CN111129555A - Carbon paper material for high-toughness high-conductivity proton exchange membrane battery - Google Patents
Carbon paper material for high-toughness high-conductivity proton exchange membrane battery Download PDFInfo
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- CN111129555A CN111129555A CN201911346111.7A CN201911346111A CN111129555A CN 111129555 A CN111129555 A CN 111129555A CN 201911346111 A CN201911346111 A CN 201911346111A CN 111129555 A CN111129555 A CN 111129555A
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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
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/10—Fuel cells with solid electrolytes
- H01M8/1004—Fuel cells with solid electrolytes characterised by membrane-electrode assemblies [MEA]
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- 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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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/10—Fuel cells with solid electrolytes
- H01M2008/1095—Fuel cells with polymeric electrolytes
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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 a carbon paper material for a high-toughness high-conductivity proton exchange membrane battery, belonging to the technical field of carbon paper materials. The invention utilizes the constant temperature liquid phase oxidation-reduction reaction between potassium permanganate and concentrated sulfuric acid to effectively load a nano manganese dioxide material on the surface of a carbon paper material, simultaneously effectively coats polydimethylsiloxane on the surface of the carbon paper material, etches the crosslinked polydimethylsiloxane through hydrofluoric acid, effectively etches the polydimethylsiloxane material and ensures the polydimethylsiloxane material to have holes to ensure the conduction of a current material, simultaneously, the technical scheme effectively coats and improves the material structure, and a layer of ultrathin nano MnO is prepared on the carbon paper substrate through a chemical oxidation-reduction method2Nano-film, so that MnO can be greatly increased2The specific surface area of the thin film electrode is increased, thereby increasing the capacity of an electric double layer and fully exerting MnO2The electrochemical performance and power performance of the material are improved, the utilization rate of the material is improved, and the material is coated with modified polydimethylsiloxaneThe siloxane effectively modifies the toughness and the strength of the material and improves the mechanical property of the material.
Description
Technical Field
The invention relates to a carbon paper material for a high-toughness high-conductivity proton exchange membrane battery, belonging to the technical field of carbon paper materials.
Background
A fuel cell is a device that directly converts chemical energy of hydrogen and oxygen into electrical energy through an electrode reaction. Compared with the traditional energy, the fuel cell does not involve combustion in the reaction process, so that the energy conversion efficiency is not limited by Carnot cycle, and the fuel cell has the remarkable characteristics of high efficiency, cleanness and the like. Proton Exchange Membrane Fuel Cells (PEMFCs) not only have the general characteristics of fuel cells, but also have the characteristics of high energy conversion efficiency, environmental friendliness, high specific energy (relative to batteries), low operating temperature and quick start, and can be widely applied to the fields of automobiles, power stations, mobile power supplies and the like.
PEMFCs are the most mature of the fuel cell family, closest to the fuel cells for commercial applications. Its basic components include: bipolar plates, gas diffusion layers, catalyst layers, and proton exchange membranes. The bipolar plate serves to separate each unit cell in the stack and to supply fuel and oxygen to the gas diffusion layer through the channels formed therein, while having high electrical conductivity so as to conduct electricity to the outside. The gas diffusion layer, the catalyst layer and the proton exchange membrane constitute a membrane electrode assembly (EMA).
The gas diffusion layer is typically comprised of a substrate layer and a microporous layer. The substrate material layer is usually selected from porous carbon paper and carbon cloth, and the thickness thereof is about 100-. Mainly functioning to support the microporous layer and the catalytic layer. Different types of substrate layers have different thicknesses, porosities, and surface resistances, directly affecting the gas permeability and electrical conductivity of the diffusion layer.
The gas diffusion layer is an important component in a proton exchange membrane fuel cell, functions to support a catalyst layer, and is also a channel for reactant gases and product water. The gas diffusion layer should also have good electrical conductivity and corrosion resistance under electrochemical reaction. Gas diffusion layers have been developed for many years, and there is a relatively comprehensive understanding of the effect of gas diffusion layers and the requirements for gas diffusion layers are given:
(1) the function of the supporting catalyst layer.
(2) The channels for transporting gas and water.
(3) The function of conduction electrons.
(4) The transfer and distribution of heat.
(5) Strong chemical corrosion resistance and electrochemical corrosion resistance.
