CN118223326A - Carbon felt, carbon paper, preparation methods of carbon felt and carbon paper and fuel cell membrane electrode - Google Patents

Carbon felt, carbon paper, preparation methods of carbon felt and carbon paper and fuel cell membrane electrode Download PDF

Info

Publication number
CN118223326A
CN118223326A CN202410379867.6A CN202410379867A CN118223326A CN 118223326 A CN118223326 A CN 118223326A CN 202410379867 A CN202410379867 A CN 202410379867A CN 118223326 A CN118223326 A CN 118223326A
Authority
CN
China
Prior art keywords
carbon
felt
fiber
paper
resin
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.)
Pending
Application number
CN202410379867.6A
Other languages
Chinese (zh)
Inventor
张水木
王士元
卢恋月
乔伟静
娄益玮
郭禹森
陈玉姣
周明正
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.)
Spic Hydrogen Energy Technology Development Co Ltd
Original Assignee
Spic Hydrogen Energy Technology Development Co Ltd
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 Spic Hydrogen Energy Technology Development Co Ltd filed Critical Spic Hydrogen Energy Technology Development Co Ltd
Priority to CN202410379867.6A priority Critical patent/CN118223326A/en
Publication of CN118223326A publication Critical patent/CN118223326A/en
Pending legal-status Critical Current

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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B33/00—Layered products characterised by particular properties or particular surface features, e.g. particular surface coatings; Layered products designed for particular purposes not covered by another single class
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B5/00—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts
    • B32B5/22—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by the presence of two or more layers which are next to each other and are fibrous, filamentary, formed of particles or foamed
    • B32B5/24—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by the presence of two or more layers which are next to each other and are fibrous, filamentary, formed of particles or foamed one layer being a fibrous or filamentary layer
    • B32B5/26—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by the presence of two or more layers which are next to each other and are fibrous, filamentary, formed of particles or foamed one layer being a fibrous or filamentary layer another layer next to it also being fibrous or filamentary
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H13/00—Pulp or paper, comprising synthetic cellulose or non-cellulose fibres or web-forming material
    • D21H13/10—Organic non-cellulose fibres
    • D21H13/12—Organic non-cellulose fibres from macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D21H13/14—Polyalkenes, e.g. polystyrene polyethylene
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H13/00—Pulp or paper, comprising synthetic cellulose or non-cellulose fibres or web-forming material
    • D21H13/10—Organic non-cellulose fibres
    • D21H13/12—Organic non-cellulose fibres from macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D21H13/16—Polyalkenylalcohols; Polyalkenylethers; Polyalkenylesters
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H13/00—Pulp or paper, comprising synthetic cellulose or non-cellulose fibres or web-forming material
    • D21H13/10—Organic non-cellulose fibres
    • D21H13/20—Organic non-cellulose fibres from macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • D21H13/24—Polyesters
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H13/00—Pulp or paper, comprising synthetic cellulose or non-cellulose fibres or web-forming material
    • D21H13/36—Inorganic fibres or flakes
    • D21H13/46—Non-siliceous fibres, e.g. from metal oxides
    • D21H13/50—Carbon fibres
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
    • D21H17/03—Non-macromolecular organic compounds
    • D21H17/05—Non-macromolecular organic compounds containing elements other than carbon and hydrogen only
    • D21H17/06—Alcohols; Phenols; Ethers; Aldehydes; Ketones; Acetals; Ketals
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
    • D21H17/20—Macromolecular organic compounds
    • D21H17/33—Synthetic macromolecular compounds
    • D21H17/46—Synthetic macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • D21H17/47—Condensation polymers of aldehydes or ketones
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
    • D21H17/20—Macromolecular organic compounds
    • D21H17/33—Synthetic macromolecular compounds
    • D21H17/46—Synthetic macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • D21H17/47—Condensation polymers of aldehydes or ketones
    • D21H17/48—Condensation polymers of aldehydes or ketones with phenols
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H25/00—After-treatment of paper not provided for in groups D21H17/00 - D21H23/00
    • D21H25/005—Mechanical treatment
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H25/00—After-treatment of paper not provided for in groups D21H17/00 - D21H23/00
    • D21H25/04—Physical treatment, e.g. heating, irradiating
    • D21H25/06—Physical treatment, e.g. heating, irradiating of impregnated or coated paper
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H27/00—Special paper not otherwise provided for, e.g. made by multi-step processes
    • D21H27/30—Multi-ply
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21J—FIBREBOARD; MANUFACTURE OF ARTICLES FROM CELLULOSIC FIBROUS SUSPENSIONS OR FROM PAPIER-MACHE
    • D21J5/00—Manufacture of hollow articles by transferring sheets, produced from fibres suspensions or papier-mâché by suction on wire-net moulds, to couch-moulds
    • 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
    • H01M4/96—Carbon-based electrodes
    • 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]
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2250/00—Layers arrangement
    • B32B2250/20—All layers being fibrous or filamentary
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2250/00—Layers arrangement
    • B32B2250/40—Symmetrical or sandwich layers, e.g. ABA, ABCBA, ABCCBA
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2260/00—Layered product comprising an impregnated, embedded, or bonded layer wherein the layer comprises an impregnation, embedding, or binder material
    • B32B2260/02—Composition of the impregnated, bonded or embedded layer
    • B32B2260/021—Fibrous or filamentary layer
    • B32B2260/023—Two or more layers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2260/00—Layered product comprising an impregnated, embedded, or bonded layer wherein the layer comprises an impregnation, embedding, or binder material
    • B32B2260/04—Impregnation, embedding, or binder material
    • B32B2260/046—Synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2262/00—Composition or structural features of fibres which form a fibrous or filamentary layer or are present as additives
    • B32B2262/02—Synthetic macromolecular fibres
    • B32B2262/0223—Vinyl resin fibres
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2262/00—Composition or structural features of fibres which form a fibrous or filamentary layer or are present as additives
    • B32B2262/02—Synthetic macromolecular fibres
    • B32B2262/0276—Polyester fibres
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2262/00—Composition or structural features of fibres which form a fibrous or filamentary layer or are present as additives
    • B32B2262/10—Inorganic fibres
    • B32B2262/106—Carbon fibres, e.g. graphite fibres
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/30—Properties of the layers or laminate having particular thermal properties
    • B32B2307/302—Conductive
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/50—Properties of the layers or laminate having particular mechanical properties
    • B32B2307/546—Flexural strength; Flexion stiffness
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2457/00—Electrical equipment
    • B32B2457/10—Batteries
    • 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

