CN113322713A - Preparation method of carbon paper with gradient pore structure - Google Patents
Preparation method of carbon paper with gradient pore structure Download PDFInfo
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- CN113322713A CN113322713A CN202110468367.6A CN202110468367A CN113322713A CN 113322713 A CN113322713 A CN 113322713A CN 202110468367 A CN202110468367 A CN 202110468367A CN 113322713 A CN113322713 A CN 113322713A
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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
- D21H17/62—Rosin; Derivatives thereof
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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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- 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
- H01M4/861—Porous electrodes with a gradient in the porosity
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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 preparation method of carbon paper with a gradient pore structure, which comprises the following steps: after degumming and oxidation treatment are respectively carried out on carbon fibers with different length-diameter ratios, the carbon fibers are respectively dispersed in a dispersant solution to form carbon fiber slurry with different length-diameter ratios; sequentially carrying out gradient layering on the carbon fiber slurry according to the length-diameter ratio of the carbon fibers from high to low, and forming an inclined net to obtain a carbon felt precursor with a three-dimensional network structure; dipping the carbon felt precursor into a resin solution, taking out and drying to obtain a carbon felt; and (3) hot-pressing the carbon felt into raw paper of the carbon paper, and then carrying out carbonization and graphitization treatment to obtain the carbon paper with the gradient pore structure. According to the invention, the carbon fibers are sequentially layered in a gradient manner from high to low in length-diameter ratio according to the slurry, so that the prepared carbon paper has a gradient pore structure, communicated pores are formed in the carbon paper, the pore diameter is changed in a gradient manner along the normal direction on the plane of the carbon paper, and a pressure gradient is formed in a diffusion channel, so that the gas conveying efficiency can be improved, and the mass transfer and heat transfer performances of the carbon paper can be effectively improved.
Description
Technical Field
The invention belongs to the technical field of fuel cells, and particularly relates to a preparation method of carbon paper with a gradient pore structure.
Background
The porosity and pore structure of the carbon paper, which is an ideal substrate material of a gas diffusion layer of a fuel cell, directly influence the mass transfer and conduction performance of the diffusion layer, namely the transmission efficiency of product water and reaction gas, and influence the performance of the cell.
The conventional method for preparing carbon paper generally comprises the steps of degumming chopped carbon fiber bundles, removing a surface sizing agent, modifying carbon fibers by adopting a gas-phase or liquid-phase oxidation method, introducing oxygen-containing functional groups, improving hydrophilicity, adding pretreated carbon fibers into a dispersant solution, stirring and defibering until the fibers are completely dispersed to form stable paper making slurry for later use, making paper sheets from the carbon fiber slurry by utilizing a wet method, drying to obtain a precursor carbon felt, soaking the precursor carbon felt in a resin solution, solidifying resin among the carbon fibers by hot pressing, forming to obtain primary carbon paper, and finally carbonizing and graphitizing to obtain the finished carbon paper. However, the preparation method mainly has the following technical defects:
1. the pore structure cannot meet the requirement of high energy efficiency of the battery. The pore diameter and porosity of the carbon paper made of carbon fiber with single length-diameter ratio can not meet the mass transfer requirement of the diffusion layer. When the length of the fiber is too long, larger network pores can be formed on the carbon paper, so that the water drainage is too strong, the dehydration of the proton exchange membrane is easily caused, and the mass transfer efficiency is reduced; when short carbon fibers are used, the carbon paper network has smaller pores, insufficient porosity and poor permeability, resulting in water deposition and slow gas transport, resulting in flooding and mass transfer polarization. If the method of carbon fiber mixed papermaking with different length-diameter ratios is adopted, although the effective lap joints among the fibers can be increased, the uniformity and the density of the precursor carbon paper are improved, and the resistivity is favorably reduced; however, the pore size of the carbon paper prepared by the method is difficult to keep consistent, the porosity is low, the integral mass transfer capability is poor, and the flow velocity of gas passing through each position in the surface is different, so that the reaction gas on the surface of the catalyst is unevenly distributed, and mass transfer polarization occurs.
2. The density of the carbon paper is low, and the in-plane and longitudinal conductivity of the carbon paper is influenced. The carbon felt manufactured by the wet method has poor mechanical strength due to overlarge pores and insufficient fiber lap joint area, phenolic resin must be introduced for densification, and the fiber lap joint is firm by utilizing the filling effect of phenolic resin carbon among fibers to form a composite material of carbon fiber and resin. However, the carbon content of the phenolic resin is not more than 40% in general, the carbon content of the phenolic resin is only close to 50% even through modification, the phenolic resin is reduced into resin carbon in the high-temperature carbonization process, carbon oxides are released in a gas form, and the volume of the carbonized resin is greatly shrunk due to high oxygen content, so that huge area holes are caused, the strength and the conductivity are sharply reduced, and a further densification process for carbon paper is derived, the production line is prolonged, and the industrialization efficiency is not facilitated.
3. The graphitization temperature is high. After the primary carbon paper is carbonized, the oxygen-containing resin is degraded into resin carbon, and the conductivity is increased; in order to further improve the conductivity of the carbon paper, the resin carbon is required to be graphitized to convert the glassy resin carbon into graphite carbon. Since the graphitization temperature is over 2200 ℃, many heating devices often fail to meet the parameter requirements, resulting in heat treatment difficulties and increased cost.