Through many years of research and development, the material for the gas diffusion layer, which is mature to be applied to the fuel cell at present, is a carbon material. The carbon material has the advantages of high conductivity, high anti-corrosion performance and low cost, which are not possessed by other materials. However, the carbon material is brittle and not conducive to molding, and the control of its microstructure is also a relatively difficult point.
Several main gas diffusion layer materials in PEMFC electrodes include carbon paper, carbon fiber woven cloth, non-woven cloth, carbon black paper, etc., all of which have their own advantages and disadvantages.
Carbon paper, which has not only a uniform porous structure but also excellent electrical conductivity, chemical stability and thermal stability due to the use of carbon fiber as a main raw material, is mostly used as a gas diffusion layer base material in PEMFC electrodes. The carbon fiber is usually selected from any one of polyacrylonitrile-based, pitch-based, and cellulose-based carbon fibers, and preferably has a diameter of 5-20um and a length of 5-20 mm. Carbon paper has the disadvantage of being mechanically brittle and requiring improvement in strength. At present, the common preparation method of carbon fiber is to mix a binder and short fiber for papermaking, and carbon paper is obtained through impregnation, mould pressing, carbonization and graphitization.
Since carbon paper is brittle and lacks flexibility, it is easily damaged during the process of preparing the electrode. Therefore, a large amount of the gas diffusion layer substrate material and also the carbon fiber woven fabric are used. It has no mechanical fragility like carbon paper, has bending property, and can introduce elasticity in the thickness direction depending on the fiber structure and weaving process, thereby endowing it with certain compression resistance, and being beneficial to improving the electric contact with the electrolyte or catalyst layer by means of compression. The carbon fiber yarn for weaving is a long carbon fiber and is bundled, but it is preferable to weave a cloth by twisting the yarn by a spinning process, but the carbon cloth may be a cloth woven from a precursor of the carbon fiber and carbonized. Since the carbon fibers are not fixed, the carbon cloth is easily stretched in the plane direction and lacks dimensional stability, so that it is difficult to manufacture an electrode. In order to impart rigidity to the carbon cloth and improve its conductivity, it is common to embed conductive carbon black particles in the carbon cloth or to coat a layer of phenol resin on yarns of the carbon cloth and then carbonize it at high temperature in an inert atmosphere.
In order to overcome the defect that carbon paper lacks flexibility and carbon fiber woven cloth lacks dimensional stability, the gas diffusion layer substrate can also be made of non-woven cloth material, and the gas diffusion layer substrate has the advantages of certain mechanical strength, high flexibility, dimensional stability and the like, so that the electrode is favorably manufactured. The open porosity is between 40-99% to facilitate filling with other materials, thereby enabling the resulting gas diffusion layer porosity, electrical conductivity, and hydrophobicity to be programmable through the filler material.
The carbon black paper used as the substrate of the gas diffusion layer is a sheet with a flat surface formed by hot pressing after carbon powder and a polymer binder are uniformly dispersed. Wherein the mass ratio of the polymer to the carbon powder is between 20: 8 and 45: 55. The carbon powder can be selected from activated carbon, carbon black, acetylene black or their mixture, and has specific surface area of 50-2000m2Between/g; the polymer can be selected from fluororesin, such as PTFE, polyvinylidene fluoride 1, etc., and the fluororesin can also be used as a hydrophobic treatment agent of carbon black paper, thereby simplifying the subsequent hydrophobic treatment process and reducing the cost.
Disclosure of Invention
The technical problems to be solved by the invention are as follows: aiming at the problems of poor conductivity and uneven pore size distribution of the existing carbon paper, the carbon paper material for the conductive proton exchange membrane battery with high toughness is provided.
