CN113882186B - Carbon fiber paper and preparation method and application thereof - Google Patents
Carbon fiber paper and preparation method and application thereof Download PDFInfo
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- CN113882186B CN113882186B CN202010627370.3A CN202010627370A CN113882186B CN 113882186 B CN113882186 B CN 113882186B CN 202010627370 A CN202010627370 A CN 202010627370A CN 113882186 B CN113882186 B CN 113882186B
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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
- 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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- 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 relates to the technical field of membrane electrodeThe carbon fiber paper has carbon content not less than 95 wt%, porosity of 80-90%, and air permeability of 5 x 10 4 ‑8×10 4 mL·mm/(cm 2 h.mmHg). The method for preparing the carbon fiber paper comprises the following steps: (1) The method comprises the following steps of (1) carrying out wet papermaking on a mixture containing chopped carbon fibers, chopped porous carbon fibers, a dispersing agent, an adhesive and a solvent to obtain a carbon fiber paper precursor; (2) And impregnating the carbon fiber paper precursor by adopting a phenolic resin solution, and then curing, carbonizing and graphitizing. The carbon fiber paper has high porosity, air permeability and conductivity, and high tensile strength, and can effectively improve the electrochemical performance of a membrane electrode when being used in the membrane electrode.
Description
Technical Field
The invention relates to the technical field of membrane electrodes, in particular to carbon fiber paper and a preparation method and application thereof.
Background
Proton Exchange Membrane Fuel Cells (PEMFCs) have the characteristics of high power density, high energy conversion rate, low-temperature start, no pollution, light volume, and the like, and can be used as uninterruptible power supplies and decentralized power stations for power systems of vehicles, mobile small power supply systems and electronic devices, and emergency power supplies for military, medical, entertainment places, and the like.
The key component constituting the PEMFC is a Membrane Electrode Assembly (MEA), which includes: proton exchange membrane, catalyst layer, gas diffusion layer. The gas diffusion layer serves to support the catalyst layer, stabilize the electrode structure, and also provide gas channels, electron channels, and water drainage channels for the electrode reaction. An ideal gas diffusion layer should have good water, gas mass transfer capability, low electrical resistance and good mechanical properties. High performance carbon fiber paper has been widely used as a substrate layer of a PEMFC gas diffusion layer.
The conventional method for preparing carbon fiber paper is to disperse and bond chopped carbon fibers to prepare porous carbon fiber base paper, and then form interconnected carbon matrixes on the surfaces of the fibers through the processes of impregnation, carbonization and graphitization to obtain the final carbon fiber paper. The problems in the paper making process of the carbon fiber need to be solved, and the problems mainly focus on two aspects of dispersion of the chopped carbon fiber and paper making strength. Shorter chopped fibers are advantageous for uniform dispersion but have poor paper strength, while longer fibers are the opposite. In addition, the existing carbon fiber paper adopts a wet papermaking process mostly, the raw material basically adopts short carbon fibers, only macropores with relatively single pore diameter can be formed, the pore size is single, the uniformity of paper sheets is poor, and the effective mass transfer of water and gas and the coating of a subsequent microporous layer are not facilitated.
Disclosure of Invention
The invention aims to solve the problems of low porosity, poor air permeability, poor electrical conductivity and poor tensile strength of carbon fiber paper in the prior art, and provides carbon fiber paper, a preparation method and application thereof.
In order to achieve the above object, according to one aspect of the present invention, there is provided a carbon fiber paper having a carbon content of 95% by weight or more, a porosity of 80 to 90%, and an air permeability of 5 × 10 4 -8×10 4 mL·mm/(cm 2 ·h·mmHg)。
In a second aspect, the present invention provides a method of making a carbon fiber paper, the method comprising the steps of:
(1) The method comprises the following steps of (1) carrying out wet papermaking on a mixture containing chopped carbon fibers, chopped porous carbon fibers, a dispersing agent, an adhesive and a solvent to obtain a carbon fiber paper precursor;
(2) And impregnating the carbon fiber paper precursor by adopting a phenolic resin solution, and then curing, carbonizing and graphitizing.
Preferably, the chopped carbon fibers are contained in an amount of 60 to 97% by weight, more preferably 75 to 85% by weight, based on the total amount of the chopped carbon fibers and the chopped porous carbon fibers.
In a third aspect of the invention, there is provided a carbon fibre paper produced by the method of the second aspect.