Disclosure of Invention
The technical problem to be solved by the invention is to overcome the defects and shortcomings in the background art and provide a preparation method of carbon paper with a gradient pore structure.
In order to solve the technical problems, the technical scheme provided by the invention is as follows:
a preparation method of carbon paper with a gradient pore structure comprises the following steps:
(1) respectively degumming and oxidizing carbon fibers with different length-diameter ratios, and respectively dispersing the carbon fibers in a dispersing agent solution to form carbon fiber slurry;
(2) layering in a gradient manner in sequence according to the length-diameter ratio of carbon fibers in the slurry from high to low, and forming an inclined net to obtain a carbon felt precursor with a three-dimensional network structure;
(3) soaking the carbon felt precursor into a resin solution, taking out and drying to obtain a carbon felt;
(4) and (3) firstly hot-pressing the carbon felt into raw paper of the carbon paper, and then carrying out carbonization and graphitization treatment to obtain the carbon paper with the gradient pore structure.
In the above preparation method, preferably, in the step (1), the carbon fiber has a diameter of 7 μm and a length distribution of 3 to 20 mm.
Preferably, in the step (2), the carbon fiber slurry with the high aspect ratio to the carbon fiber slurry with the low aspect ratio is subjected to gradient layering in sequence, a carbon fiber base paper blank is formed by inclined net forming, the number of the gradient layering is not less than 4, and the carbon fiber slurry with the same aspect ratio can be subjected to layering for 2-3 times according to specific requirements.
According to the invention, through a carbon fiber multilayer layering technology with the length-diameter ratio from high to low, the carbon fibers with the low length-diameter ratio are densely stacked to form fine pores, the carbon fibers with the high length-diameter ratio are interwoven to form a carbon paper with a large pore diameter and a medium length-diameter ratio, the average pore diameter is in gradient distribution, communicated pores are formed inside the carbon paper, the pore diameter is in gradient change along the normal direction on the plane of the carbon paper, and a pressure gradient is formed in a diffusion channel. According to the Bernoulli (Venturi) principle, pressure difference is formed along the pressure reduction direction by utilizing the gradient change of the aperture of the flow channel, the gas flow velocity is gradually increased, the gas is compressed, and then the diffusion is accelerated, so that the gas can stably and quickly pass through the diffusion layer, is uniformly distributed on the surface of the catalyst layer, and the gas permeability is improved; and the gradient pore structure can also improve the water management capability of the diffusion layer, and water generated on the cathode catalyst layer flows into the carbon paper from the microporous layer and then smoothly flows out along the diffusion channel, so that the water logging phenomenon is prevented.
The invention utilizes the gradient change of the aperture of the flow channel to form pressure difference along the direction of pressure reduction, the flow rate of the gas is gradually increased, the timely supply of the reaction gas and the transportation of the excessive product water are ensured, and the membrane electrode keeps the best working state. The adopted multilayer laying technology ensures the regularity, the orderliness and the construction of a gradient pore structure of the pore structure, the pore diameter in the same layer is uniformly distributed, the change width is small, a two-dimensional ordered porous network is formed, gas can stably pass through each layer at a constant speed, the diffusion resistance is reduced, the turbulence is prevented, the circulation is accelerated along the gradient pores, and the surface air permeability can be improved by 20 percent compared with the carbon paper made by a mixed length-diameter ratio system.
In the above preparation method, preferably, in the step (3), the resin solution is 25 to 50 vol% of polyethyleneimine aqueous solution or 5 to 10 wt% of benzoxazine toluene solution.
The invention creatively selects Polyethyleneimine (PEI) or benzoxazine as a densifier for preparing precursor carbon paper. PEI does not contain oxygen atoms, only partial amino and alkyl are removed under high-temperature carbonization, the mass loss is less, better compactness can be kept after carbonization, the carbon residue rate is generally more than 60%, the overlap joint between fibers is enhanced by residual carbon, the carbon paper is favorably kept compact, the carbon paper is densified, and in addition, PEI is used as the inherent high chemical reaction activity of amines, so that PEI can be conveniently and effectively modified under the condition of keeping the original characteristics, the carbon paper is further densified, and the electrical conductivity is optimized. The benzoxazine is subjected to ring-opening polymerization reaction in the curing and forming process, does not release water molecules, has small shrinkage rate and high carbon content, and the prepared carbon paper has good compactness when being used for preparing the densifier of precursor carbon paper.
In the above preparation method, preferably, the resin solution further includes a boride, and the boride is selected from at least two of boron powder, boron nitride, boron carbide, borax, nickel boride and cobalt boride; the addition amount of the boride accounts for 0.1 to 1wt percent of the resin solution. Boron atoms enter a disordered graphite structure to form a replacement type solid solution in the high-temperature graphitization process, and the ordered graphitization conversion of carbon can be catalyzed on the premise of not disturbing a carbon microcrystal structure, so that the disordered carbon atoms are rearranged into graphite layer carbon atoms in a short distance, the structural conversion from glassy carbon to graphitic carbon is completed at a lower temperature, the fiber strength loss and the internal thermal stress are reduced, and the heat treatment cost is saved.