In order to solve the technical problems, the invention adopts the technical scheme that:
(1) cutting the carbon paper, soaking the cut carbon paper into a soaking solution according to the mass ratio of 1: 10, heating in a heat-preservation water bath, standing and cooling to room temperature, filtering, collecting the soaked carbon paper, washing and drying to obtain modified carbon paper; stirring and mixing 1, 3-dioxolane and xylene according to the mass ratio of 1: 1, standing to obtain a dissolving solvent, adding polydimethylsiloxane into the dissolving solvent according to the mass ratio of 1: 20, stirring for dissolving, performing ultrasonic dispersion, collecting a dispersion dissolving solution, adding modified carbon paper into the dispersion dissolving solution according to the mass ratio of 1: 15, stirring, mixing, soaking for 3-5 hours, filtering, collecting a filter cake, performing leaching treatment and drying to obtain etched and coated modified carbon paper;
(2) respectively weighing 45-50 parts by weight of deionized water, 1-2 parts by weight of manganese sulfate, 1-2 parts by weight of ammonium persulfate and 1-2 parts by weight of ammonium sulfate, adding the weighed materials into a beaker, stirring, mixing, carrying out hydrothermal heat preservation reaction to obtain a mixed reaction liquid, filtering, collecting a filter cake, washing and drying to obtain a reactant; respectively weighing 45-50 parts by weight of deionized water, 1-2 parts by weight of dopamine and 1-2 parts by weight of reactants, placing the deionized water, the dopamine and the reactants into a beaker, stirring and mixing the mixture and adjusting the pH value to 8.5, stirring and mixing the mixture and carrying out heat preservation reaction, standing and cooling the mixture to room temperature and filtering the mixture, collecting a filter cake, placing the filter cake into a tubular atmosphere furnace, introducing argon to remove air, drying the filter cake after the introduction is finished, heating the filter cake, and carrying out heat preservation calcination to obtain modified composite particles;
(3) respectively weighing 45-50 parts by weight of graphene water suspension, 1-2 parts by weight of modified composite particles and 45-50 parts by weight of deionized water, stirring, mixing, placing in a mortar for grinding and dispersing, collecting dispersed slurry, placing in a hydrothermal reaction at 125-150 ℃ for 10-12 h to obtain a hydrothermal gel liquid; and respectively weighing 45-50 parts by weight of absolute ethyl alcohol, 1-2 parts by weight of polyvinyl butyral and 10-15 parts by weight of hydrothermal gel liquid, stirring and mixing, soaking the etched coated modified carbon paper into the hydrothermal gel liquid, soaking, drying, washing with a phenolic resin solution, drying, collecting to obtain dried coated modified carbon paper, placing the dried coated modified carbon paper into a flat vulcanizing machine, performing compression molding, and performing high-temperature treatment to obtain the carbon paper material for the high-toughness high-conductivity proton exchange membrane battery.
The preparation method of the soaking solution comprises the steps of weighing 45-50 parts by weight of deionized water, 10-15 parts by weight of 25% sulfuric acid and 1-2 parts by weight of potassium permanganate respectively, placing the materials in a beaker, and stirring and mixing the materials to obtain the soaking solution.
And the leaching treatment is to leach 1-2 times by using hydrofluoric acid solution with the mass fraction of 0.01%.
The hydrothermal heat preservation reaction is a heat preservation reaction at 200-250 ℃ for 80-90 h.
The pH value is adjusted to 8.5 by adopting 1% ammonia water by mass fraction.
The argon gas introducing speed is 20-30 mL/min.
The drying treatment, temperature rise heating and heat preservation calcining are drying at 100-110 ℃ to constant weight, then raising the temperature to 750-850 ℃ at 5 ℃/min, and carrying out heat preservation calcining for 3-5 h.
The concentration of the graphene aqueous suspension is 1% by mass.
The compression molding is performed at the curing temperature of 165-170 ℃ and under 10-15 MPa.
The high-temperature treatment is carried out at 2750-2800 ℃ for 15-20 min.