The fourth aspect of the invention provides a use of the carbon fiber paper of the first or third aspect in a membrane electrode.
The carbon fiber paper prepared by the technical scheme of the invention has higher porosity, air permeability and tensile strength, wherein the air permeability can reach 5.5 multiplied by 10 4 mL·mm/(cm 2 H mmHg) or more, the tensile strength can reach 41MPa, the surface resistance is low (can reach below 7m omega cm), the conductivity is good, and the membrane electrode can be well applied to membrane electrodes.
Detailed Description
The endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and these ranges or values should be understood to encompass values close to these ranges or values. For ranges of values, between the endpoints of each of the ranges and the individual points, and between the individual points may be combined with each other to give one or more new ranges of values, and these ranges of values should be considered as specifically disclosed herein.
In the present invention, the pore diameter refers to a pore diameter without specific description.
In a first aspect, the present invention provides a carbon fiber paper having a carbon content of not less than 95% by weight, a porosity of 80% to 90%, and an air permeability of 5 × 10 4 -8×10 4 mL·mm/(cm 2 ·h·mmHg)。
According to the present invention, in order to further improve the conductivity of the carbon fiber paper, it is preferable that the carbon content of the carbon fiber paper is 98 to 99.9 wt%.
In the invention, the carbon content of the carbon fiber paper is measured by an element analyzer.
According to the present invention, in order to further improve the mass transfer capacity of the carbon fiber paper, preferably, the porosity of the carbon fiber paper is 82 to 90%. The porosity of prior art carbon fiber papers is generally less than 80%.
According to the present invention, in order to further improve the mass transfer capacity of the carbon fiber paper, it is preferable that the carbon fiber paper has an air permeability of 5.5 × 10 4 -7.5×10 4 mL·mm/(cm 2 h.mmHg). The air permeability of the prior art carbon fiber paper is generally less than 5 x 10 4 mL·mm/(cm 2 ·h·mmHg)。
The inventor of the invention discovers through research that in a solvent, chopped carbon fibers and chopped porous carbon fibers are matched, a dispersing agent and an adhesive are added, a carbon fiber paper precursor is obtained through wet papermaking, the carbon fiber paper precursor is impregnated with phenolic resin, and then curing, carbonization and graphitization are carried out, so that the prepared carbon fiber paper has high porosity, good air permeability, good electrical conductivity and good tensile strength. Particularly, carbon fiber paper prepared by mixing chopped carbon fibers, chopped porous carbon fibers, a dispersing agent, a binder and a solvent in a specific ratio has more excellent performance.
In a second aspect, the present invention provides a method of making a carbon fiber paper, the method comprising the steps of:
(1) The method comprises the following steps of (1) carrying out wet papermaking on a mixture containing chopped carbon fibers, chopped porous carbon fibers, a dispersing agent, an adhesive and a solvent to obtain a carbon fiber paper precursor;
(2) And impregnating the carbon fiber paper precursor by adopting a phenolic resin solution, and then curing, carbonizing and graphitizing.
According to the present invention, it is preferable that the chopped carbon fibers are contained in an amount of 60 to 97% by weight, preferably 75 to 85% by weight, based on the total amount of the chopped carbon fibers and the chopped porous carbon fibers. With the preferred range of the content of the chopped carbon fibers, the porosity and air permeability of the carbon fiber paper can be further improved, and the carbon fiber paper has high tensile strength.
According to the invention, the solids content of the mixture is preferably from 0.005 to 0.5% by weight, preferably from 0.01 to 0.1% by weight. The preferred solid content is more favorable for forming the carbon fiber paper precursor by the mixture through wet papermaking.
According to the invention, the content of dispersant in the mixture is preferably 0.01 to 1% by weight, preferably 0.1 to 0.5% by weight.
According to the invention, the binder is preferably present in the mixture in an amount of 0.01 to 1% by weight, preferably 0.01 to 0.1% by weight. The binder with the optimal content can be more beneficial to forming the carbon fiber paper precursor, so that the tensile strength of the carbon fiber paper is further improved.
According to the present invention, the kind of the solvent is not particularly limited, and preferably, the solvent is water.
According to the present invention, in the step (1), as long as the mixture is obtained, there is no particular limitation on the specific mixing manner, and one or two of the materials may be mixed with the other remaining materials, and preferably, the mixture is prepared by a method comprising: the preparation method comprises the steps of mixing chopped carbon fibers and chopped porous carbon fibers in a solvent to obtain mixed carbon fibers, and then mixing the mixed carbon fibers with a dispersing agent and a binder to obtain the mixture.