In the preparation method, preferably, in the step (4), the hot-pressing temperature in the hot-pressing process is 120-.
In the preparation method, preferably, in the step (4), the carbonization temperature is 900-1000 ℃, the carbonization time is 0.5-1.5h, and the resin is carbonized at high temperature into carbon particles which are filled among fibers and coated on the surfaces of the fibers, so that the spot welding of the fibers and the densification of carbon paper are realized; the graphitization temperature is 1800-2100 ℃, the graphitization time is 1-2h, the carbon particles are graphitized, and various physical properties such as conductivity of the carbon paper are improved.
In the preparation method, preferably, in the step (1), the degumming process includes: the carbon fiber is firstly subjected to alkali cleaning, then is placed in a muffle furnace for heat treatment at the temperature of 450-460 ℃ for 1-2 hours, the sizing agent on the surface of the fiber is fully removed, the carbon fiber is changed from a bundled aggregation state to a dispersed loose single state, and is immersed in absolute ethyl alcohol for ultrasonic treatment for 5-15min after being cooled along with the furnace, and the carbon fiber is washed by deionized water and dried.
In the preparation method, preferably, in the step (1), the oxidation treatment specifically comprises: soaking the degummed carbon fiber in concentrated nitric acid, and carrying out condensation reflux for 2-6h at the temperature of 80-100 ℃, or soaking the degummed carbon fiber in concentrated sulfuric acid for 8-24h at normal temperature, or carrying out heat treatment oxidation for 0.5-1.5h at the temperature of 430-.
In the above preparation method, preferably, in step (1), the dispersion liquid mainly comprises 0.02 to 0.1 wt% of polyethylene oxide, 0.001 to 0.02 wt% of polyvinyl alcohol, 0.0005 to 0.001 wt% of surfactant, 5 to 20 vol% of ethanol and the balance of deionized water, wherein the surfactant is one or more selected from sodium dodecyl benzene sulfonate, sodium stearate and trimethyl ammonium bromide.
The dispersion liquid is selected from polyoxyethylene dispersion liquid, on one hand, a layer of hydrophilic film is formed on the surface of the fiber based on polyoxyethylene, so that the hydrophilic film can be wetted by water molecules, the aggregation among the fibers is obviously reduced, and the addition of the macromolecular dispersant also greatly improves the viscosity of the solution and limits the free movement of the fibers, thereby hindering the sedimentation process and keeping the uniformity and stability of a dispersion system; the addition of the surfactant is also beneficial to regulating the wettability relation between the carbon fibers and water, the polar groups are combined with water molecules, and the non-polar ends are connected on the surfaces of the carbon fibers to play a role of an intermediate bridge, so that the dispersion stability of a system is improved; the addition of the polyvinyl alcohol endows the dried carbon paper precursor with certain strength, so that smooth screen release is facilitated.
Compared with the prior art, the invention has the advantages that:
(1) according to the invention, the carbon fibers are sequentially layered in a gradient manner from high to low in length-diameter ratio according to the slurry, so that the prepared carbon paper has a gradient pore structure, communicated pores are formed in the carbon paper, the pore diameter is changed in a gradient manner along the normal direction on the plane of the carbon paper, and a pressure gradient is formed in a diffusion channel, so that the gas conveying efficiency can be improved, and the mass transfer and heat transfer performances of the carbon paper can be effectively improved.
(2) The construction of the gradient pore structure in the carbon paper improves the water management capability of the diffusion layer, when the cell works, water generated on the cathode catalyst layer flows into the carbon paper from the microporous layer and then smoothly flows out along the diffusion channel, so that the flooding phenomenon is prevented, and the relative humidity of the membrane electrode is kept below 60%.
(3) Compared with the conventional phenolic resin and epoxy resin in the prior art, the high residual carbon content of the polyethyleneimine or benzoxazine can reduce the mass loss during carbonization, maintain the fiber lap joint strength and the carbon paper density, and improve the conductivity and the mechanical strength of the final carbon paper.
(4) The invention adopts the high carbon content resin to compound with the carbon paper, thus reducing the proportion of elements participating in gas generation during carbonization, having less component loss and having the volume shrinkage within a reasonable range; because the resin has high carbon residue rate, the residual carbon realizes the lap joint enhancement among fibers, is beneficial to keeping the carbon paper compact and realizing the carbon paper densification, and avoids the densification process of further post-treatment by adopting a chemical vapor deposition method.
(5) According to the invention, the composite auxiliary agent consisting of boron or boride is added into the resin slurry, the composite auxiliary agent shows a synergistic effect among components, and a remarkable catalytic effect can be generated on the graphitization of the carbon paper by virtue of a trace concentration.
(6) According to the invention, the composite auxiliary agent consisting of boron or boride is added into the resin slurry, so that the graphitization temperature can be reduced to a certain degree, the graphitization temperature can be reduced to 1800 ℃ on the premise of ensuring that the graphitization rate is not less than 85%, and the heat treatment cost is saved.
Drawings
FIG. 1 is a scanning electron micrograph of a carbon paper prepared in example 1 of the present invention.
FIG. 2 is a scanning electron micrograph of a carbon paper prepared in example 1 of the present invention.
Detailed Description
In order to facilitate an understanding of the invention, the invention will be described more fully and in detail below with reference to the accompanying drawings and preferred embodiments, but the scope of the invention is not limited to the specific embodiments below.