Compared with other methods, the method has the beneficial technical effects that:
(1) the technical scheme of the invention adopts an oxidation-reduction method, utilizes a constant-temperature liquid-phase oxidation-reduction reaction between potassium permanganate and concentrated sulfuric acid to effectively load a nano manganese dioxide material onto the surface of a carbon paper material, effectively coats polydimethylsiloxane on the surface of the carbon paper material, etches the crosslinked polydimethylsiloxane through hydrofluoric acid, effectively etches the polydimethylsiloxane material and ensures that holes appear in the polydimethylsiloxane material to ensure the conduction of a current material, effectively coats and improves the material structure, and prepares a layer of ultrathin nano MnO on a carbon paper substrate through a chemical oxidation-reduction method2Nano-film, so that MnO can be greatly increased2The specific surface area of the thin film electrode is increased, thereby increasing the capacity of an electric double layer and fully exerting MnO2The electrochemical performance and the power performance of the material are improved, the utilization rate of the material is improved, and meanwhile, the toughness strength of the material is effectively modified by coating the modified polydimethylsiloxane, so that the mechanical property of the material is improved;
(2) in the technical scheme of the invention, the structural performance and the conductivity of the material are improved by a composite gel system, the active functional groups are increased by effectively adding a polyvinyl butyral material, the chemical bonding degree is enhanced, the bonding degree of a matrix and a carbon fiber interface is increased, once the interface is formed, a-C-C-framework still remains after high-temperature treatment, the bonding strength of the interface in carbon paper is improved along with the increase of PVB (polyvinyl butyral) mass concentration, the carbon fiber and the matrix interface are bridges between the carbon fiber and the matrix to play a role in relieving stress concentration and transferring load, simultaneously, a network structure formed by connecting matrix carbon and carbon fiber is more compact, the pore diameter of pores on the surface of the carbon paper is obviously reduced, the number of the small pores in matrix carbon is greatly increased to further improve the strength of the carbon paper, and simultaneously, due to the formation of a good conductive network structure in the carbon paper and the improvement of the interface, the good conductive mesh structure can provide more transmission channels for carriers, and the good phase interface can provide more bridges for carrier movement, so that a continuous passage is formed, and the conductivity of the carbon paper is improved.
Detailed Description
Respectively weighing 45-50 parts by weight of deionized water, 10-15 parts by weight of 25% sulfuric acid and 1-2 parts by weight of potassium permanganate, placing the deionized water, 10-15 parts by weight of 25% sulfuric acid and 1-2 parts by weight of potassium permanganate into a beaker, stirring and mixing to obtain a soaking solution, taking and cutting carbon paper, soaking the cut carbon paper into the soaking solution according to the mass ratio of 1: 10, soaking for 20-30 min, heating in a heat-preservation water bath at 75-85 ℃ for 2-3 h, standing and cooling to room temperature, filtering and collecting the soaked carbon paper, washing with deionized water until the washing solution is neutral, and then carrying out vacuum drying at 45-50 ℃ for 1-2 h to obtain modified carbon paper; stirring and mixing 1, 3-dioxolane and xylene according to the mass ratio of 1: 1, standing for 6-8 hours to obtain a dissolving solvent, adding polydimethylsiloxane into the dissolving solvent according to the mass ratio of 1: 20, stirring for dissolving, ultrasonically dispersing, collecting a dispersion dissolving solution according to the mass ratio of 1: 15, adding modified carbon paper into the dispersion dissolving solution, stirring, mixing, soaking for 3-5 hours, filtering, collecting a filter cake, carrying out vacuum drying for 3-5 hours at the temperature of 45-50 ℃, leaching for 1-2 times by using a hydrofluoric acid solution with the mass fraction of 0.01%, washing by using deionized water until a washing solution is neutral, and naturally airing to obtain etching coated modified carbon paper; respectively weighing 45-50 parts by weight of deionized water, 1-2 parts by weight of manganese sulfate, 1-2 parts by weight of ammonium persulfate and 1-2 parts by weight of ammonium sulfate, adding the materials into a beaker, stirring and mixing, placing the mixture at 200-250 ℃ for heat preservation reaction for 80-90 hours to obtain mixed reaction liquid, filtering the mixed reaction liquid, collecting a filter cake, washing the filter cake for 3-5 times by using deionized water, and performing vacuum drying to obtain a reactant; respectively weighing 45-50 parts by weight of deionized water, 1-2 parts by weight of dopamine and 1-2 parts by weight of reactants, placing the deionized water, the dopamine and the reactants into a beaker, stirring and mixing the mixture, dropwise adding ammonia water with the mass fraction of 1% to adjust the pH value to 8.5, stirring and mixing the mixture, placing the mixture at 75-80 ℃ for heat preservation reaction for 3-5 hours, standing and cooling the mixture to room temperature and filtering the mixture, collecting a filter cake, placing the filter cake into a tubular atmosphere furnace, introducing argon to remove air, controlling the introduction rate of the argon to be 20-30 mL/min, drying the mixture at 100-110 ℃ to constant weight after the introduction is finished, heating the mixture to 750-850 ℃ at the speed of 5 ℃/min, and performing heat preservation calcination for; respectively weighing 45-50 parts by weight of graphene water suspension with the mass fraction of 1%, 1-2 parts by weight of modified composite particles and 45-50 parts by weight of deionized water, stirring, mixing, grinding and dispersing in a mortar, collecting dispersed slurry, and carrying out hydrothermal reaction at 125-150 ℃ for 10-12 h to obtain hydrothermal gel liquid; and respectively weighing 45-50 parts by weight of absolute ethyl alcohol, 1-2 parts by weight of polyvinyl butyral and 10-15 parts by weight of hydrothermal gel liquid, stirring and mixing, soaking the etched coated modified carbon paper into the hydrothermal gel liquid, soaking, drying for 6-8 hours at 55-60 ℃, rinsing for 3-5 times by using a phenolic resin solution with the mass fraction of 0.01%, drying for 2-3 hours at 75-85 ℃, collecting the dried coated modified carbon paper, placing the dried coated modified carbon paper into a flat-plate vulcanizing machine, pressing and molding at the curing temperature of 165-170 ℃ and 10-15 MPa, and then treating at the high temperature of 2750-2800 ℃ for 15-20 minutes to prepare the carbon paper material for the high-toughness high-conductivity proton exchange membrane battery.