Landscapes

  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Mechanical Engineering (AREA)
  • Inorganic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Sustainable Development (AREA)
  • Sustainable Energy (AREA)
  • Paper (AREA)

Abstract

The embodiment of the invention provides a carbon felt, carbon paper, a preparation method thereof and a fuel cell membrane electrode, belonging to the technical field of fuel cells. The carbon felt obtained by the preparation method of the carbon felt is provided with a carbon fiber layer, a reinforced fiber layer and a carbon fiber layer, and the carbon paper prepared by the carbon felt is provided with a carbon fiber resin carbon layer, a resin carbon layer and a main structure of the carbon fiber resin carbon layer, so that the porosity degree of the carbon paper can be improved, a Venturi tube effect can be generated on a diffusion channel, a pressure gradient is formed, the conveying efficiency of gas and liquid is improved, and the mass transfer and heat transfer efficiency of a fuel cell is effectively improved; the strength and the bending resistance of the carbon paper can be effectively improved.

Description

Carbon felt, carbon paper, preparation methods of carbon felt and carbon paper and fuel cell membrane electrode
Technical Field
The invention belongs to the technical field of fuel cells, and particularly relates to a carbon felt, carbon paper, a preparation method thereof and a fuel cell membrane electrode.
Background
Carbon paper is an ideal substrate for a gas diffusion layer of a fuel cell, and mainly plays roles of hydrophobic exhaust, electric conduction and supporting a membrane electrode in the fuel cell. The main body of the carbon paper is carbon fiber and resin carbon, and the conductivity is good. The porosity and pore structure of the carbon paper directly affect the overall transmission efficiency of the carbon paper as a gas diffusion layer, and meanwhile, the strength of the carbon paper directly affects the durability of the membrane electrode and the overall performance of the battery.
At present, the method for preparing the carbon paper generally utilizes chopped carbon fiber for paper making, and is characterized in that the carbon fiber paper is obtained by dipping a base paper in a resin solution and then carrying out high-temperature treatment. Specifically, the continuously prepared carbon fibers are subjected to chopping to obtain chopped carbon fibers with the same length. Adding chopped carbon fibers into a dispersing agent solution to form a carbon fiber dispersion liquid, and pulping the carbon fiber dispersion liquid to obtain chopped carbon fiber slurry; filtering the chopped carbon fiber slurry in paper making equipment to obtain a chopped carbon fiber wet felt; then carrying out negative pressure dehumidification, sizing and drying on the chopped carbon fiber wet felt to obtain a carbon fiber surface felt, namely a carbon felt for short; and then, immersing the carbon felt in a resin solution, performing hot press molding to obtain carbon fiber prepreg, and finally, carbonizing and graphitizing to obtain the finished carbon paper. However, this preparation method has the following technical drawbacks:
1. The pore structure is single, and the requirement of high energy density of the battery can not be met. The carbon paper prepared from the single carbon fiber has small pore size range and low pore size. The current papermaking meets the requirements of lower fiber length, the network pores of the carbon paper are smaller, the permeability is poor, and the gas and water in the gas diffusion layer on the fuel cell are conveyed slowly, so that flooding in the operation process of the fuel cell is caused, and the operation is unfavorable especially for high-current density operation.
2. The strength of the carbon paper is low, and the bending resistance degree of the carbon paper is poor. The fiber structure of the carbon felt prepared by the common wet method and the glue adding form are randomly arranged, so that the whole structure is almost consistent. After the resin is filled and densified, the structure of the lap joint of the fibers is not changed, the distribution of the resin carbon is mainly determined by the structure of the carbon felt, the combination property of the carbon fibers and the resin carbon is poor, and the carbon paper is easy to peel and is not beneficial to the improvement of the strength and the bending property of the carbon paper.
Disclosure of Invention
The present invention aims to solve at least one of the technical problems in the related art to some extent. Therefore, the embodiment of the invention provides a carbon felt, carbon paper, a preparation method thereof and a fuel cell membrane electrode, and the carbon felt and the carbon paper have various pore structures, high strength and good bending resistance.
A first aspect of an embodiment of the present invention provides a method for preparing a carbon felt, including the steps of:
S1, dispersing carbon fibers in a first dispersing agent solution, pulping to obtain carbon fiber slurry, and filtering the carbon fiber slurry to obtain a carbon fiber wet felt; dispersing reinforcing fibers in a second dispersing agent solution, pulping to obtain reinforcing fiber slurry, and filtering the reinforcing fiber slurry to obtain a reinforcing fiber wet felt;
s2, sequentially layering and stacking the carbon fiber wet felt, the reinforced fiber wet felt and the carbon fiber wet felt to obtain a composite wet felt, and carrying out negative pressure dehumidification, sizing and drying on the composite wet felt to obtain the carbon felt.
The preparation method of the carbon felt provided by the embodiment of the invention has the following advantages and technical effects:
(1) Step S2 of the preparation method of the carbon felt of the embodiment of the invention is to sequentially lay layers according to the order of the carbon fiber wet felt, the reinforced fiber wet felt and the carbon fiber wet felt, the obtained carbon felt is provided with a carbon fiber layer, a reinforced fiber layer and a carbon fiber layer, and the carbon paper prepared by subsequent resin impregnation and high-temperature treatment is provided with a main body structure of a carbon fiber resin carbon layer, a resin carbon layer (marked as an intermediate layer/reinforced layer) and a carbon fiber resin carbon layer.
(2) The carbon felt has the pores distributed in multiple layers, is favorable for the orientation of resin and the orientation of resin carbon in the preparation process of the carbon paper, and the prepared carbon paper has the resin carbon distribution with multiple layers of distributed pores and a net structure, so that the porosity degree of the carbon paper can be improved, a Venturi tube effect can be generated on a diffusion channel, a pressure gradient is formed, the conveying efficiency of gas and liquid is improved, and the mass transfer and heat transfer efficiency of a fuel cell is effectively improved.
(3) Compared with the carbon paper in the prior art, the intermediate resin carbon layer in the carbon paper provided by the embodiment of the invention becomes the reinforcing layer for providing the strength of the main body of the carbon paper, and the integral strength of the carbon paper can be effectively improved. In addition, the resin carbon of the carbon fiber resin carbon layer can be used as an adhesive, so that the combination property of the carbon fiber and the resin carbon is improved, and the bending resistance degree of the carbon paper is improved.
In some embodiments, the reinforcing fibers are at least one of polyvinyl alcohol fibers, polyester fibers, polyethylene fibers, and polypropylene fibers.
In some embodiments, the reinforcing fibers have a length of 3mm to 20mm.
In some embodiments, the carbon fibers are water-soluble carbon fibers; and/or the diameter of the carbon fiber is 5-7 μm; and/or the length of the carbon fiber is 3 mm-20 mm.
In some embodiments, the ratio of the areal density of the carbon fibers to the areal density of the reinforcing fibers in the carbon mat is (1-3): 1.
In some embodiments, the carbon mat has an areal density of 20g/m 2～80g/m2.
A second aspect of embodiments of the present invention provides a carbon felt obtained by the method of producing a carbon felt of the first aspect.
The carbon felt provided by the embodiment of the invention has the following advantages and technical effects:
(1) The carbon felt provided by the embodiment of the invention is provided with a carbon fiber layer, a reinforced fiber layer and a carbon fiber layer, and the carbon paper prepared by subsequent resin impregnation and high-temperature treatment is provided with a main body structure of the carbon fiber resin carbon layer, the resin carbon layer (marked as an intermediate layer/reinforced layer) and the carbon fiber resin carbon layer.
(2) The carbon felt has the pores distributed in multiple layers, is favorable for the orientation of resin and the orientation of resin carbon in the preparation process of the carbon paper, and the prepared carbon paper has the resin carbon distribution with multiple layers of distributed pores and a net structure, so that the porosity degree of the carbon paper can be improved, a Venturi tube effect can be generated on a diffusion channel, a pressure gradient is formed, the conveying efficiency of gas and liquid is improved, and the mass transfer and heat transfer efficiency of a fuel cell is effectively improved.
(3) Compared with the carbon paper in the prior art, the intermediate resin carbon layer in the carbon paper provided by the embodiment of the invention becomes the reinforcing layer for providing the strength of the main body of the carbon paper, and the integral strength of the carbon paper can be effectively improved. In addition, the resin carbon of the carbon fiber resin carbon layer can be used as an adhesive, so that the combination property of the carbon fiber and the resin carbon is improved, and the bending resistance degree of the carbon paper is improved.
A third aspect of the embodiment of the present invention provides a method for preparing carbon paper, including the steps of:
(1) Impregnating the carbon felt according to the second aspect of the embodiment of the invention with a resin solution, and then performing hot press molding to obtain a composite prepreg;
(2) And carrying out high-temperature treatment on the composite prepreg to obtain the carbon paper.
The preparation method of the carbon paper provided by the embodiment of the invention has the following advantages and technical effects:
because the carbon felt of the second aspect of the embodiment of the invention is adopted, the carbon paper obtained by the preparation method of the carbon paper of the embodiment of the invention has a main structure with a carbon fiber resin carbon layer, a resin carbon layer (marked as an intermediate layer/a reinforcing layer) and a carbon fiber resin carbon layer, so that the conveying efficiency of gas and liquid can be effectively improved, and the strength and the bending resistance degree of the carbon paper can be improved.
A fourth aspect of the embodiment of the present invention provides a carbon paper obtained by the method for producing a carbon paper according to the third aspect.
The carbon paper provided by the embodiment of the invention has the following advantages and technical effects:
because the preparation method of the carbon paper of the third aspect of the embodiment of the invention is adopted, the carbon paper obtained by the preparation method of the carbon paper of the embodiment of the invention has a main structure with a carbon fiber resin carbon layer, a resin carbon layer (marked as an intermediate layer/a reinforcing layer) and a carbon fiber resin carbon layer, can effectively improve the conveying efficiency of gas and liquid, and can also improve the strength and the bending resistance degree of the carbon paper.
A fifth aspect of an embodiment of the present invention provides a fuel cell membrane electrode, where a base material of a gas diffusion layer of the fuel cell membrane electrode is the carbon paper described in the fourth aspect.
The fuel cell membrane electrode of the embodiment of the invention has the following advantages and technical effects:
Because the carbon paper in the fourth aspect of the invention is adopted as the base material of the gas diffusion layer, the membrane electrode in the embodiment of the invention is applied to the fuel cell, and the power of the fuel cell can be obviously improved.
Drawings
FIG. 1 is a schematic diagram of a carbon paper according to an embodiment of the present invention;
FIG. 2 is a surface scanning electron microscope image of the carbon felt of example 1;
FIG. 3 is a cross-sectional scanning electron microscope image of the carbon paper of example 1;
FIG. 4 is a cross-sectional scanning electron microscope image of the carbon paper of comparative example 1.
Detailed Description
Reference will now be made in detail to embodiments of the present invention, examples of which are illustrated in the accompanying drawings. The embodiments described below by referring to the drawings are illustrative and intended to explain the present invention and should not be construed as limiting the invention.
A first aspect of an embodiment of the present invention provides a method for preparing a carbon felt, including the steps of:
S1, dispersing carbon fibers in a first dispersing agent solution, pulping to obtain carbon fiber slurry, and filtering the carbon fiber slurry to obtain a carbon fiber wet felt; dispersing reinforcing fibers in a second dispersing agent solution, pulping to obtain reinforcing fiber slurry, and filtering the reinforcing fiber slurry to obtain a reinforcing fiber wet felt;
s2, sequentially layering and stacking the carbon fiber wet felt, the reinforced fiber wet felt and the carbon fiber wet felt to obtain a composite wet felt, and carrying out negative pressure dehumidification, sizing and drying on the composite wet felt to obtain the carbon felt.
In the method for preparing the carbon felt according to the embodiment of the invention, in addition to preparing the carbon fiber wet felt in the step S1, the reinforced fiber wet felt is also prepared. Step S2, sequentially layering the carbon fiber wet felt, the reinforced fiber wet felt and the carbon fiber wet felt in sequence, wherein the obtained carbon felt is provided with a carbon fiber layer, a reinforced fiber layer and a carbon fiber layer, and the carbon paper prepared by subsequent resin impregnation and high-temperature treatment is provided with a main structure of a carbon fiber resin carbon layer, a resin carbon layer (marked as an intermediate layer/a reinforced layer) and a carbon fiber resin carbon layer, and the structural schematic diagram of the carbon paper in the embodiment of the invention is shown in figure 1.
It should be noted that, the affinity (or wettability) of the resin with the carbon fibers is smaller than that of the resin with the reinforcing fibers, so that the resin is more concentrated in the reinforcing fiber layer after the carbon felt is subsequently impregnated with the resin, and a small portion of the resin is infiltrated in the carbon fiber layer. Carbonizing resin impregnated in a carbon fiber layer in the carbon felt through high-temperature treatment to form carbon coated on the surface of the carbon fiber to obtain a carbon fiber resin carbon layer in the carbon paper; the resin impregnated by the reinforcing fiber layer in the carbon felt is carbonized by high-temperature treatment to form resin carbon, and the residual carbon formed by the reinforcing fiber layer in the carbon felt after being carbonized by high-temperature treatment is low, so that the carbon felt can be considered to be basically removed, and the formed vacancies are the main spaces of macropores of the middle layer, so that the middle layer of the carbon paper is the resin carbon layer.
The carbon residue of the resin carbon layer in the middle of the carbon paper is lower than that of the carbon fiber resin carbon layers at the two sides, so that the pores of the middle layer are higher than those at the two sides, and the flow passage of the membrane electrode has the following results: the catalytic layer microporous layer (micropore), the carbon fiber resin carbon layer (mesopore), the resin carbon layer (macropore), the carbon fiber resin carbon layer (mesopore) and the bipolar plate (macropore), so that a Venturi tube effect can be generated on a diffusion channel to form a pressure gradient, the conveying efficiency of gas and liquid is improved, and the mass transfer and heat transfer efficiency of the fuel cell is effectively improved.