Unless otherwise defined, all terms of art used hereinafter have the same meaning as commonly understood by one of ordinary skill in the art. The terminology used herein is for the purpose of describing particular embodiments only and is not intended to limit the scope of the present invention.
Unless otherwise specifically stated, various raw materials, reagents, instruments, equipment and the like used in the present invention are commercially available or can be prepared by existing methods.
Example 1:
the invention relates to a preparation method of carbon paper with a gradient pore structure, which comprises the following steps:
(1) degumming: respectively carrying out alkali washing on polyacrylonitrile-based carbon fibers (with the diameter of 7 micrometers and the lengths of 5mm, 7mm, 9mm and 11 mm) with different length-diameter ratios, then carrying out heat treatment for 2 hours at 850 ℃ in a nitrogen atmosphere, cooling along with a furnace, then immersing the carbon fibers in absolute ethyl alcohol for ultrasonic treatment for 15min, finally washing with deionized water, and drying.
(2) And (3) oxidation: and (3) carrying out condensation reflux on the degummed carbon fiber for 4 hours at the temperature of 95 ℃ under the soaking of concentrated nitric acid, then washing the carbon fiber by deionized water until the pH value is neutral to obtain the modified carbon fiber, and drying the modified carbon fiber for later use.
(3) Dispersing: modified carbon fibers with different length-diameter ratios are respectively put into a prepared dispersant solution (containing polyoxyethylene with the molecular weight of 400 ten thousand, 0.05 wt%, polyvinyl alcohol, 0.015 wt%, 0.0005 wt% sodium dodecyl benzene sulfonate, 10 vol% ethanol and the balance of deionized water), and are stirred for 1 hour to prepare carbon fiber slurry with the concentration of 0.3 wt%.
(4) Papermaking: under the condition of vacuum water filtration, constant pressure difference of 0.08-0.09MPa is kept, multiple inclined net laying and forming are adopted, carbon fiber length-diameter ratio of pulp is sequentially laid according to the sequence from high to low (taking a 20-mesh filter screen and short carbon fiber with the diameter of 7 mu m as an example, carbon fiber pulp with the length of 11mm is firstly laid, carbon fiber pulp with the length of 9mm is then laid, carbon fiber pulp with the length of 7mm is then laid, carbon fiber pulp with the length of 5mm is finally laid), and then the carbon felt precursor with the three-dimensional network structure is obtained after vacuum drying for 20min at 80 ℃ and screen removal.
(5) Sizing: the carbon felt precursor is soaked in a resin solution (a solution consisting of 25 vol% of Polyethyleneimine (PEI) water solution, 0.1 wt% of boron powder and 0.3 wt% of cobalt boride), soaked for 1.5h at normal temperature, taken out and dried for 30min at 50 ℃.
(6) Hot pressing: and (4) cutting the carbon felt impregnated with the resin in the step (5) into a size of 15cm multiplied by 15cm, and placing the carbon felt into a flat vulcanizing machine for hot press molding to obtain the carbon paper base paper (the hot press temperature is 120 ℃, the pressure is 10MPa, and the hot press time is 5 min).
(7) Carbonizing: and (3) placing the carbon paper base paper in a tubular resistance furnace, heating to 1000 ℃ at a heating rate of 10 ℃/min under the protection of nitrogen atmosphere, and preserving heat for 90min to finish high-temperature carbonization of the carbon base paper.
(8) Graphitization: placing the carbonized carbon base paper in the step (7) into a graphitization sintering furnace, and under the protection of argon, raising the temperature at 10 ℃/minThe temperature is raised to 1800 ℃ at a speed rate, and the temperature is kept for 60min to complete the graphitization of the carbon paper, so that the finished carbon paper has an average graphitization degree of 89.3 percent and an average surface resistivity of 3.5m omega cm-2Average volume resistivity of 14.3 m.OMEGA.cm and average areal density of 86.2g/m2An average porosity of 73.7% and an average air permeability of 2000ml · mm/(cm)2Hr · mmAq), the thermal conductivity in the perpendicular-to-plane direction and the parallel-to-plane direction respectively reach 1.7W/m · K and 22W/m · K. During the operation of the assembled cell, the relative humidity of the membrane electrode is 54.8%. The resistivity is measured according to a carbon material resistivity measuring method specified in GB/T2425 ~ 2009GB, and the thermal conductivity is measured according to a carbon material thermal conductivity measuring method specified in GB/T8722 ~ 2019.
The scanning electron microscope images of the carbon paper prepared in this example are shown in fig. 1 and fig. 2, and it can be observed from the images that the fibers are arranged in a three-dimensional disordered net shape, and the lap joints between the fibers are bonded by carbonized resin to form a dense porous structure.
Example 2:
the invention relates to a preparation method of carbon paper with a gradient pore structure, which comprises the following steps:
(1) degumming: respectively carrying out alkali washing on polyacrylonitrile-based carbon fibers (with the diameter of 7 micrometers and the lengths of 3, 5, 7, 9 and 11 millimeters) with different length-diameter ratios, then carrying out heat treatment at 850 ℃ for 2 hours in a nitrogen atmosphere to remove a surface sizing agent, cooling along with a furnace, then immersing into absolute ethyl alcohol for ultrasonic treatment for 15 minutes, finally washing with deionized water, and drying.
