CN112030604A - Low-cost high-vertical-conductivity carbon paper and manufacturing method thereof - Google Patents
Low-cost high-vertical-conductivity carbon paper and manufacturing method thereof Download PDFInfo
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- 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
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- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21F—PAPER-MAKING MACHINES; METHODS OF PRODUCING PAPER THEREON
- D21F11/00—Processes for making continuous lengths of paper, or of cardboard, or of wet web for fibre board production, on paper-making machines
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- 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
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- 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
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- 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
- D21H17/34—Synthetic macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- D21H17/37—Polymers of unsaturated acids or derivatives thereof, e.g. polyacrylates
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- 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
- D21H17/34—Synthetic macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- D21H17/41—Synthetic macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing ionic groups
- D21H17/44—Synthetic macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing ionic groups cationic
- D21H17/45—Nitrogen-containing groups
- D21H17/455—Nitrogen-containing groups comprising tertiary amine or being at least partially quaternised
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- 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
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- 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
- D21H17/63—Inorganic compounds
- D21H17/67—Water-insoluble compounds, e.g. fillers, pigments
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- 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
- D21H23/00—Processes or apparatus for adding material to the pulp or to the paper
- D21H23/02—Processes or apparatus for adding material to the pulp or to the paper characterised by the manner in which substances are added
- D21H23/22—Addition to the formed paper
- D21H23/32—Addition to the formed paper by contacting paper with an excess of material, e.g. from a reservoir or in a manner necessitating removal of applied excess material from the paper
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- 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
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- 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
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- 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
- D21H25/08—Rearranging applied substances, e.g. metering, smoothing; Removing excess material
- D21H25/12—Rearranging applied substances, e.g. metering, smoothing; Removing excess material with an essentially cylindrical body, e.g. roll or rod
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/8605—Porous electrodes
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- 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
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
Abstract
The invention discloses a method for manufacturing carbon paper with low cost and high vertical conductivity, which is characterized by comprising the following steps: step S1, preparing a carbon paper blank; and step S2, forming the carbon paper. The invention also discloses the carbon paper with low cost and high vertical conductivity, which is obtained by the method for manufacturing the carbon paper with low cost and high vertical conductivity. The manufacturing method of the carbon paper with low cost and high vertical conductivity, disclosed by the invention, is simple and easy to operate, low in cost, high in manufacturing efficiency and high in finished product yield; the low-temperature carbonization process after the carbon paper blank is impregnated with the resin is adopted, so that various negative problems caused by high-temperature graphitization are avoided; the low-temperature carbonization process effectively improves the mechanical properties of the carbon paper, such as tensile strength, bending strength, compressive strength and the like, and simultaneously avoids the contradiction problems of low conductivity, low thermal conductivity and poor corrosion resistance of the carbon paper caused by the low-temperature carbonization process.
Description
Technical Field
The invention belongs to the technical field of fuel cell materials, relates to a fuel cell component, and particularly relates to carbon paper with low cost and high vertical conductivity and a manufacturing method thereof.
Background
The carbon paper is an important material for preparing the electrode diffusion layer of the fuel cell, has a uniform porous structure, good strength and excellent conductivity, is a core component of the fuel cell, can play a role in supporting the catalyst layer and providing an electron channel, a gas channel and a water drainage channel for electrode reaction. Therefore, the development of fuel cell carbon paper with excellent performance is a hot topic of research in the industry.
The carbon paper is used as a porous medium for transmitting gas, conducting electrons and conducting heat, and plays an important role in stable operation of the fuel cell electrode. In the actual fuel cell structure, the carbon paper is partially exposed in the gas flow grooves of the bipolar plate and is partially tightly pressed by the ridges of the bipolar plate. In order to meet the requirements of high current density fuel cells for vehicles, the width of the ridges and grooves in the current bipolar plate design is generally narrow, and is generally less than 1 mm. Fuel cell operationIn the process, electron current generated at the groove part position of the electrode is conducted through the carbon paper of the ridge part, and meanwhile, the carbon paper of the ridge part also plays a role in conducting most of heat generated by the groove part electrode. Because the parallel electrical conductivity and the thermal conductivity of the carbon paper are far greater than the vertical electrical conductivity, the electron current and the heat of the groove part of the electrode are easier to be transferred to the ridge part through the carbon paper in the parallel direction, and because the vertical electrical resistivity of the carbon paper is relatively high and the thermal conductivity is relatively low, the resistance of the ridge part carbon paper in the process of transferring the electron and the heat to the ridge of the bipolar plate in the vertical direction is relatively high, and the transfer actually constitutes a key influence factor of the carbon paper for conducting the current and the heat, and the influence of the factor is particularly obvious when a high-current-density electrode is operated. How to reduce the vertical resistance and improve the vertical thermal conductivity of the carbon paper is that the fuel cell is under the condition of large current density (more than 1.5A/CM)2) A very important issue for applications.