According to the invention, the wet papermaking is a papermaking method commonly used in the field, and the mixture is mainly subjected to defibering and dispersing and papermaking drying in sequence, preferably, the time for defibering and dispersing is 0.05-0.5h, and more preferably 0.1-0.2h. The specific operation of the dispersion breaking is not particularly limited in the present invention, and the dispersion breaking can be carried out according to the conventional operation in the art. For example by defibration or high speed stirring. It will be appreciated that the defibering dispersion is carried out under stirring, preferably at a speed of 1000-20000rpm, more preferably 5000-20000rpm.
The specific operation of the paper drying in the present invention is not particularly limited, and the paper drying can be carried out according to the conventional operation in the art. For example, sheet making is performed on a paper sampler, followed by vacuum drying.
Preferably, the drying temperature of the papermaking paper is 60-120 ℃, and more preferably 80-100 ℃; the time is 0.5 to 3 hours, more preferably 1 to 1.5 hours.
According to the present invention, the chopped carbon fibers refer to carbon fibers obtained without pore-forming during the production process, and have a low porosity, generally a porosity of less than 20%, preferably 10 to 18%.
According to the present invention, preferably, the chopped carbon fibers have a tensile modulus of 200 to 400Gpa, more preferably 230 to 350Gpa.
According to the present invention, it is preferable that the chopped carbon fibers have a tensile strength of 3.5 to 6.5GPa.
According to the present invention, it is preferable that the electrical resistivity of the chopped carbon fibers is 0.001 to 0.01 Ω · cm, preferably 0.001 to 0.002 Ω · cm.
According to the present invention, preferably, the length of the chopped carbon fibers is 3 to 18mm, preferably 5 to 15mm. By adopting the optimal length, the prepared carbon fiber paper has higher tensile strength and uniformity, and the higher uniformity is realized by better air permeability and higher porosity of the carbon fiber paper.
According to the present invention, preferably, the chopped carbon fibers are polyacrylonitrile-based carbon fibers and/or pitch-based carbon fibers.
According to the present invention, the chopped porous carbon fiber refers to a carbon fiber obtained after pore formation in a production process, and preferably, the porosity of the chopped porous carbon fiber is 30 to 80%, and more preferably, 60 to 80%. The adoption of the preferred embodiment is more beneficial to further improving the porosity and air permeability of the carbon fiber paper.
According to the present invention, it is preferred that the pore size of the chopped porous carbon fibers is 0.01 to 5 μm, preferably 0.05 to 1 μm.
According to the present invention, preferably, the chopped porous carbon fibers have a specific surface area of 50 to 200m 2 A/g, preferably from 100 to 180m 2 (ii) in terms of/g. The air permeability of the carbon fiber paper can be further improved by adopting the preferable specific surface area.
According to the present invention, preferably, the chopped porous carbon fibers have a length of 1 to 5mm, preferably 2 to 3mm. By adopting the optimal length, the carbon fiber paper has better uniformity, and further the porosity, air permeability and tensile strength of the carbon fiber paper are further improved.
According to the present invention, preferably, the diameter of the chopped porous carbon fibers is 0.2 to 30 μm, preferably 0.5 to 10 μm, more preferably 0.5 to 5 μm. The preferred diameter can enable the prepared carbon fiber paper to have high tensile strength and porosity.
According to the present invention, it is preferable that the electrical resistivity of the chopped porous carbon fibers is 0.001 to 0.01 Ω · cm, preferably 0.001 to 0.002 Ω · cm.
According to the invention, the selection range of the types of the chopped porous carbon fibers is wide, and preferably, the chopped porous carbon fibers are polyacrylonitrile-based carbon fibers and/or pitch-based carbon fibers.
According to the present invention, the kind of the dispersant is selected from a wide range, and in order to further improve the homogeneity of the mixture, the dispersant is preferably selected from at least one of polyacrylamide, polyethylene oxide, and a cellulose derivative.
More preferably, the derivative of cellulose is selected from at least one of methylcellulose, sodium carboxymethylcellulose, and hydroxyethylcellulose.
According to the present invention, the kind of the binder is selected from a wide range as long as it can fix and mold the carbon fiber paper precursor, and preferably, the binder is selected from at least one of polyvinyl alcohol, phenol resin, and polytetrafluoroethylene.