(2) And (3) oxidation: and soaking the degummed carbon fiber in concentrated sulfuric acid at 60 ℃ for 12h, washing with deionized water until the pH value is neutral to obtain the modified carbon fiber, and drying for later use.
(3) Dispersing: the carbon fibers after pretreatment with different length-diameter ratios are respectively put into a prepared dispersant solution (containing polyoxyethylene with molecular weight of 400 ten thousand, 0.05 wt%, polyvinyl alcohol, 0.02 wt%, 0.0009 wt% of trimethyl ammonium bromide, 5 vol.% of ethanol and the balance of deionized water), and are stirred for 1 hour to prepare carbon fiber slurry with concentration of 0.3 wt%.
(4) Papermaking: under the condition of vacuum water filtration, constant pressure difference of 0.08-0.09MPa is kept, multiple inclined net laying and forming are adopted, carbon fiber diameter ratio of pulp is sequentially laid according to the sequence from top to bottom (taking a 20-mesh filter screen and short carbon fiber with the diameter of 7 mu m as an example, carbon fiber pulp with the length of 11mm is firstly laid for 1 time, carbon fiber pulp with the length of 9mm is then laid for 1 time, carbon fiber pulp with the length of 7mm is then laid for 1 time, carbon fiber pulp with the length of 5mm is then laid for 2 times, carbon fiber pulp with the length of 3mm is finally laid for 2 times), then vacuum drying is carried out at 80 ℃ for 20min, and then net removal is carried out, so that the carbon felt precursor with the three-dimensional network structure is obtained.
(5) Sizing: the carbon felt precursor is soaked in a resin solution (a solution consisting of 25 vol% of Polyethyleneimine (PEI) water solution, 0.5 wt% of boric acid and 0.1 wt% of boron nitride), soaked for 1.5h at normal temperature, taken out and dried for 30min at 50 ℃.
(6) Hot pressing: and (4) cutting the carbon felt impregnated with the resin in the step (5) into a size of 15cm multiplied by 15cm, and placing the carbon felt into a flat vulcanizing machine for hot press molding to obtain the carbon paper base paper (the hot press temperature is 120 ℃, the pressure is 8MPa, and the hot press time is 8 min).
(7) Carbonizing: and (3) placing the carbon paper base paper in a tubular resistance furnace, heating to 1100 ℃ at a heating rate of 10 ℃/min under the protection of nitrogen atmosphere, and preserving heat for 90min to finish high-temperature carbonization of the carbon paper.
(8) Graphitization: placing the carbonized carbon fiber paper in a graphitization sintering furnace, heating to 1900 ℃ at the heating rate of 10 ℃/min under the protection of argon, and preserving the heat for 60min to complete the graphitization of the carbon paper to obtain the finished carbon paper, wherein the average graphitization degree is 88.6%, and the average surface resistivity is 4.0m omega cm-2Average volume resistivity of 11.2 m.OMEGA.cm and average areal density of 88.9g/m2Average porosity 75.6%, average air permeability 1950 ml.mm/(cm)2·hr·mmAq)。
Example 3:
the invention relates to a preparation method of carbon paper with a gradient pore structure, which comprises the following steps:
(1) degumming: respectively carrying out alkali washing on polyacrylonitrile-based carbon fibers (with the diameter of 7 micrometers and the lengths of 3, 6, 9 and 12 millimeters) with different length-diameter ratios, then carrying out heat treatment at 850 ℃ for 2 hours in a nitrogen atmosphere to remove a surface sizing agent, cooling along with a furnace, then immersing into absolute ethyl alcohol for ultrasonic treatment for 15 minutes, finally washing with deionized water, and drying.
(2) And (3) oxidation: and (3) carrying out surface oxidation treatment on the degummed carbon fiber, carrying out air oxidation for 1h at 450 ℃ in a muffle furnace, rinsing with ethanol, washing with deionized water, and drying for later use.
(3) Dispersing: the pretreated carbon fibers with different length-diameter ratios are respectively put into a prepared dispersant solution (containing polyoxyethylene with the molecular weight of 600 ten thousand, 0.1 wt%, polyvinyl alcohol, 0.02 wt%, 0.0006 wt% of sodium stearate, 9 vol.% of ethanol and the balance of deionized water), and are stirred for 1 hour to prepare carbon fiber slurry with the concentration of 0.6 wt%.
(4) Papermaking: under the condition of vacuum water filtration, constant pressure difference of 0.08-0.09MPa is kept, multiple inclined net laying and forming are adopted, carbon fiber slurry with the length of 12mm is laid in sequence according to the sequence from the high length-diameter ratio to the low length-diameter ratio (taking a 20-mesh filter screen and short carbon fiber with the diameter of 7 mu m as an example, carbon fiber slurry with the length of 9mm is laid firstly, carbon fiber slurry with the length of 6mm is laid secondly, carbon fiber slurry with the length of 3mm is laid thirdly for 2 times), and then the carbon felt precursor with a three-dimensional network structure is obtained after vacuum drying at 80 ℃ for 20min and screen separation.