The method commonly used in the prior art is to achieve the above purpose by reducing the thickness of the carbon paper under the condition of constant vertical thermal conductivity and vertical resistivity, and we are currently studying and trying thinner carbon paper. However, as the thickness of the carbon paper decreases, the tensile strength and bending strength of the carbon paper also decrease. Currently, suitable carbon papers are typically between 0.12 and 0.25mm thick. In order to deal with the heavy current density (1.5A/CM) for the vehicle2Above) the requirements of the fuel cell electrode on the electric conduction and heat transfer of the carbon paper, and especially the improvement of the electric conductivity and heat conductivity of the carbon paper, especially the vertical electric conductivity and heat conductivity, are particularly important.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide the carbon paper with low cost and high vertical conductivity and the manufacturing method thereof. And the low-temperature carbonization process after the carbon paper blank is impregnated with the resin is adopted, so that various negative problems caused by high-temperature graphitization are avoided. The low-temperature carbonization process effectively improves the mechanical properties of the carbon paper, such as tensile strength, bending strength, compressive strength and the like, and simultaneously avoids the contradiction problems of low conductivity, low thermal conductivity and poor corrosion resistance of the carbon paper caused by the low-temperature carbonization process. The method solves the problem that domestic carbon paper is difficult to be used in the electrode of the high-current-density fuel cell, and is a method suitable for high flux, short flow, low energy consumption and low cost.
In order to achieve the purpose, the invention adopts the technical scheme that: a manufacturing method of carbon paper with low cost and high vertical conductivity is characterized by comprising the following steps:
step S1, preparation of a carbon paper blank: chopping high-strength, medium-mode and high-conductivity carbon fibers T600 to a length of 3-25 mm; dispersing the obtained carbon fiber in water, and adding a cationic polymer PDDA and a binder; then stirring and pulping the mixture at a low speed to obtain carbon fiber-resin slurry; finally, the carbon fiber-resin slurry is subjected to inclined forming, filter screen dehydration, drying and curing, online rolling and other processes to obtain a carbon paper blank;
step S2, forming carbon paper: unreeling the carbon paper blank prepared in the step S1, performing online treatment on the carbon paper blank by using resin-containing slurry, continuously removing redundant slurry by double-roller extrusion, conveying the carbon paper blank soaked with the slurry into a continuous online drying tunnel furnace by using small traction tension, performing rolling forming by using a hot roller before complete resin curing, and performing medium-temperature carbonization (<1300 ℃) and reeling to obtain carbon paper.
Preferably, in the step S1, the mass ratio of the carbon fiber, the water, the cationic polymer PDDA and the binder is 1 (6-12): 0.03-0.08): 0.01.
Preferably, the binder in step S1 is at least one of PAM, PEO, and PVA.
Preferably, the resin-containing slurry in step S2 includes water, alcohol, impregnating resin, carbon fiber powder filler, micron-sized graphite powder or/and graphene powder filler.
Preferably, the impregnating resin is one or more of alcohol-soluble phenolic resin, water-soluble polyvinylpyrrolidone or high-residue carbon resin.
Preferably, the carbon fiber powder filler is carbon fiber with high conductivity and surface infiltration treatment, the diameter is 5-7 microns, the length is 20-200 microns,
preferably, the carbon fiber powder filler has a length of 30-80 microns and is obtained by ball milling in a ball mill.
Preferably, the particle size of the micron-sized graphite powder or/and graphene powder filler is 3000-18000 meshes.
Preferably, the micron-sized graphite powder or/and the graphene powder filler is 8000-12000 meshes.
Preferably, the mass ratio of the water, the alcohol, the impregnating resin, the carbon fiber powder filler, the micron-sized graphite powder or/and the graphene powder filler is (10-40): 90-60): 10-20): 10-80): 10-20.
Preferably, the alcohol is at least one of ethanol, isopropanol, ethylene glycol and glycerol.
Another object of the present invention is to provide a carbon paper with low cost and high vertical conductivity, which is manufactured by the method for manufacturing the carbon paper with low cost and high vertical conductivity.