In addition, compared with the carbon paper in the prior art, the intermediate resin carbon layer in the carbon paper provided by the embodiment of the invention becomes a reinforcing layer for providing the strength of the main body of the carbon paper, and the strength of the whole carbon paper can be effectively improved. In addition, it can be understood that the carbon paper in the prior art is formed by combining carbon fibers and resin carbon, but the carbon paper in the embodiment of the invention has the combination of the carbon fibers and the resin carbon, and the combination of the resin carbon and the resin carbon in the three-layer structure, and the combination degree between the two substances is not as good as that between the resin carbon and the resin carbon, so that the combination degree between the substances in the carbon paper in the embodiment of the invention is better than that between the substances in the carbon paper in the prior art, therefore, the resin carbon in the carbon fiber resin carbon layer in the carbon paper in the embodiment of the invention can be used as an adhesive, the combination property of the carbon fibers and the resin carbon is improved, and the resin carbon is not easy to peel, thereby improving the bending resistance degree of the carbon paper.
In some embodiments, the carbon fibers are water-soluble carbon fibers. The water-soluble carbon fiber can be obtained by the following method: high-temperature degumming is carried out on the carbon fiber coiled wire, the epoxy sizing agent on the surface is removed, then an electrochemical, gas/liquid phase oxidation method or surface dispersion treatment is adopted for modification, and oxygen-containing functional groups such as hydroxyl, carboxyl and the like on the surface of the carbon fiber are increased, so that the hydrophilicity of the carbon fiber is improved, and the water-soluble carbon fiber is obtained. The water-soluble carbon fibers are more easily uniformly dispersed in the first dispersant solution than the non-water-soluble carbon fibers, thereby improving uniformity of the carbon felt and the carbon paper. Or pre-oxidizing and re-carbonizing polyacrylonitrile fiber to obtain water soluble carbon fiber.
In some embodiments, the carbon fibers have a diameter of 5 μm to 7 μm, e.g., 5 μm, 5.5 μm, 6 μm, 6.5 μm, 7 μm, etc., and a length of 3mm to 20mm, e.g., 3mm, 4mm, 6mm, 8mm, 10mm, 12mm, 14mm, 16mm, 18mm, 20mm, etc. When the diameter of the carbon fiber is too small, the distribution of the surface groups is not easy, the dispersion effect is poor, and the uniformity of the carbon felt and the carbon paper is not easy to improve. When the diameter of the carbon fiber is too large, the structural distribution of the carbon fiber is uneven and the strength is poor, which is also unfavorable for improving the uniformity and strength of the carbon felt and the carbon paper. When the length of the carbon fiber is too short, it is disadvantageous to maintain the strength of the carbon felt, and the porosity of the carbon felt is lowered. When the length of the carbon fiber is too long, uniform dispersion of the fiber in the preparation process of the carbon felt is not facilitated, so that uniformity of the carbon felt and the carbon paper is not facilitated to be improved.
In some embodiments, the reinforcing fiber is at least one of a polyvinyl alcohol (PVA) fiber, a polyester fiber, a Polyethylene (PE) fiber, and a polypropylene (PP) fiber. The fiber materials of the above types have rich hydroxyl and carbonyl groups, good combination with impregnating resin and low carbon residue rate, and are convenient for pore formation and reserving vacancies for resin carbon.
In some embodiments, the length of the reinforcing fibers is 3mm to 20mm, such as 3mm, 4mm, 6mm, 8mm, 10mm, 12mm, 14mm, 16mm, 18mm, 20mm, etc. When the reinforcing fiber is too short, the carbon felt pores are occupied, which is unfavorable for achieving the resin loading rate. When the reinforcing fiber is too long and exceeds the dispersion capacity of the second dispersing agent solution, the uniform molding of the carbon felt is not facilitated.
The method of preparing the carbon felt of the embodiment of the present invention is not particularly limited to the first dispersant solution and the second dispersant solution. For example, the first dispersant solution and the second dispersant solution are solutions formed by dissolving a dispersant in a solvent, and the dispersant may be at least one of methylcellulose, carboxymethylcellulose, hydroxyethylcellulose, polyethylene oxide, polyacrylamide and the like; the solvent may be water or the like. Classically, the first and second dispersant solutions may be aqueous solutions of carboxymethyl cellulose at a mass concentration of 0.05% to 0.2%, or aqueous solutions of hydroxyethyl cellulose at a mass concentration of 0.1% to 0.3%.
In some embodiments, the ratio of the areal density of the carbon fibers to the areal density of the reinforcing fibers in the carbon mat is (1-3): 1, e.g., 1:1, 1.5:1, 2:1, 2.5:1, 3:1, etc. The ratio is to control the content of the reinforcing layer in the carbon paper. When the ratio is too small, the reinforcing layer remaining in the middle eventually becomes too large, and the conductivity of the carbon paper deviates. When the ratio is too large, it is not advantageous to improve the conveying efficiency of gas and liquid, and also to improve the strength and bending resistance of the carbon paper.
In some embodiments, the carbon mat has an areal density of 20g/m 2～80g/m2, such as 20g/m2、30g/m2、40g/m2、50g/m2、60g/m2、70g/m2、80g/m2, or the like. The surface density of the carbon felt is directly related to the thickness of the carbon felt, and when the surface density of the carbon felt is too large, the thickness is too large, so that the performance of the carbon paper in fuel cell application is not improved. When the surface density of the carbon felt is too low, the process preparation problem exists, the carbon paper cannot reach the target parameter, the target surface density of the carbon paper is 20g/m 2～80g/m2, and the target thickness of the carbon paper is 0.15-0.2 mm.
A second aspect of embodiments of the present invention provides a carbon felt obtained by the method of producing a carbon felt of the first aspect.
A third aspect of the embodiment of the present invention provides a method for preparing carbon paper, including the steps of:
(1) Impregnating the carbon felt according to the second aspect of the embodiment of the invention with a resin solution, and then performing hot press molding to obtain a composite prepreg;
(2) And carrying out high-temperature treatment on the composite prepreg to obtain the carbon paper.
The method for preparing the carbon paper according to the embodiment of the present invention is not particularly limited to the impregnating resin solution. For example, the resin solution may be a methanol solution of phenolic resin having a volume concentration of 5 to 25vol.%, or an ethanol solution of furfuryl ketone resin having a mass concentration of 5 to 10 wt.%. As for the dipping time, it may be 5min to 10min.
Phenolic resin and furfuryl ketone resin are used as densifiers of the carbon felt, and the mass loss is low under the condition of high temperature. Because both resins have a ring structure, cyclization reaction is easy to generate in the high-temperature treatment process, and meanwhile, the phenolic resin and the furfuryl ketone resin have low oxygen content and can keep higher carbon residue rate which is generally more than 50 percent, so that the phenolic resin and/or the furfuryl ketone resin can be used as a densifier to improve the density of the carbon paper and optimize the conductivity of the carbon paper.
In some embodiments, the temperature of the hot press forming may be 150 ℃ to 200 ℃, the pressure of the hot press forming may be 3MPa to 10MPa, and the time of the hot press forming may be 3min to 5min.
The high temperature treatment is carbonization and graphitization. The carbonization temperature can be 900-1100 ℃, and the carbonization time can be 0.5-2 h; the graphitization temperature can be 2000-2500 ℃, and the graphitization time can be 1-3 h.
A fourth aspect of the embodiment of the present invention provides a carbon paper obtained by the method for producing a carbon paper according to the third aspect.