(5) Sizing: the carbon felt precursor is soaked in a resin solution (a solution consisting of 10 wt% of benzoxazine in toluene, 0.5 wt% of nickel boride and 0.1 wt% of boron nitride), soaked for 1.5h at normal temperature, taken out and dried for 30min at 50 ℃.
(6) Hot pressing: and (4) cutting the carbon felt impregnated with the resin in the step (5) into a size of 15cm multiplied by 15cm, and placing the carbon felt into a flat vulcanizing machine for hot press molding to obtain the carbon paper base paper (the hot press temperature is 180 ℃, the pressure is 8MPa, and the hot press time is 15 min).
(7) Carbonizing: and (3) placing the carbon paper in a tubular resistance furnace, heating to 1100 ℃ at a heating rate of 10 ℃/min under the protection of nitrogen atmosphere, and preserving heat for 60min to finish high-temperature carbonization of the carbon paper, thereby obtaining carbonized carbon fiber paper.
(8) Graphitization: placing the carbonized carbon fiber paper in a graphitization sintering furnace, heating to 1850 ℃ at the heating rate of 10 ℃/min under the protection of argon, and preserving the heat for 60min to complete the graphitization of the carbon paper, wherein the average graphitization degree of the obtained finished carbon paper is 92.4 percent, and the average surface resistivity is 3.5mΩ·cm-2The average volume resistivity was 10.9 m.OMEGA.cm. The other physical properties meet the specified technical requirements of the fuel cell.
Comparative example 1:
the preparation process of the carbon paper with the non-gradient pore structure in the comparative example is as follows:
(1) degumming: respectively carrying out alkali washing on polyacrylonitrile-based carbon fibers (with the diameter of 7 micrometers and the lengths of 5mm, 7mm, 9mm and 11 mm) with different length-diameter ratios, then carrying out heat treatment for 2 hours at 850 ℃ in a nitrogen atmosphere, cooling along with a furnace, then immersing the carbon fibers in absolute ethyl alcohol for ultrasonic treatment for 15min, finally washing with deionized water, and drying.
(2) And (3) oxidation: and (3) carrying out condensation reflux on the degummed carbon fiber for 4 hours at the temperature of 95 ℃ under the soaking of concentrated nitric acid, then washing the carbon fiber by deionized water until the pH value is neutral to obtain the modified carbon fiber, and drying the modified carbon fiber for later use.
(3) Dispersing: after mixing modified carbon fibers with different lengths (fibers with the diameter of 7 micrometers and the lengths of 5, 7, 9 and 11 millimeters in a mass ratio of 1:1:1:1), putting the mixture into a prepared dispersant solution (containing polyethylene oxide with the molecular weight of 400 ten thousand, 0.015 wt% of polyvinyl alcohol, 0.0005 wt% of sodium dodecyl benzene sulfonate, 10 vol.% of ethanol and the balance of deionized water), and stirring for 1 hour to prepare mixed carbon fiber slurry with the concentration of 0.3 wt%.
(4) Papermaking: and (3) under the condition of vacuum water filtration, keeping a constant pressure difference of 0.08-0.09MPa, carrying out inclined net forming on the mixed carbon fiber slurry prepared in the step (3), making the mixed carbon fiber slurry into a single layer, and then carrying out vacuum drying at 80 ℃ for 20min and then carrying out screen removal to obtain the carbon felt precursor with the three-dimensional network structure.
(5) Sizing: the carbon felt precursor is soaked in a resin solution (a solution consisting of 25 vol% of Polyethyleneimine (PEI) water solution, 0.1 wt% of boron powder and 0.3 wt% of cobalt boride), soaked for 1.5h at normal temperature, taken out and dried for 30min at 50 ℃.
(6) Hot pressing: cutting the carbon felt impregnated with the resin in the step (5) into the size of 15cm multiplied by 15cm, stacking four carbon felts, and placing the carbon felts in a flat vulcanizing machine for hot pressing and forming to obtain the carbon paper base paper (the hot pressing temperature is 120 ℃, the pressure is 10MPa, and the hot pressing time is 5 min).
(7) Carbonizing: and (3) placing the carbon paper base paper in a tubular resistance furnace, heating to 1000 ℃ at a heating rate of 10 ℃/min under the protection of nitrogen atmosphere, and preserving heat for 90min to finish high-temperature carbonization of the carbon paper base paper.
(8) Graphitization: placing carbonized carbon paper base paper in a graphitization sintering furnace, heating to 1900 ℃ at the heating rate of 10 ℃/min under the protection of argon, and preserving heat for 120min to complete graphitization of the carbon paper to obtain the finished carbon paper with the average graphitization degree of 84.2% and the surface density of 75g/m260% of porosity, 15m omega cm of surface resistance and 1600ml mm/(cm) of average air permeability2·hr·mmAq)。
In the comparative example, four carbon felts were laminated and molded in step (6) in order to keep the same number of layers as the carbon felts of the multi-layer in example 1 and to compare the areal density and air permeability while ensuring the same thickness. Compared with the test result of example 1, the comparative example shows that the carbon paper with the gradient pore structure has obviously better air permeability and slightly different electrical conductivity, so that the layering effect of the gradient length-diameter ratio can improve the mass transfer efficiency.