Example 1
Respectively weighing 45 parts by weight of deionized water, 10 parts by weight of 25% sulfuric acid and 1 part by weight of potassium permanganate, placing the deionized water, 10 parts by weight of 25% sulfuric acid and 1 part by weight of potassium permanganate in a beaker, stirring and mixing to obtain a soaking solution, taking and cutting carbon paper, soaking the cut carbon paper into the soaking solution according to the mass ratio of 1: 10, soaking for 20min, heating in a heat-preservation water bath at 75 ℃ for 2h, standing and cooling to room temperature, filtering and collecting the soaked carbon paper, washing with deionized water until a washing solution is neutral, and then drying in vacuum at 45 ℃ for 1h to obtain modified carbon paper; stirring and mixing 1, 3-dioxolane and xylene according to the mass ratio of 1: 1, standing for 6 hours to obtain a dissolved solvent, adding polydimethylsiloxane into the dissolved solvent according to the mass ratio of 1: 20, stirring for dissolving, ultrasonically dispersing and collecting a dispersion solution, adding modified carbon paper into the dispersion solution according to the mass ratio of 1: 15, stirring, mixing, soaking for 3 hours, filtering, collecting a filter cake, carrying out vacuum drying at 45 ℃ for 3 hours, leaching for 1 time by using a hydrofluoric acid solution with the mass fraction of 0.01%, washing with deionized water until a washing solution is neutral, and naturally airing to obtain the etching coated modified carbon paper; respectively weighing 45 parts of deionized water, 1 part of manganese sulfate, 1 part of ammonium persulfate and 1 part of ammonium sulfate according to parts by weight, adding the materials into a beaker, stirring and mixing the materials, placing the mixture at 200 ℃ for heat preservation reaction for 80 hours to obtain mixed reaction liquid, filtering the mixed reaction liquid, collecting a filter cake, washing the filter cake for 3 times by using the deionized water, and drying the filter cake in vacuum to obtain a reactant; respectively weighing 45 parts of deionized water, 1 part of dopamine and 1 part of reactant according to parts by weight, placing the materials into a beaker, stirring and mixing the materials, dropwise adding ammonia water with the mass fraction of 1% to adjust the pH value to 8.5, stirring and mixing the materials, placing the materials at 75 ℃ for heat preservation reaction for 3 hours, standing and cooling the materials to room temperature and filtering the materials, collecting a filter cake, placing the filter cake into a tubular atmosphere furnace, introducing argon to remove air, controlling the argon introduction rate to be 20mL/min, drying the materials at 100 ℃ to constant weight, heating the materials to 750 ℃ at the speed of 5 ℃/min, and calcining the materials for 3 hours in a heat preservation manner to obtain modified composite particles; respectively weighing 45 parts by weight of graphene aqueous suspension with the mass fraction of 1%, 1 part by weight of modified composite particles and 45 parts by weight of deionized water, stirring, mixing, grinding and dispersing in a mortar, collecting dispersed slurry, and carrying out hydrothermal reaction at 125 ℃ for 10 hours to obtain hydrothermal gel liquid; respectively weighing 45 parts by weight of absolute ethyl alcohol, 1 part by weight of polyvinyl butyral and 10 parts by weight of hydrothermal gel liquid, stirring and mixing, soaking the etched coated modified carbon paper into the hydrothermal gel liquid, soaking, drying at 55 ℃ for 6 hours, leaching for 3 times by using a phenolic resin solution with the mass fraction of 0.01%, drying at 75 ℃ for 2 hours, collecting the dried coated modified carbon paper, placing the dried coated modified carbon paper into a flat-plate vulcanizing machine, pressing and molding at the curing temperature of 165 ℃ and 10MPa, and then treating at 2750 ℃ for 15 minutes to obtain the carbon material for the high-conductivity proton exchange membrane battery with high toughness.