Because the preparation method of the carbon paper of the third aspect of the embodiment of the invention is adopted, the carbon paper obtained by the preparation method of the carbon paper of the embodiment of the invention has a main structure with a carbon fiber resin carbon layer, a resin carbon layer (marked as an intermediate layer/a reinforcing layer) and a carbon fiber resin carbon layer, can effectively improve the conveying efficiency of gas and liquid, and can also improve the strength and the bending resistance degree of the carbon paper.
A fifth aspect of an embodiment of the present invention provides a fuel cell membrane electrode, where a base material of a gas diffusion layer of the fuel cell membrane electrode is the carbon paper described in the fourth aspect.
Because the carbon paper in the fourth aspect of the invention is adopted as the base material of the gas diffusion layer, the membrane electrode in the embodiment of the invention is applied to the fuel cell, and the power of the fuel cell can be obviously improved.
The present invention will be described in detail with reference to the following examples and drawings.
Example 1
The preparation method of the carbon paper for the proton exchange membrane fuel cell comprises the following specific steps:
① Taking 30 parts by weight of polyacrylonitrile-based water-soluble 6 mm-length chopped carbon fibers (namely, pre-oxidizing and re-carbonizing the polyacrylonitrile fibers to obtain water-soluble carbon fibers, chopping the water-soluble carbon fibers to obtain water-soluble 6 mm-length chopped carbon fibers), putting the chopped carbon fibers into a carboxymethyl cellulose aqueous solution (first dispersing agent solution) with the mass concentration of 0.1wt.%, starting a high-speed stirrer, stirring at 2000 revolutions per minute, stopping stirring after stirring for 10 minutes, observing whether all the fibers are uniformly dispersed, and stopping stirring to prepare the carbon fiber slurry. And (3) carrying out solid-liquid separation on the carbon fiber slurry through a 80-mesh filter screen, and squeezing and dehydrating to obtain the carbon fiber wet felt.
② 20 Parts by weight of a4 mm-long polyester staple fiber (i.e., a reinforcing fiber) was put into a carboxymethyl cellulose aqueous solution (second dispersant solution) having a mass concentration of 0.1wt.%, and the stirring was stopped after stirring at a stirring speed of 2000 rpm by a high-speed stirrer for 5 minutes, and the stirring was stopped to prepare a reinforcing fiber slurry by observing whether all the fibers were uniformly dispersed. And (3) solid-liquid separation and squeezing dehydration are carried out on the reinforced fiber slurry through a 120-mesh filter screen, so that the reinforced fiber wet felt is obtained.
③ Stacking the carbon fiber wet felt, the reinforced fiber wet felt and the carbon fiber wet felt in sequence to obtain a composite wet felt; and carrying out negative pressure dehumidification on the composite wet felt, spraying polyvinyl alcohol solution with the weight of 20 parts of glue, drying by using an oven/drying cylinder, and coiling to obtain the carbon fiber surface felt, namely the carbon felt, wherein the surface density of the carbon felt is 50g/m 2, and the ratio of the surface density of the carbon fiber in the carbon felt to the surface density of the reinforcing fiber is 3:1. Fig. 2 is a surface scanning electron microscope image of the carbon felt of example 1.
④ A phenolic resin methanol solution with the volume concentration of 10vol.% is immersed on the carbon felt by using an immersion coater, and then the carbon felt is dried by hot air at 100 ℃. The resin loading was 100% of the carbon felt areal density. And carrying out hot press curing at 170 ℃ and 3MPa on the dried sample, and keeping for 3 minutes to obtain the composite prepreg.
⑤ And heating the composite prepreg to 1000 ℃ in a carbonization furnace, preserving heat for 1 hour, taking out, and naturally cooling to obtain a carbonized product. Transferring the carbonized product into a graphitization furnace, heating to 2000 ℃ for 30 minutes, naturally cooling, and obtaining graphitized product, namely the carbon paper, wherein the surface density of the carbon paper is 70g/m 2, and the thickness of the carbon paper is 0.16mm. Fig. 3 is a cross-sectional scanning electron microscope image of the carbon paper of example 1.
Example 2
The preparation method of the carbon paper for the proton exchange membrane fuel cell comprises the following specific steps:
① 36 parts by weight of polyacrylonitrile-based water-soluble 6 mm-length chopped carbon fibers are put into a carboxymethyl cellulose water solution (first dispersing agent solution) with the mass concentration of 0.1wt.%, a high-speed stirrer is started, stirring is stopped after stirring for 10 minutes at the stirring speed of 2000 rpm, whether all fibers are uniformly dispersed or not is observed, and stirring is stopped to prepare the carbon fiber slurry. And (3) carrying out solid-liquid separation on the carbon fiber slurry through a 80-mesh filter screen, and squeezing and dehydrating to obtain the carbon fiber wet felt.
② 18 Parts by weight of 4mm length PVA short fibers (namely reinforcing fibers) are taken and put into a carboxymethyl cellulose water solution (second dispersant solution) with the mass concentration of 0.1wt.%, a high-speed stirrer is started, stirring speed is 2000 revolutions per minute, stirring is stopped after stirring for 5 minutes, whether all fibers are uniformly dispersed is observed, and stirring is stopped to prepare the reinforcing fiber slurry. And (3) solid-liquid separation is carried out on the reinforced fiber slurry through a 120-mesh filter screen, and the wet felt of the reinforced fiber is obtained after squeezing and dehydration.
③ Stacking the carbon fiber wet felt, the reinforced fiber wet felt and the carbon fiber wet felt in sequence to obtain a composite wet felt; and (3) carrying out negative-pressure dehumidification on the composite wet felt, spraying 10 parts by weight of polyvinyl alcohol solution, drying by using an oven/drying cylinder, and coiling to obtain the carbon felt, wherein the surface density of the carbon felt is 50g/m 2, and the ratio of the surface density of the carbon fibers in the carbon felt to the surface density of the reinforcing fibers is 4:1.
④ The carbon felt is impregnated with a furfuryl alcohol resin ethanol solution with a volume concentration of 10vol.% by using an impregnation coater, and then dried by hot air at 100 ℃. The resin loading was 90% of the carbon felt areal density. And carrying out hot press curing at 170 ℃ and 3MPa on the dried sample, and keeping for 3 minutes to obtain the composite prepreg.
⑤ And heating the composite prepreg to 1000 ℃ in a carbonization furnace, preserving heat for 1 hour, taking out, and naturally cooling to obtain a carbonized product. Transferring the carbonized product into a graphitization furnace, heating to 2000 ℃ for 30 minutes, naturally cooling, and obtaining graphitized product, namely carbon paper, wherein the surface density of the carbon paper is 80g/m 2, and the thickness of the carbon paper is 0.18mm.
Comparative example 1
The preparation method of the carbon paper for the proton exchange membrane fuel cell comprises the following specific steps:
① 60 parts by weight of polyacrylonitrile-based water-soluble 6 mm-length chopped carbon fibers and 20 parts by weight of polyester staple fibers (namely reinforcing fibers) are put into a carboxymethyl cellulose water solution with the mass concentration of 0.1wt.%, a high-speed stirrer is started, the stirring speed is 2000 revolutions per minute, stirring is stopped after stirring for 10 minutes, whether all fibers are uniformly dispersed is observed, and stirring is stopped to prepare mixed fiber slurry. And (3) carrying out solid-liquid separation on the mixed fiber slurry through a 80-mesh filter screen, and squeezing and dehydrating to obtain the mixed fiber wet felt.
② And carrying out negative pressure dehumidification on the mixed fiber wet felt, spraying polyvinyl alcohol solution with the weight of 20 parts of glue, drying by an oven/drying cylinder, and coiling to obtain the carbon felt, wherein the surface density of the carbon felt is 50g/m 2, and the ratio of the surface density of the carbon fiber in the carbon felt to the surface density of the reinforcing fiber is 3:1.