Due to the application of the technical scheme, compared with the prior art, the invention has the following advantages: the invention provides the carbon paper with low cost and high vertical conductivity and the manufacturing method thereof, and the manufacturing method is simple and easy to operate, low in cost, high in manufacturing efficiency and high in finished product yield. And the low-temperature carbonization process after the carbon paper blank is impregnated with the resin is adopted, so that various negative problems caused by high-temperature graphitization are avoided. The low-temperature carbonization process effectively improves the mechanical properties of the carbon paper, such as tensile strength, bending strength, compressive strength and the like, and simultaneously avoids the contradiction problems of low conductivity, low thermal conductivity and poor corrosion resistance of the carbon paper caused by the low-temperature carbonization process. The method solves the problem that domestic carbon paper is difficult to be used in the electrode of the high-current-density fuel cell, and is a method suitable for high flux, short flow, low energy consumption and low cost.
Detailed Description
The following detailed description of preferred embodiments of the invention will be made.
A manufacturing method of carbon paper with low cost and high vertical conductivity is characterized by comprising the following steps:
step S1, preparation of a carbon paper blank: chopping high-strength, medium-mode and high-conductivity carbon fibers T600 to a length of 3-25 mm; dispersing the obtained carbon fiber in water, and adding a cationic polymer PDDA and a binder; then stirring and pulping the mixture at a low speed to obtain carbon fiber-resin slurry; finally, the carbon fiber-resin slurry is subjected to inclined forming, filter screen dehydration, drying and curing, online rolling and other processes to obtain a carbon paper blank;
step S2, forming carbon paper: unreeling the carbon paper blank prepared in the step S1, performing online treatment on the carbon paper blank by using a resin-containing prepreg, continuously removing redundant slurry by double-roller extrusion, conveying the carbon paper blank soaked with the slurry into a continuous online drying tunnel furnace by using small traction tension, performing rolling forming by using a hot roller before complete resin curing, and performing medium-temperature carbonization (<1300 ℃) and reeling to obtain the carbon paper.
Preferably, in the step S1, the mass ratio of the carbon fiber, the water, the cationic polymer PDDA and the binder is 1 (6-12): 0.03-0.08): 0.01.
Preferably, the binder in step S1 is at least one of PAM, PEO, and PVA.
Preferably, the resin-containing slurry in step S2 includes water, alcohol, impregnating resin, carbon fiber powder filler, micron-sized graphite powder or/and graphene powder filler.
Preferably, the impregnating resin is one or more of alcohol-soluble phenolic resin, water-soluble polyvinylpyrrolidone or high-residue carbon resin.
Preferably, the carbon fiber powder filler is carbon fiber with high conductivity and surface infiltration treatment, the diameter is 5-7 microns, the length is 20-200 microns,
preferably, the carbon fiber powder filler has a length of 30-80 microns and is obtained by ball milling in a ball mill.
Preferably, the particle size of the micron-sized graphite powder or/and graphene powder filler is 3000-18000 meshes.
Preferably, the micron-sized graphite powder or/and the graphene powder filler is 8000-12000 meshes.
Preferably, the mass ratio of the water, the alcohol, the impregnating resin, the carbon fiber powder filler, the micron-sized graphite powder or/and the graphene powder filler is (10-40): 90-60): 10-20): 10-80): 10-20.
Preferably, the alcohol is at least one of ethanol, isopropanol, ethylene glycol and glycerol.
Another object of the present invention is to provide a carbon paper with low cost and high vertical conductivity, which is manufactured by the method for manufacturing the carbon paper with low cost and high vertical conductivity.
Due to the application of the technical scheme, compared with the prior art, the invention has the following advantages: the invention provides the carbon paper with low cost and high vertical conductivity and the manufacturing method thereof, and the manufacturing method is simple and easy to operate, low in cost, high in manufacturing efficiency and high in finished product yield. And the low-temperature carbonization process after the carbon paper blank is impregnated with the resin is adopted, so that various negative problems caused by high-temperature graphitization are avoided. The low-temperature carbonization process effectively improves the mechanical properties of the carbon paper, such as tensile strength, bending strength, compressive strength and the like, and simultaneously avoids the contradiction problems of low conductivity, low thermal conductivity and poor corrosion resistance of the carbon paper caused by the low-temperature carbonization process. The method solves the problem that domestic carbon paper is difficult to be used in the electrode of the high-current-density fuel cell, and is a method suitable for high flux, short flow, low energy consumption and low cost.