According to the present invention, the concentration of the phenolic resin solution may be selected within a wide range as long as it facilitates the entry of the phenolic resin solution into the voids between the carbon fibers, preferably the concentration of the phenolic resin solution is 2 to 10 parts by weight, more preferably 5 to 10 parts by weight.
According to the present invention, in the step (2), the amount of the phenolic resin is selected to be in a wide range, and preferably, the amount of the phenolic resin to be attached is 50 to 200 parts by weight, preferably 60 to 120 parts by weight, based on 100 parts by weight of the carbon fiber paper precursor, based on the fact that the phenolic resin is completely attached to the pores of the carbon fiber paper precursor.
According to a preferred embodiment of the invention, the phenolic resin is a thermosetting phenolic resin.
In the present invention, the phenolic resin may be commercially available.
According to the present invention, the kind of the phenol resin solution is not particularly limited, and preferably, the solvent in the phenol resin solution is an alcohol.
According to the present invention, the kind of alcohol in the phenolic resin solution may be selected from a wide range as long as the alcohol and phenolic resin can be uniformly mixed and easily removed under curing conditions, and preferably, the alcohol is selected from alcohols having 1 to 6 carbon atoms, and more preferably, methanol and/or ethanol.
According to the invention, the impregnation time is preferably between 0.5 and 3h, more preferably between 1 and 2h. The tensile strength of the carbon fiber paper can be further improved by adopting the preferable dipping time.
According to the present invention, preferably, the curing conditions include: the temperature is 100-200 ℃, preferably 140-160 ℃; the hot pressing pressure is 2-10MPa, preferably 4-6MPa; the time is 0.5-3h, preferably 1-2h. The tensile strength of the carbon fiber paper can be further improved by adopting the preferable curing condition.
According to the present invention, preferably, the carbonization conditions include: the temperature is 300-1100 ℃, preferably 700-900 ℃; the time is 0.5-3h, preferably 1-2h. The porosity and conductivity of the carbon fiber paper can be further improved by adopting the preferable carbonization condition.
According to the present invention, preferably, the graphitization conditions include: the temperature is 1200-2800 ℃, and 1800-2500 ℃ is preferred; the time is 0.5-3h, preferably 1-2h.
In a third aspect, the present invention provides a carbon fiber paper prepared by the method of the second aspect.
According to the invention, the carbon fiber paper has high porosity, air permeability, conductivity and tensile strength.
Preferably, the carbon content of the carbon fiber paper is more than or equal to 95 wt%, preferably 98-99.9 wt%; the porosity is 80-90%, preferably 82-90%; air permeability of 5X 10 4 -8×10 4 mL·mm/(cm 2 h.mmHg), preferably 5.5X 10 4 -7.5×10 4 mL·mm/(cm 2 ·h·mmHg)。
In a fourth aspect, the invention provides a use of the carbon fiber paper of the first or third aspect in a membrane electrode.
The carbon fiber paper has high porosity, good air permeability, conductivity, tensile strength and other excellent performances, and is extremely suitable for the field of membrane electrodes. The membrane electrode containing the carbon fiber paper has excellent conductivity, tensile strength and mass transfer capacity.
The present invention will be described in detail below by way of examples. In the following examples of the present invention,
the tensile strength is measured by referring to a method of GB _ T20042.7-2014 (a proton exchange membrane fuel cell 7 part carbon paper characteristic test method);
the surface resistance is measured by referring to the method of GB _ T20042.7-2014 (test method for the carbon paper characteristics of the 7 th part of the proton exchange membrane fuel cell);
the porosity is measured by referring to the method of GB _ T20042.7-2014 (test method for the carbon paper property of the 7 th part of the proton exchange membrane fuel cell);
the air permeability is measured by referring to the method of GB _ T20042.7-2014 (test method for the carbon paper property of the 7 th part of the proton exchange membrane fuel cell);
the carbon content was measured by a VAEIOEL type III elemental analyzer of elmendor, germany;
the weight average molecular weight of the polyacrylamide is 300 ten thousand;
the polymerization degree of the polyvinyl alcohol is 1700, and the alcoholysis degree is 88%;
the thermosetting phenolic resin has viscosity of 120-150 poise (25 deg.c), solid content not less than 80 wt%, water content not more than 3 wt%, free phenol not more than 10 wt% and pH value of 6.8-7.2.