③ A phenolic resin methanol solution with the volume concentration of 10vol.% is immersed on the carbon felt by using an immersion coater, and then the carbon felt is dried by hot air at 100 ℃. The resin loading was 100% of the carbon felt areal density. And carrying out hot press curing at 170 ℃ and 3MPa on the dried sample, and keeping for 3 minutes to obtain the mixed prepreg.
④ Heating the mixed prepreg to 1000 ℃ in a carbonization furnace, preserving heat for 1 hour, taking out, and naturally cooling to obtain a carbonized product. Transferring the carbonized product into a graphitization furnace, heating to 2000 ℃ for 30 minutes, naturally cooling, and obtaining graphitized product, namely the carbon paper, wherein the mass density of the carbon paper is 70g/m 2, and the thickness of the carbon paper is 0.16mm. FIG. 4 is a cross-sectional scanning electron microscope image of the carbon paper of comparative example 1.
Comparative example 2
The preparation method of the carbon paper for the proton exchange membrane fuel cell comprises the following specific steps:
① 72 parts by weight of polyacrylonitrile water-soluble 6 mm-length chopped carbon fibers and 18 parts by weight of PVA short fibers (namely reinforcing fibers) are put into a carboxymethyl cellulose water solution with the mass concentration of 0.1wt.%, a high-speed stirrer is started, the stirring speed is 2000 revolutions per minute, stirring is stopped after stirring for 10 minutes, whether all fibers are uniformly dispersed is observed, and stirring is stopped to prepare mixed fiber slurry. And (3) carrying out solid-liquid separation on the mixed fiber slurry through a 80-mesh filter screen, and squeezing and dehydrating to obtain the mixed fiber wet felt.
② And carrying out negative pressure dehumidification on the mixed fiber wet felt, spraying 10 parts by weight of polyvinyl alcohol solution, drying by a drying oven/drying cylinder, and coiling to obtain the carbon felt, wherein the surface density of the carbon felt is 50g/m 2, and the ratio of the surface density of the carbon fiber in the carbon felt to the surface density of the reinforcing fiber is 4:1.
③ A phenolic resin methanol solution with the volume concentration of 10vol.% is immersed on the carbon felt by using an immersion coater, and then the carbon felt is dried by hot air at 100 ℃. The resin loading was 100% of the carbon felt areal density. And carrying out hot press curing at 170 ℃ and 3MPa on the dried sample, and keeping for 3 minutes to obtain the mixed prepreg.
④ Heating the mixed prepreg to 1000 ℃ in a carbonization furnace, preserving heat for 1 hour, taking out, and naturally cooling to obtain a carbonized product. Transferring the carbonized product into a graphitization furnace, heating to 2000 ℃ for 30 minutes, naturally cooling, and obtaining graphitized product, namely the carbon paper, wherein the surface density of the carbon paper is 70g/m 2, and the thickness of the carbon paper is 0.16mm.
Comparative example 3
The preparation method of the carbon paper for the proton exchange membrane fuel cell comprises the following specific steps:
① 72 parts by weight of polyacrylonitrile water-soluble 6 mm-length chopped carbon fibers are put into a carboxymethyl cellulose water solution with the mass concentration of 0.1wt.%, a high-speed stirrer is started, stirring is stopped after stirring is carried out for 10 minutes at the stirring speed of 2000 rpm, whether all fibers are uniformly dispersed is observed, and stirring is stopped to prepare the carbon fiber slurry. And (3) carrying out solid-liquid separation on the carbon fiber slurry through a 80-mesh filter screen, and squeezing and dehydrating to obtain the carbon fiber wet felt.
② And carrying out negative pressure dehumidification on the carbon fiber wet felt, spraying polyvinyl alcohol solution with the weight of 28 parts of glue, drying by an oven/drying cylinder, and coiling to obtain the carbon felt, wherein the surface density of the carbon felt is 50g/m 2.
③ The carbon felt is impregnated with a furfuryl alcohol resin ethanol solution with a volume concentration of 10vol.% by using an impregnation coater, and then dried by hot air at 100 ℃. The resin loading was 90% of the carbon felt areal density. And carrying out hot pressing solidification at 170 ℃ and 3MPa on the dried sample, and keeping for 3 minutes to obtain the carbon fiber prepreg.
④ Heating the carbon fiber prepreg to 1000 ℃ in a carbonization furnace, preserving heat for 1 hour, taking out, and naturally cooling to obtain a carbonized product. Transferring the carbonized product into a graphitization furnace, heating to 2000 ℃ for 30 minutes, naturally cooling, and obtaining graphitized product, namely carbon paper, wherein the surface density of the carbon paper is 80g/m 2, and the thickness of the carbon paper is 0.18mm.
Performance testing
1. The carbon papers of the above examples and comparative examples were each tested for air permeability according to test method GB/T22819, and the results are shown in Table 1, where the unit L/m 2. S represents the volume of gas passing per second in an area of one square meter.
2. The tensile strength of the carbon papers of the above respective examples and comparative examples was measured according to test method GB/T12914, and the results are shown in Table 1.
3. The carbon papers of the above respective examples and comparative examples were respectively tested for horizontal resistivity using a four-probe method, and the results are shown in table 1.
4. The deflection of the carbon papers of the above examples and comparative examples, respectively, was tested according to test method GB/T9341, and the results are shown in Table 1.
TABLE 1 air permeability, tensile strength, horizontal resistivity and deflection of the carbon papers of the respective examples and comparative examples
Performance of Air permeability Tensile strength Resistivity in horizontal direction Deflection of
Unit (B) L/m2·s kN/m mΩ·cm mm
Example 1 400 2.7 8 3.3
Example 2 380 3.1 7 3.6
Comparative example 1 330 2.6 6 2
Comparative example 2 340 2.4 6.8 2.1
Comparative example 3 320 2.3 6.3 2.2
From a comparison of example 1 and comparative example 1 in table 1, it can be seen that the air permeability of the carbon paper of example 1 is significantly higher than that of comparative example 1, and the deflection of the carbon paper of example 1 is also significantly higher than that of comparative example 1, and the tensile strength of the carbon paper of example 1 is also slightly higher than that of comparative example 1.
From a comparison of example 2 and comparative example 2 in table 1, it can be seen that the air permeability of the carbon paper of example 2 is significantly higher than that of comparative example 2, and that the tensile strength and flexibility of the carbon paper of example 2 are also significantly higher than that of comparative example 2.
From a comparison of example 2 and comparative example 3 in table 1, it can be seen that the carbon paper of example 2 has a significantly higher air permeability than comparative example 3, and that the tensile strength and deflection of example 2 are also significantly higher than comparative example 3.
In summary, the carbon paper provided by the embodiment of the invention has high air permeability and good permeability, and the speed block for conveying the gas and water in the gas diffusion layer on the fuel cell can effectively avoid flooding in the operation process of the fuel cell, and is particularly beneficial to high-current density operation; in addition, the strength and the bending resistance degree of the carbon paper are high.
For purposes of this disclosure, the terms "one embodiment," "some embodiments," "example," "a particular example," or "some examples," etc., mean that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the invention. In this specification, schematic representations of the above terms are not necessarily directed to the same embodiment or example. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples. Furthermore, the different embodiments or examples described in this specification and the features of the different embodiments or examples may be combined and combined by those skilled in the art without contradiction.
While embodiments of the present invention have been shown and described above, it will be understood that the above embodiments are illustrative and not to be construed as limiting the invention, and that variations, modifications, alternatives and variations may be made to the above embodiments by one of ordinary skill in the art within the scope of the invention.