The invention will be further described with reference to specific examples, but the scope of protection of the invention is not limited thereto:
example 1
Embodiment 1 provides a method for manufacturing a carbon paper with low cost and high vertical conductivity, which is characterized by comprising the following steps:
step S1, preparation of a carbon paper blank: chopping high-strength middle-mode and high-conductivity carbon fibers T600 with the length of 3 mm; dispersing the obtained carbon fiber in water, and adding a cationic polymer PDDA and a binder; then stirring and pulping the mixture at a low speed to obtain carbon fiber-resin slurry; finally, the carbon fiber-resin slurry is subjected to inclined forming, filter screen dehydration, drying and curing, online rolling and other processes to obtain a carbon paper blank;
step S2, forming carbon paper: unreeling the carbon paper blank prepared in the step S1, performing online treatment on the carbon paper blank by using resin-containing slurry, continuously extruding and removing redundant slurry by using double rollers, conveying the carbon paper blank soaked with the slurry into a continuous online drying tunnel furnace by using small traction tension, performing rolling forming by using a hot roller before complete resin curing, and performing medium-temperature carbonization (1200 ℃) and reeling on the carbon paper blank subjected to sizing forming to obtain the carbon paper.
In the step S1, the mass ratio of the carbon fibers, the water, the cationic polymer PDDA and the binder is 1:6:0.03: 0.01; the binder in step S1 is PAM.
In the step S2, the resin-containing slurry includes water, alcohol, impregnating resin, carbon fiber powder filler, micron-sized graphite powder or/and graphene powder filler; the impregnating resin is alcohol-soluble phenolic resin; the carbon fiber powder filler is carbon fiber subjected to high-conductivity surface infiltration treatment, the diameter is 5 micrometers, and the length is 20 micrometers; the carbon fiber powder filler is 30 microns in length and is obtained by adopting a ball milling mode; the particle size of the micron-sized graphite powder or/and graphene powder filler is 3000 meshes of graphite powder.
The mass ratio of the water to the alcohol to the impregnating resin to the carbon fiber powder filler to the micron-sized graphite powder or/and the graphene powder filler is 10:90:10:10: 10; the alcohol is ethanol.
The carbon paper with low cost and high vertical conductivity is prepared according to the preparation method of the carbon paper with low cost and high vertical conductivity.
Example 2
Embodiment 2 provides a method for manufacturing a carbon paper with low cost and high vertical conductivity, which is substantially the same as embodiment 1, except that the mass ratio of the carbon fibers, the water, the cationic polymer PDDA and the binder in the step S1 is 1:8:0.04: 0.01; the mass ratio of the water to the alcohol to the impregnating resin to the carbon fiber powder filler to the micron-sized graphite powder or/and the graphene powder filler is 20:80:13:25: 13.
Example 3
Embodiment 3 provides a method for manufacturing a carbon paper with low cost and high vertical conductivity, which is substantially the same as embodiment 1, except that the mass ratio of the carbon fibers, the water, the cationic polymer PDDA and the binder in the step S1 is 1:9:0.05: 0.01; the mass ratio of the water to the alcohol to the impregnating resin to the carbon fiber powder filler to the micron-sized graphite powder or/and the graphene powder filler is 25:75:15:60: 15.
Example 4
Embodiment 4 provides a method for manufacturing a carbon paper with low cost and high vertical conductivity, which is substantially the same as embodiment 1, except that the mass ratio of the carbon fibers, the water, the cationic polymer PDDA and the binder in the step S1 is 1:11:0.07: 0.01; the mass ratio of the water, the alcohol, the impregnating resin, the carbon fiber powder filler and the micron-sized graphite powder or/and the graphene powder filler is 35:65) to 18:75: 18.
Example 5
Embodiment 5 provides a method for manufacturing a carbon paper with low cost and high vertical conductivity, which is substantially the same as embodiment 1, except that the mass ratio of the carbon fibers, the water, the cationic polymer PDDA and the binder in the step S1 is 1:12:0.08: 0.01; the mass ratio of the water, the alcohol, the impregnating resin, the carbon fiber powder filler and the micron-sized graphite powder or/and the graphene powder filler is 40:60:20:80: 20.
Comparative example 1
Comparative example 1 provides a method of manufacturing a low-cost high vertical conductivity carbon paper, substantially the same as in example 1, except that the cationic polymer PDDA was not added.
Comparative example 2
Comparative example 2 provides a method of manufacturing a carbon paper having a high vertical conductivity at a low cost, substantially the same as in example 1, except that no carbon fiber powder filler is added.