Example 1
(1) Chopped carbon fibers (polyacrylonitrile-based carbon fibers, tensile modulus of 290GPa, length of 10mm and resistivity of 0.0014 omega-cm) and chopped porous carbon fibers (polyacrylonitrile-based carbon fibers, porosity of 70%, pore diameter of 0.07 mu m and specific surface area of 140 m) 2 G, diameter of 5 μm, length of 2.5mm, resistivity of 0.0015. Omega. Cm) anduniformly mixing to obtain mixed carbon fibers, wherein the content of the chopped carbon fibers is 80 wt% based on the total amount of the chopped carbon fibers and the chopped porous carbon fibers; mixing the obtained mixed carbon fiber with polyacrylamide, polyvinyl alcohol and water to obtain a mixture; the resulting mixture had a solids content of 0.05 wt%; the resulting mixture had a polyacrylamide content of 0.25 wt.% and a polyvinyl alcohol content of 0.05 wt.%;
performing wet papermaking (defibering, dispersing, papermaking and drying) on the obtained mixture to obtain a carbon fiber paper precursor; wherein, under the stirring speed of 10000rpm, the time for defibering and dispersing is 0.15h; the temperature for drying the papermaking paper is 90 ℃ and the time is 1.2h.
(2) The carbon fiber paper precursor is impregnated by using a thermosetting phenolic resin-ethanol solution (with the concentration of 7 wt%) for 1.5h, the adhering amount of the thermosetting phenolic resin is 90 parts by weight relative to 100 parts by weight of the carbon fiber precursor, then the carbon fiber paper precursor adhered with the thermosetting phenolic resin is cured for 1.5h at the temperature of 150 ℃ and the hot pressing pressure of 5MPa, then carbonized for 1.5h at the temperature of 800 ℃, and graphitized for 1.5h at the temperature of 2000 ℃, so that the carbon fiber paper product is prepared.
The porosity, air permeability, resistivity, carbon content and tensile strength of the resulting carbon fiber paper are shown in table 1.
Example 2
(1) Chopped carbon fibers (polyacrylonitrile-based carbon fibers, tensile modulus 230GPa, length 5mm, resistivity 0.0017 omega cm) and chopped porous carbon fibers (polyacrylonitrile-based carbon fibers, porosity 60%, pore diameter 0.05 μm, specific surface area 100 m) 2 0.5 μm in diameter, 2mm in length, and 0.002 Ω · cm in resistivity) to obtain a mixed carbon fiber, wherein the content of the chopped carbon fiber is 75 wt% based on the total amount of the chopped carbon fiber and the chopped porous carbon fiber; mixing the obtained mixed carbon fiber with polyacrylamide, polyvinyl alcohol and water to obtain a mixture; the resulting mixture had a solids content of 0.01% by weight; the resulting mixture had a polyacrylamide content of 0.1 wt.% and a polyvinyl alcohol content of 0.01 wt.%;
performing wet papermaking (defibering, dispersing, papermaking and drying) on the obtained mixture to obtain a carbon fiber paper precursor; wherein, under the stirring speed of 5000rpm, the time for defibering and dispersing is 0.1h; the temperature for drying the papermaking paper is 80 ℃, and the time is 1h.
(2) The carbon fiber paper precursor is impregnated by using a thermosetting phenolic resin-ethanol solution (with the concentration of 5 weight percent), the impregnation time is 1h, the adhesion amount of the thermosetting phenolic resin is 60 weight parts relative to 100 weight parts of the carbon fiber precursor, then the carbon fiber paper precursor with the thermosetting phenolic resin is cured for 2h at the temperature of 140 ℃ and the hot pressing pressure of 4MPa, then carbonized for 1h at the temperature of 700 ℃, and graphitized for 1h at the temperature of 1800 ℃, so that the carbon fiber paper product is prepared.
The porosity, air permeability, resistivity, carbon content and tensile strength of the resulting carbon fiber paper are shown in table 1.