Claims (10)

1. The preparation method of the carbon felt is characterized by comprising the following steps of:
S1, dispersing carbon fibers in a first dispersing agent solution, pulping to obtain carbon fiber slurry, and filtering the carbon fiber slurry to obtain a carbon fiber wet felt; dispersing reinforcing fibers in a second dispersing agent solution, pulping to obtain reinforcing fiber slurry, and filtering the reinforcing fiber slurry to obtain a reinforcing fiber wet felt;
s2, sequentially layering and stacking the carbon fiber wet felt, the reinforced fiber wet felt and the carbon fiber wet felt to obtain a composite wet felt, and carrying out negative pressure dehumidification, sizing and drying on the composite wet felt to obtain the carbon felt.
2. The method of producing a carbon felt according to claim 1, wherein the reinforcing fiber is at least one of a polyvinyl alcohol fiber, a polyester fiber, a polyethylene fiber and a polypropylene fiber.
3. The method of producing a carbon felt according to claim 1 or 2, wherein the reinforcing fiber has a length of 3mm to 20mm.
4. The method of producing a carbon felt according to claim 1, wherein the carbon fiber is a water-soluble carbon fiber; and/or the diameter of the carbon fiber is 5-7 μm; and/or the length of the carbon fiber is 3 mm-20 mm.
5. The method of producing a carbon felt according to claim 1, wherein the ratio of the areal density of the carbon fibers to the areal density of the reinforcing fibers in the carbon felt is (1 to 3): 1.
6. The method of claim 1, wherein the carbon felt has an areal density of 20g/m 2～80g/m2.
7. A carbon felt, characterized in that it is obtained by the production method according to any one of claims 1 to 6.
8. The preparation method of the carbon paper is characterized by comprising the following steps of:
(1) Impregnating the carbon felt in the resin solution according to claim 7, and then performing hot press molding to obtain a composite prepreg;
(2) And carrying out high-temperature treatment on the composite prepreg to obtain the carbon paper.
9. A carbon paper obtained by the method for producing a carbon paper according to claim 8.
10. A fuel cell membrane electrode, wherein the substrate of the gas diffusion layer of the fuel cell membrane electrode is the carbon paper of claim 9.
CN202410379867.6A 2024-03-29 2024-03-29 Carbon felt, carbon paper, preparation methods of carbon felt and carbon paper and fuel cell membrane electrode Pending CN118223326A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202410379867.6A CN118223326A (en) 2024-03-29 2024-03-29 Carbon felt, carbon paper, preparation methods of carbon felt and carbon paper and fuel cell membrane electrode