Comparative example 3
Comparative example 3 provides a method of making a low cost high vertical conductivity carbon paper, substantially the same as example 1, except that no micron-sized graphite powder or/and graphene powder filler is added.
To further illustrate the technical effects of the examples of the present invention, the carbon papers having low cost and high vertical conductivity prepared in examples 1 to 5 of the present invention and comparative examples 1 to 3 were tested, and the test results are shown in table 1.
TABLE 1
| Detecting items | Void ratio (%) | Resistivity (omega. cm) | Tensile strength (N/cm) |
| Example 1 | 73 | 0.028 | 67 |
| Example 2 | 76 | 0.030 | 69 |
| Example 3 | 77 | 0.032 | 70 |
| Example 4 | 79 | 0.036 | 72 |
| Example 5 | 80 | 0.040 | 74 |
| Comparative example 1 | 63 | 0.128 | 58 |
| Comparative example 2 | 65 | 0.110 | 60 |
| Comparative example 3 | 61 | 0.102 | 62 |
As can be seen from the above table, the carbon paper with low cost and high vertical conductivity disclosed by the embodiment of the invention has higher porosity and tensile strength and better conductivity.
The above-mentioned embodiments are merely illustrative of the technical concept and features of the present invention, and the purpose thereof is to enable those skilled in the art to understand the content of the present invention and implement the invention, and not to limit the scope of the present invention, and all equivalent changes or modifications made according to the spirit of the present invention should be covered by the scope of the present invention.
Claims (10)
1. A manufacturing method of carbon paper with low cost and high vertical conductivity is characterized by comprising the following steps:
step S1, preparation of a carbon paper blank: chopping high-strength, medium-mode and high-conductivity carbon fibers T600 to a length of 3-25 mm; dispersing the obtained carbon fiber in water, and adding a cationic polymer PDDA and a binder; then stirring and pulping the mixture at a low speed to obtain carbon fiber-resin slurry; finally, the carbon fiber-resin slurry is subjected to inclined forming, filter screen dehydration, drying and curing, online rolling and other processes to obtain a carbon paper blank;
step S2, forming carbon paper: unreeling the carbon paper blank prepared in the step S1, performing online treatment on the carbon paper blank by using resin-containing slurry, continuously removing redundant slurry by double-roller extrusion, conveying the carbon paper blank soaked with the slurry into a continuous online drying tunnel furnace by using small traction tension, performing rolling forming by using a hot roller before complete resin curing, and performing medium-temperature carbonization (<1300 ℃) and reeling to obtain carbon paper.
2. The method for making the carbon paper with low cost and high vertical conductivity as claimed in claim 1, wherein the mass ratio of the carbon fibers, the water, the cationic polymer PDDA and the binder in step S1 is 1 (6-12): 0.03-0.08): 0.01.
3. The method for manufacturing carbon paper with low cost and high vertical conductivity according to claim 1, wherein the binder in step S1 is at least one of PAM, PEO, and PVA.
4. The method of claim 1, wherein the resin-containing slurry in step S2 comprises water, alcohol, impregnating resin, carbon fiber powder filler, micron-sized graphite powder or/and graphene powder filler.
5. The method for manufacturing the carbon paper with low cost and high vertical conductivity according to claim 4, wherein the impregnating resin is one or more of alcohol-soluble phenolic resin, water-soluble polyvinylpyrrolidone or high-residual carbon resin.
6. The method for making the carbon paper with low cost and high vertical conductivity according to claim 4, wherein the carbon fiber powder filler is carbon fiber with high conductivity and surface infiltration treatment, the diameter is 5-7 microns, and the length is 20-200 microns.
7. The method as claimed in claim 4, wherein the micron-sized graphite powder or/and graphene powder filler has a particle size of 3000-18000 meshes.
8. The method for making the carbon paper with low cost and high vertical conductivity as claimed in claim 4, wherein the mass ratio of the water, the alcohol, the impregnating resin, the carbon fiber powder filler, the micron-sized graphite powder or/and the graphene powder filler is (10-40): (90-60): (10-20): (10-80): (10-20).
9. The method for making the carbon paper with low cost and high vertical conductivity according to claim 4, wherein the alcohol is at least one of ethanol, isopropanol, ethylene glycol and glycerol.
10. A low-cost high vertical conductivity carbon paper produced by the method for producing a low-cost high vertical conductivity carbon paper according to any one of claims 1 to 9.
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