Example 3
(1) Chopped carbon fibers (polyacrylonitrile-based carbon fibers, modulus of 350GPa, length of 15mm and resistivity of 0.001 omega cm) and chopped porous carbon fibers (polyacrylonitrile-based carbon fibers, porosity of 80%, pore diameter of 1 μm and specific surface area of 180 m) 2 /g, the diameter is 10 μm, the length is 3mm, and the resistivity is 0.0011 Ω · cm) to obtain mixed carbon fibers, wherein the content of the chopped carbon fibers is 85 wt% based on the total amount of the chopped carbon fibers and the chopped porous carbon fibers; mixing the obtained mixed carbon fiber with polyacrylamide, polyvinyl alcohol and water to obtain a mixture; the resulting mixture had a solids content of 0.1% by weight; the content of polyacrylamide in the obtained mixture was 0.5 wt%, and the content of polyvinyl alcohol was 0.1 wt%;
performing wet papermaking (defibering, dispersing, papermaking and drying) on the obtained mixture to obtain a carbon fiber paper precursor; wherein, under the stirring speed of 20000rpm, the time for defibering and dispersing is 0.2h; the temperature for drying the papermaking paper is 100 ℃, and the time is 1.5h.
(2) The carbon fiber paper precursor is impregnated by adopting a phenolic resin-ethanol solution (with the concentration of 10 weight percent), the dosage concentration of the phenolic resin is 10 weight percent, the impregnation time is 2 hours, the adhesion amount of the thermosetting phenolic resin is 120 weight percent relative to 100 weight percent of the carbon fiber precursor, then the carbon fiber paper precursor adhered with the thermosetting phenolic resin is cured for 1 hour at the temperature of 160 ℃ and the hot pressing pressure of 6MPa, and then carbonized for 2 hours at the temperature of 900 ℃, and graphitized for 2 hours at the temperature of 2500 ℃, so as to prepare the carbon fiber paper product.
The porosity, air permeability, resistivity, carbon content and tensile strength of the resulting carbon fiber paper are shown in table 1.
Example 4
(1) Chopped carbon fibers (polyacrylonitrile-based carbon fibers, modulus of 230GPa, length of 12mm and resistivity of 0.0015 omega cm) and chopped porous carbon fibers (polyacrylonitrile-based carbon fibers, porosity of 75%, pore diameter of 0.09 mu m and specific surface area of 150 m) 2 /g, the diameter is 4 μm, the length is 3mm, and the resistivity is 0.0014 Ω · cm) to obtain mixed carbon fibers, wherein the content of the chopped carbon fibers is 83 wt% based on the total amount of the chopped carbon fibers and the chopped porous carbon fibers; mixing the obtained mixed carbon fiber with polyacrylamide, polyvinyl alcohol and water to obtain a mixture; the resulting mixture had a solids content of 0.06 wt%; the resulting mixture had a polyacrylamide content of 0.3 wt.% and a polyvinyl alcohol content of 0.1 wt.%;
performing wet papermaking (defibering, dispersing, papermaking and drying) on the obtained mixture to obtain a carbon fiber paper precursor; wherein, under the stirring speed of 15000rpm, the time for defibering and dispersing is 0.2h; the temperature for drying the papermaking paper is 100 ℃, and the time is 1.5h.
(2) The carbon fiber paper precursor is impregnated by using a thermosetting phenolic resin-ethanol solution (with the concentration of 9 wt%) for 1.2h, the adhering amount of the thermosetting phenolic resin is 100 parts by weight relative to 100 parts by weight of the carbon fiber precursor, then the carbon fiber paper precursor adhered with the thermosetting phenolic resin is cured for 1h at the temperature of 145 ℃ and the hot-pressing pressure of 5MPa, then carbonized for 1.5h at the temperature of 850 ℃, and graphitized for 1h at the temperature of 2000 ℃, so that the carbon fiber paper product is prepared.
The porosity, air permeability, resistivity, carbon content and tensile strength of the resulting carbon fiber paper are shown in table 1.
Example 5
A carbon fiber paper was prepared by following the procedure of example 1, except that the chopped carbon fibers (pitch-based carbon fibers) had a length of 18mm, a tensile modulus of 350GPa, and a resistivity of 0.001. Omega. Cm)
The porosity, air permeability, resistivity, carbon content and tensile strength of the resulting carbon fiber paper are shown in table 1.
Example 6
A carbon fiber paper was prepared according to the method of example 1, except that the short cut porous carbon fibers (pitch-based carbon fibers) had a porosity of 80%, a pore diameter of 5 μm, and a specific surface area of 200m 2 A diameter of 0.2 μm, a length of 1mm, and a resistivity of 0.001. Omega. Cm.