Comparative example 2:
the comparative example used a conventional densifier to prepare carbon paper with a gradient pore structure, and the preparation method was as follows:
(1) degumming: respectively carrying out alkali washing on polyacrylonitrile-based carbon fibers (with the diameter of 7 micrometers and the lengths of 3, 6, 9 and 12 millimeters) with different length-diameter ratios, then carrying out heat treatment at 850 ℃ for 2 hours in a nitrogen atmosphere to remove a surface sizing agent, cooling along with a furnace, then immersing into absolute ethyl alcohol for ultrasonic treatment for 15 minutes, finally washing with deionized water, and drying.
(2) And (3) oxidation: and (3) carrying out surface oxidation treatment on the degummed carbon fiber, carrying out air oxidation for 1h at 450 ℃ in a muffle furnace, rinsing with ethanol, washing with deionized water, and drying for later use.
(3) Dispersing: the pretreated carbon fibers with different length-diameter ratios are respectively put into a prepared dispersant solution (containing polyoxyethylene with the molecular weight of 600 ten thousand, 0.1 wt%, polyvinyl alcohol, 0.02 wt%, 0.0006 wt% of sodium stearate, 9 vol.% of ethanol and the balance of deionized water), and are stirred for 1 hour to prepare carbon fiber slurry with the concentration of 0.6 wt%.
(4) Papermaking: under the condition of vacuum water filtration, constant pressure difference of 0.08-0.09MPa is kept, multiple inclined net laying and forming are adopted, carbon fiber slurry with high length-diameter ratio to low length-diameter ratio is sequentially laid according to the sequence of the carbon fiber slurry with high length-diameter ratio to low length-diameter ratio (taking a 20-mesh filter screen and short carbon fiber with the diameter of 7 mu m as an example, carbon fiber slurry with the diameter of 12mm is laid firstly, then carbon fiber slurry with the diameter of 9mm is laid, then carbon fiber slurry with the diameter of 6mm is laid for 2 times, finally carbon fiber slurry with the diameter of 3mm is laid for 2 times), and then the carbon felt precursor with a three-dimensional network structure is obtained after vacuum drying at 80 ℃ for 20min and then is subjected to net removal.
(5) Sizing: the carbon felt precursor is soaked in a resin solution (a solution consisting of 10 wt% of phenolic resin ethanol solution, 0.5 wt% of nickel boride and 0.1 wt% of boron nitride), soaked for 1.5h at normal temperature, taken out and dried for 30min at 50 ℃.
(6) Hot pressing: and (4) cutting the carbon felt impregnated with the resin in the step (5) into 15cm multiplied by 15cm, and placing the carbon felt into a flat vulcanizing machine for hot press molding to obtain the carbon paper base paper (the hot press temperature is 180 ℃, the pressure is 8MPa, and the hot press time is 15 min).
(7) Carbonizing: and (3) placing the carbon paper in a tubular resistance furnace, heating to 1100 ℃ at a heating rate of 10 ℃/min under the protection of nitrogen atmosphere, and preserving heat for 60min to finish high-temperature carbonization of the carbon paper.
(8) Graphitization: placing the carbon fiber paper of the carbonized base paper in a graphitization sintering furnace, heating to 1850 ℃ at the heating rate of 10 ℃/min under the protection of argon, and preserving the heat for 60min to complete the graphitization of the carbon paper, wherein the average surface density of the carbon paper is 80.2g/m2The average porosity was 84.4%, and it was found that the effect of densification by the phenol resin was not good.
Comparative example 3:
the preparation method of the carbon paper with the gradient pore structure by using the single boride as the catalyst comprises the following steps:
(1) degumming: respectively carrying out alkali washing on polyacrylonitrile-based carbon fibers (with the diameter of 7 micrometers and the lengths of 3, 5, 7, 9 and 11 millimeters) with different length-diameter ratios, then carrying out heat treatment for 2 hours at 850 ℃ in a nitrogen atmosphere to remove a surface sizing agent, cooling along with a furnace, then immersing into absolute ethyl alcohol for ultrasonic treatment for 15 minutes, finally washing with deionized water, and drying;
(2) and (3) oxidation: soaking the degummed carbon fiber in concentrated sulfuric acid at 60 ℃ for 12h, washing with deionized water until the pH value is neutral to obtain modified carbon fiber, and drying for later use;
(3) dispersing: the carbon fibers after pretreatment with different length-diameter ratios are respectively put into a prepared dispersant solution (containing polyoxyethylene with molecular weight of 400 ten thousand, 0.05 wt%, polyvinyl alcohol, 0.02 wt%, 0.0009 wt% of trimethyl ammonium bromide, 5 vol.% of ethanol and the balance of deionized water), and are stirred for 1 hour to prepare carbon fiber slurry with concentration of 0.3 wt%.
(4) Papermaking: under the condition of vacuum water filtration, constant pressure difference of 0.08-0.09MPa is kept, multiple inclined net laying and forming are adopted, carbon fiber diameter ratio of pulp is sequentially laid according to the sequence from top to bottom (taking a 20-mesh filter screen and short carbon fiber with the diameter of 7 mu m as an example, firstly 11mm carbon fiber pulp is laid for 1 time, then 9mm carbon fiber pulp is laid for 1 time, then 7mm carbon fiber pulp is laid for 1 time, then 5mm carbon fiber pulp is laid for 2 times, and finally 3mm carbon fiber is laid for 2 times), and then the carbon felt precursor with a three-dimensional network structure is obtained after vacuum drying at 80 ℃ for 20min and then is subjected to net removal.
