solution compounded by sodium sulfate and ammonium sulfate;
(2) uniformly dispersing pretreated microporous conductive carbon, soluble salt particles, hot-melt polymer and fiber material, adding the mixture into a mixing roll for hot mixing, calendering by a calender, carrying out unidirectional stretching, and finally carrying out needling roller treatment to obtain a sheet which penetrates through micropores and has an average thickness of 0.3 mm; the soluble salt particles are sodium chloride particles; the hot melt polymer is polypropylene; the fiber material is short-cut viscose-based carbon fiber; in the mixed material, the mass ratio of the hot-melt polymer, the pretreated microporous conductive carbon, the soluble salt particles and the fiber material is 100: 20: 13: 26; the mixing roll adopts a screw extruder, the temperature of hot mixing is 210 ℃, the rotating speed is 150rpm, and the mixing time is 20 min; the temperature of the roller for calendering by the calender is 180 ℃, and the roller speed is 35 m/min; the temperature of the unidirectional stretching is 60 ℃, and the stretching ratio is 2; the diameter of the felting needles processed by the felting roller is 0.05mm, and the arrangement interval of the felting needles is 50 meshes;
(3) the method comprises the steps of firstly, guiding a sheet into a solvent pool to continuously pass through a guide roller, applying 50N traction tension to enable the sheet to be kept in the solvent to be soaked for 5min, forming a microporous and loose sheet, drying the sheet at 100 ℃ for 60min after the sheet is guided out of the solvent pool, enabling the soaked solvent to be fully volatilized, then guiding the sheet into a cleaning pool for 30min, eluting salt, further drying, cutting edges and coiling after the sheet is guided out, and obtaining the carbon paper of the gas diffusion layer of the fuel cell; the solvent in the solvent pool is N, N-dimethylformamide.
The test was carried out by the method of example 1, and the test results are shown in Table 1.
Example 4
(1) Immersing the microporous conductive carbon into a saturated salt solution for 1.5h to enable the microporous conductive carbon to fully adsorb salt liquid, then filtering out redundant liquid salt liquid, and drying to enable salt to occupy gaps of the microporous conductive carbon to obtain pretreated microporous conductive carbon; the microporous conductive carbon is conductive carbon black with micropores; the saturated salt solution is a saturated solution compounded by sodium sulfate and ammonium phosphate;
(2) uniformly dispersing pretreated microporous conductive carbon, soluble salt particles, hot-melt polymer and fiber material, adding the mixture into a mixing roll for hot mixing, calendering by a calender, carrying out unidirectional stretching, and finally carrying out needling roller treatment to obtain a sheet which penetrates through micropores and has an average thickness of 0.25 mm; the soluble salt particles are sodium sulfate particles; the hot-melt polymer is polyimide; the fiber material is short-cut phenolic carbon fiber; in the mixed material, the mass ratio of the hot-melt polymer, the pretreated microporous conductive carbon, the soluble salt particles and the fiber material is 100:15:11: 23; the mixing roll adopts an internal mixer, the temperature of hot mixing is 200 ℃, the rotating speed is 120rpm, and the mixing time is 30 min; the temperature of the roller for calendering by the calender is 165 ℃, and the roller speed is 30 m/min; the temperature of the unidirectional stretching is 50 ℃, and the stretching ratio is 1.8; the diameter of the felting needles processed by the felting roller is 0.04mm, and the arrangement interval of the felting needles is 50 meshes;
(3) guiding the thin sheet into a solvent pool to continuously pass through a guide roller, applying 40N traction tension to enable the thin sheet to be kept in the solvent for soaking for 4min to form a microporous and loose thin sheet, guiding the thin sheet out of the solvent pool, drying for 75min at 90 ℃ to enable the soaked solvent to be fully volatilized, guiding the thin sheet into a cleaning pool for 25min, eluting salt, guiding out, and further drying, cutting edges and coiling to obtain the carbon paper of the gas diffusion layer of the fuel cell; the solvent in the solvent pool is N-methyl pyrrolidone.
The test was carried out by the method of example 1, and the test results are shown in Table 1.
Comparative example 1
Comparative example 1 compared with example 1, the carbon paper for the gas diffusion layer prepared without impregnating the microporous conductive carbon with salt was tested by the method of example 1, and the test results are shown in table 1.