The porosity, air permeability, electrical resistivity, carbon content and tensile strength of the resulting carbon fiber paper are shown in table 1.
Example 7
A carbon fiber paper was prepared according to the method of example 1, except that the content of the chopped carbon fibers was 60% by weight based on the total amount of the chopped carbon fibers and the chopped porous carbon fibers.
The porosity, air permeability, resistivity, carbon content and tensile strength of the resulting carbon fiber paper are shown in table 1.
Example 8
Carbon fiber paper was prepared according to the method of example 1 except that the carbonization temperature was 500 ℃ and the time was 2 hours.
The porosity, air permeability, electrical resistivity, carbon content and tensile strength of the resulting carbon fiber paper are shown in table 1.
Example 9
A carbon fiber paper was prepared according to the method of example 1, except that, in the step (1), the polyacrylamide content of the resultant mixture was 1% by weight.
The porosity, air permeability, resistivity, carbon content and tensile strength of the resulting carbon fiber paper are shown in table 1.
Comparative example 1
Carbon fiber paper was prepared according to the method of example 1, except that the chopped porous carbon fibers were replaced with an equal amount of chopped carbon fibers.
The porosity, air permeability, electrical resistivity, carbon content and tensile strength of the resulting carbon fiber paper are shown in table 1.
Comparative example 2
A carbon fiber paper was prepared according to the method of example 1, except that the chopped carbon fibers were replaced with the same amount of chopped porous carbon fibers.
The porosity, air permeability, resistivity, carbon content and tensile strength of the resulting carbon fiber paper are shown in table 1.
Comparative example 3
A carbon fiber paper was prepared according to the method of example 1, except that in step (1), polyacrylamide was replaced with an equal amount of water.
The porosity, air permeability, resistivity, carbon content and tensile strength of the resulting carbon fiber paper are shown in table 1.
TABLE 1
The results in table 1 show that the carbon fiber papers prepared in examples 1 to 9 according to the technical solution of the present invention have high porosity, air permeability, and tensile strength, and have low sheet resistance and good electrical conductivity. The carbon fiber paper prepared by the embodiments 1-4 of the preferred technical scheme of the invention has obviously better performance.
The preferred embodiments of the present invention have been described above in detail, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, many simple modifications can be made to the technical solution of the invention, including combinations of various technical features in any other suitable way, and these simple modifications and combinations should also be regarded as the disclosure of the invention, and all fall within the scope of the invention.
Claims (24)
1. A carbon fiber paper is characterized in that the carbon content of the carbon fiber paper is 98-99.9 wt%, the porosity is 82-90%, and the air permeability is 5 multiplied by 10 4 -8×10 4 mL•mm/（cm 2 H.mmhg); the method for preparing the carbon fiber paper comprises the following steps: (1) Will contain chopped carbon fibersWet papermaking of the mixture of the fiber, the chopped porous carbon fiber, the dispersant, the adhesive and the solvent to obtain a carbon fiber paper precursor;
(2) Impregnating the carbon fiber paper precursor by adopting a phenolic resin solution, and then curing, carbonizing and graphitizing; wherein, based on the total amount of the chopped carbon fibers and the chopped porous carbon fibers, the content of the chopped carbon fibers is 60 to 97 percent by weight, in the mixture, the content of the dispersing agent is 0.01 to 1 percent by weight, and the content of the adhesive is 0.01 to 1 percent by weight; the porosity of the chopped porous carbon fibers is 30-80%.
2. The carbon fiber paper according to claim 1,
the air permeability of the carbon fiber paper is 5.5 multiplied by 10 4 -7.5×10 4 mL•mm/（cm 2 •h•mmHg）。
3. A method of making the carbon fiber paper of claim 1 or 2, characterized in that it comprises the steps of:
(1) The method comprises the following steps of (1) carrying out wet papermaking on a mixture containing chopped carbon fibers, chopped porous carbon fibers, a dispersing agent, an adhesive and a solvent to obtain a carbon fiber paper precursor;
(2) Impregnating the carbon fiber paper precursor by adopting a phenolic resin solution, and then curing, carbonizing and graphitizing;
wherein, based on the total amount of the chopped carbon fibers and the chopped porous carbon fibers, the content of the chopped carbon fibers is 60 to 97 weight percent, and in the mixture, the content of the dispersant is 0.01 to 1 weight percent, and the content of the adhesive is 0.01 to 1 weight percent; the porosity of the chopped porous carbon fibers is 30-80%.