(5) Sizing: the carbon felt precursor is soaked in a resin solution (a solution consisting of 25 vol% of Polyethyleneimine (PEI) water solution and 0.75 wt% of boric acid), soaked for 1.5h at normal temperature, taken out and dried for 30min at 50 ℃.
(6) Hot pressing: and (4) cutting the carbon felt impregnated with the resin in the step (5) into a size of 15cm multiplied by 15cm, and placing the carbon felt into a flat vulcanizing machine for hot press molding to obtain the carbon paper base paper (the hot press temperature is 120 ℃, the pressure is 8MPa, and the hot press time is 8 min).
(7) Carbonizing: and (3) placing the carbon paper base paper in a tubular resistance furnace, heating to 1100 ℃ at a heating rate of 10 ℃/min under the protection of nitrogen atmosphere, and preserving heat for 90min to finish high-temperature carbonization of the carbon paper.
(8) Graphitization: and (3) placing the carbonized carbon paper base paper in a graphitization sintering furnace, heating to 1900 ℃ at the heating rate of 10 ℃/min under the protection of argon, and preserving the heat for 60min to complete the graphitization of the carbon paper, so as to obtain the finished carbon paper with the average graphitization degree of 83.2%.
In the comparative example, the boric acid and boron nitride composite boride in the step (5) in the example 2 is replaced by the single boric acid with the equivalent concentration, the total boron atom amount of the front and rear systems is kept unchanged, and the graphitization degree is greatly different under the same condition, which shows that the synergistic effect exists in the composite auxiliary agent consisting of more than two borides, the catalytic process of graphitization is accelerated, and the final graphitization degree is remarkably improved.
Claims (10)
1. A preparation method of carbon paper with a gradient pore structure is characterized by comprising the following steps:
(1) after degumming and oxidation treatment are respectively carried out on carbon fibers with different length-diameter ratios, the carbon fibers are respectively dispersed in a dispersant solution to form carbon fiber slurry with different length-diameter ratios;
(2) sequentially carrying out gradient layering on the carbon fiber slurry according to the length-diameter ratio of the carbon fibers from high to low, and forming an inclined net to obtain a carbon felt precursor with a three-dimensional network structure;
(3) soaking the carbon felt precursor into a resin solution, taking out and drying to obtain a carbon felt;
(4) and hot-pressing the carbon felt into raw paper of the carbon paper, and then carrying out carbonization and graphitization treatment to obtain the carbon paper with the gradient pore structure.
2. The method according to claim 1, wherein in the step (1), the carbon fiber has a diameter of 7 μm and a length distribution of 3 to 20 mm.
3. The method of claim 1, wherein in step (2), the gradient mat has no less than 4 layers.
4. The production method according to claim 1, wherein in the step (3), the resin solution is a 25 to 50 vol% polyethyleneimine aqueous solution or a 5 to 10 wt% benzoxazine toluene solution.
5. The method according to claim 4, wherein the resin solution further comprises a boride selected from at least two of boron powder, boron nitride, boron carbide, borax, nickel boride and cobalt boride; the addition amount of the boride accounts for 0.1 to 1wt percent of the resin solution.
6. The method according to any one of claims 1 to 5, wherein in the step (4), the hot pressing temperature of the hot pressing process is 120-200 ℃, the pressure is 8-12MPa, and the hot pressing time is 5-15 min.
7. The method according to any one of claims 1 to 5, wherein in the step (4), the temperature of the carbonization is 900-1000 ℃, and the time of the carbonization is 0.5-1.5 h; the graphitization temperature is 1800-2100 ℃, and the graphitization time is 1-2 h.
8. The preparation method according to any one of claims 1 to 5, wherein in the step (1), the degumming is carried out by the following specific processes: firstly, performing alkali washing on carbon fibers, then placing the carbon fibers in a muffle furnace for heat treatment at the temperature of 450-460 ℃ for 1-2h, cooling the carbon fibers along with the furnace, then immersing the carbon fibers in absolute ethyl alcohol, performing ultrasonic treatment for 5-15min, washing the carbon fibers with deionized water, and drying the carbon fibers.
9. The production method according to any one of claims 1 to 5, wherein in the step (1), the oxidation treatment is carried out by a specific process comprising: soaking the degummed carbon fiber in concentrated nitric acid, and carrying out condensation reflux for 2-6h at the temperature of 80-100 ℃, or soaking in concentrated sulfuric acid for 8-24h at normal temperature, or carrying out heat treatment oxidation for 0.5-1.5h at the temperature of 430-450 ℃ in air atmosphere.
10. The method according to any one of claims 1 to 5, wherein in step (1), the dispersion consists essentially of polyethylene oxide in an amount of 0.02 to 0.1 wt%, polyvinyl alcohol in an amount of 0.001 to 0.02 wt%, a surfactant in an amount of 0.0005 to 0.001 wt%, ethanol in an amount of 5 to 20 vol%, and the balance deionized water, wherein the surfactant is one or more selected from sodium dodecylbenzenesulfonate, sodium stearate, and trimethyl ammonium bromide.
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