Table 1:
| performance index | Porosity (%) |
| Example 1 | 88.9 |
| Example 2 | 88.3 |
| Example 3 | 88.6 |
| Example 4 | 88.2 |
| Comparative example 1 | 42.1 |
Claims (10)
1. A method for preparing carbon paper of a gas diffusion layer of a fuel cell by rolling is characterized in that the carbon paper of the gas diffusion layer is prepared by uniformly dispersing microporous conductive carbon fully soaked in saturated salt solution, soluble salt particles, hot-melt polymers and fiber materials, mixing, rolling, stretching and needling to obtain a sheet, continuously passing the sheet through a guide roller in a solvent pool, guiding the sheet into a clean water pool after being guided out and dried, and finally guiding out and drying, cutting edges and coiling; the preparation method comprises the following steps:
(1) immersing the microporous conductive carbon into a saturated salt solution for 1-2h to enable the microporous conductive carbon to fully adsorb a salt solution, then filtering out redundant liquid salt solution, and drying to enable salt to occupy gaps of the microporous conductive carbon to obtain pretreated microporous conductive carbon;
(2) uniformly dispersing pretreated microporous conductive carbon, soluble salt particles, hot-melt polymer and fiber material, adding the mixture into a mixing roll for hot mixing, calendering by a calender, carrying out unidirectional stretching, and finally carrying out needling roller treatment to obtain a sheet which penetrates through micropores and has the thickness of 0.2-0.3 mm;
(3) the method comprises the steps of firstly, guiding a sheet into a solvent pool to continuously pass through a guide roller, applying 30-50N traction tension to enable the sheet to be kept in the solvent to be soaked for 1-5min to form a microporous and loose sheet, drying the sheet at 80-100 ℃ for 60-90min after the sheet is led out of the solvent pool to enable the soaked solvent to be fully volatilized, then guiding the sheet into a cleaning pool for 20-30min, eluting salt, leading out, further drying, cutting edges and coiling to obtain the carbon paper of the gas diffusion layer of the fuel cell.
2. The method for preparing the carbon paper for the gas diffusion layer of the fuel cell by calendering according to the claim 1, wherein the saturated salt solution is a saturated solution compounded by sodium chloride or sodium sulfate and ammonium sulfate or ammonium phosphate.
3. The method for preparing the carbon paper for the gas diffusion layer of the fuel cell by calendering according to claim 1, wherein the microporous conductive carbon is one or a combination of more than two of conductive carbon black, graphene aerogel and carbon fiber balls with micropores, the particle size of the conductive carbon is 50-100 μm, and the pore diameter of the micropores is 1-5 μm.
4. The method for preparing the carbon paper for the gas diffusion layer of the fuel cell by calendering according to claim 1, wherein the soluble salt particles are one of sodium chloride particles and sodium sulfate particles, and the particle diameter of the particles is 10-20 μm.
5. The method for preparing the carbon paper for the gas diffusion layer of the fuel cell by calendering according to claim 1, wherein the hot-melt polymer is one or the combination of more than two of polyimide, polytetrafluoroethylene and polypropylene.
6. The method for preparing the carbon paper for the gas diffusion layer of the fuel cell by calendering according to claim 1, wherein the fiber material is one or a combination of more than two of chopped carbon fiber and softwood pulp fiber, and the carbon fiber is one or a combination of more than two of polyacrylonitrile-based carbon fiber, asphalt-based carbon fiber, viscose-based carbon fiber and phenolic-based carbon fiber.
7. The method for preparing the carbon paper for the gas diffusion layer of the fuel cell by calendering according to the claim 1, wherein in the step (2), the mass ratio of the hot-melt polymer, the pretreated microporous conductive carbon, the soluble salt particles and the fiber material is 100:10-20:8-13: 20-26.
8. The method for preparing the carbon paper for the gas diffusion layer of the fuel cell by calendering as claimed in claim 1, wherein the mixing roll in the step (2) is one of a screw extruder and an internal mixer, the temperature of thermal mixing is 180-210 ℃, the rotation speed is 100-150rpm, and the mixing time is 20-40 min; the temperature of the roller for calendering by the calender is 150 ℃ and 180 ℃, and the speed of the roller is 25-35 m/min; the temperature of the unidirectional stretching is 40-60 ℃, and the stretching ratio is 1.5-2; the diameter of the felting needles processed by the felting roller is 0.03-0.05mm, and the arrangement interval of the felting needles is 50 meshes.
9. The method for preparing the carbon paper for the gas diffusion layer of the fuel cell by calendering according to the claim 1, wherein the solvent in the solvent pool is one of N-methyl pyrrolidone, dimethyl sulfoxide and N, N-dimethylformamide.
10. A carbon paper for a gas diffusion layer of a fuel cell produced by the production method according to any one of claims 1 to 9.
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