4. The method according to claim 3, wherein the chopped carbon fibers are present in an amount of 75-85% by weight, based on the total amount of chopped carbon fibers and chopped porous carbon fibers.
5. A process as claimed in claim 3 or 4, wherein the solids content of the mixture is from 0.005 to 0.5% by weight.
6. The process of claim 5, wherein the mixture has a solids content of 0.01-0.1 wt%.
7. A process as claimed in claim 3 or 4, wherein the dispersant is present in the mixture in an amount of from 0.1 to 0.5% by weight.
8. The method of claim 3 or 4, wherein the chopped carbon fibers have an electrical resistivity of 0.001-0.01 Ω -cm;
and/or the length of the chopped carbon fiber is 3-18mm;
and/or the chopped carbon fibers are polyacrylonitrile-based carbon fibers and/or asphalt-based carbon fibers.
9. The method of claim 8, wherein the chopped carbon fibers have an electrical resistivity of 0.001-0.002 Ω -cm;
and/or the length of the chopped carbon fiber is 5-15mm.
10. The method according to claim 3 or 4, wherein the pore size of the chopped porous carbon fibers is 0.01-5 μm;
and/or the specific surface area of the chopped porous carbon fiber is 50-200m 2 /g；
And/or the length of the chopped porous carbon fiber is 1-5 mm;
and/or the diameter of the chopped porous carbon fiber is 0.2-30 μm;
and/or the electrical resistivity of the chopped porous carbon fibers is 0.001-0.01 omega cm;
and/or the chopped porous carbon fibers are polyacrylonitrile-based carbon fibers and/or pitch-based carbon fibers.
11. The method of claim 10, wherein the pore size of the chopped porous carbon fibers is 0.05-1 μ ι η;
and/or, said chopped strand porosityThe specific surface area of the carbon fiber is 100-180m 2 /g；
And/or the chopped porous carbon fibers have a length of 2-3mm;
and/or the diameter of the chopped porous carbon fiber is 0.5-10 μm;
and/or the resistivity of the chopped porous carbon fibers is 0.001-0.002 ohm cm.
12. The method according to claim 3 or 4, wherein the dispersant is selected from at least one of polyacrylamide, polyethylene oxide, and cellulose derivatives.
13. The method of claim 12, wherein the cellulose derivative is selected from at least one of methylcellulose, sodium hydroxymethylcellulose, and hydroxyethylcellulose.
14. The method of claim 3 or 4, wherein the binder is selected from at least one of polyvinyl alcohol, phenolic resin, and polytetrafluoroethylene.
15. The method according to claim 3 or 4, wherein in step (2), the concentration of the phenolic resin solution is 2-10 weight percent;
and/or, the curing conditions include: the temperature is 100-200 ℃; the hot pressing pressure is 2-10MPa; the time is 0.5 to 3 hours;
and/or, the carbonization conditions comprise: the temperature is 300-1100 ℃; the time is 0.5 to 3 hours;
and/or, the graphitizing conditions comprise: the temperature is 1200-2800 ℃; the time is 0.5-3h.
16. The method of claim 15, wherein in step (2), the concentration of the phenolic resin solution is 5-10 weight parts%.
17. The method according to claim 3 or 4, wherein the adhering amount of the phenolic resin is 50 to 200 parts by weight with respect to 100 parts by weight of the carbon fiber paper precursor.
18. The method of claim 17, wherein the amount of phenolic resin deposited is 60 to 120 parts by weight relative to 100 parts by weight of the carbon fiber paper precursor.
19. A process according to claim 3 or 4, wherein the phenolic resin is a thermosetting phenolic resin.
20. A process according to claim 3 or 4, wherein the solvent in the phenolic resin solution is an alcohol.
21. The method of claim 20, wherein the alcohol is selected from alcohols having 1-6 carbon atoms.
22. The method of claim 21, wherein the alcohol is methanol and/or ethanol.
23. The method of claim 15, wherein the curing conditions comprise: the temperature is 140-160 ℃; the hot pressing pressure is 4-6MPa; the time is 1-2h;
and/or, the carbonization conditions comprise: the temperature is 700-900 ℃; the time is 1-2h;
and/or, the graphitizing conditions comprise: the temperature is 1800-2500 ℃; the time is 1-2h.
24. Use of the carbon fiber paper of claim 1 or 2 in a membrane electrode.
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