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202410379867.6A CN118223326A (en) 2024-03-29 2024-03-29 Carbon felt, carbon paper, preparation methods of carbon felt and carbon paper and fuel cell membrane electrode

Publications (1)

Publication Number Publication Date
CN118223326A true CN118223326A (en) 2024-06-21

Family

ID=91511676

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202410379867.6A Pending CN118223326A (en) 2024-03-29 2024-03-29 Carbon felt, carbon paper, preparation methods of carbon felt and carbon paper and fuel cell membrane electrode

Country Status (1)

Country Link
CN (1) CN118223326A (en)

Similar Documents

Publication Publication Date Title
CN113322713B (en) Preparation method of carbon paper with gradient pore structure
CN111576079B (en) Conductive carbon paper and preparation method thereof
US11876232B2 (en) Gas diffusion layer for proton exchange membrane fuel cell and preparation method thereof
JP2004511672A (en) Conductive non-woven fabric
CN115387148B (en) Gradient structure carbon fiber paper with high conductivity and high air permeability and preparation method thereof
CN100415987C (en) A porous carbon fiber paper for fuel cell with proton exchange membrane and preparation method thereof
CN111129555A (en) Carbon paper material for high-toughness high-conductivity proton exchange membrane battery
CN115262265A (en) Carbon paper, preparation method thereof, gas diffusion layer and fuel cell
CN117913308A (en) Fuel cell aperture multilayer gradient gas diffusion layer and preparation method thereof
CN113882186B (en) Carbon fiber paper and preparation method and application thereof
CN106684397B (en) A kind of modified carbon/carbon composite preparation method of graphene oxide
CN111146468B (en) Porous carbon film of fuel cell gas diffusion layer and preparation method thereof
CN118223326A (en) Carbon felt, carbon paper, preparation methods of carbon felt and carbon paper and fuel cell membrane electrode
CN114538947A (en) Preparation method for roll-to-roll continuous production of carbon material substrate of gas diffusion layer
JP6183065B2 (en) Porous carbon electrode and manufacturing method thereof
CA1320802C (en) Corrosion resistant fuel cell substrates
JP5590419B2 (en) Porous electrode substrate precursor sheet manufacturing method, porous electrode substrate manufacturing method, porous electrode substrate, membrane-electrode assembly, and polymer electrolyte fuel cell
JP7554175B2 (en) Anode gas diffusion layer substrate
CN115233489B (en) Carbon fiber paper and preparation method and application thereof
CN114457620B (en) Carbon paper for proton exchange membrane fuel cell and preparation method thereof
CN116289319B (en) Preparation and processing method of ordered array pore structure carbon paper
CN117497791A (en) Integrated gas diffusion layer for PEMFC membrane electrode and preparation method and application thereof
CN116960382A (en) Ordered sieve-tube-shaped porous fiber membrane, preparation method and application thereof
CN118073579A (en) Diffusion layer for fuel cell, preparation method of diffusion layer and fuel cell
CN115411275A (en) Fuel cell gas diffusion layer containing microporous layer and preparation method thereof

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