Example 2
Respectively weighing 47 parts by weight of deionized water, 12 parts by weight of 25% sulfuric acid and 1 part by weight of potassium permanganate, placing the deionized water, 12 parts by weight of 25% sulfuric acid and 1 part by weight of potassium permanganate in a beaker, stirring and mixing to obtain a soaking solution, taking and cutting carbon paper, soaking the cut carbon paper into the soaking solution according to the mass ratio of 1: 10, soaking for 25min, heating in a heat-preservation water bath at 80 ℃ for 2h, standing and cooling to room temperature, filtering and collecting the soaked carbon paper, washing with deionized water until a washing solution is neutral, and then drying in vacuum at 47 ℃ for 1h to obtain modified carbon paper; stirring and mixing 1, 3-dioxolane and xylene according to the mass ratio of 1: 1, standing for 7 hours to obtain a dissolved solvent, adding polydimethylsiloxane into the dissolved solvent according to the mass ratio of 1: 20, stirring for dissolving, ultrasonically dispersing and collecting a dispersion solution, adding modified carbon paper into the dispersion solution according to the mass ratio of 1: 15, stirring, mixing, soaking for 4 hours, filtering, collecting a filter cake, carrying out vacuum drying at 47 ℃ for 4 hours, leaching for 1 time by using a hydrofluoric acid solution with the mass fraction of 0.01%, washing with deionized water until a washing solution is neutral, and naturally airing to obtain the etching coated modified carbon paper; respectively weighing 47 parts by weight of deionized water, 1 part by weight of manganese sulfate, 1 part by weight of ammonium persulfate and 1 part by weight of ammonium sulfate, adding the materials into a beaker, stirring and mixing the materials, placing the mixture at 225 ℃ for heat preservation reaction for 85 hours to obtain mixed reaction liquid, filtering the mixed reaction liquid, collecting a filter cake, washing the filter cake for 4 times by using the deionized water, and drying the filter cake in vacuum to obtain a reactant; respectively weighing 47 parts by weight of deionized water, 1 part by weight of dopamine and 1 part by weight of reactant, placing the deionized water, the dopamine and the reactant in a beaker, stirring and mixing the mixture, dropwise adding ammonia water with the mass fraction of 1% to adjust the pH value to 8.5, stirring and mixing the mixture, placing the mixture at 78 ℃ for heat preservation reaction for 4 hours, standing and cooling the mixture to room temperature and filtering the mixture, collecting a filter cake, placing the filter cake in a tubular atmosphere furnace, introducing argon to remove air, controlling the argon introduction rate to be 25mL/min, drying the mixture at 105 ℃ to constant weight, heating the mixture to 800 ℃ at the speed of 5 ℃/min, and calcining the mixture for 4 hours to obtain modified composite; respectively weighing 47 parts by weight of 1% graphene aqueous suspension, 1 part by weight of modified composite particles and 47 parts by weight of deionized water, stirring, mixing, grinding and dispersing in a mortar, collecting dispersed slurry, and carrying out hydrothermal reaction at 135 ℃ for 11 hours to obtain a hydrothermal gel solution; respectively weighing 47 parts by weight of absolute ethyl alcohol, 1 part by weight of polyvinyl butyral and 12 parts by weight of hydrothermal gel liquid, stirring and mixing, soaking the etched coated modified carbon paper into the hydrothermal gel liquid, soaking, drying at 58 ℃ for 7 hours, leaching for 4 times by using a phenolic resin solution with the mass fraction of 0.01%, drying at 80 ℃ for 2 hours, collecting the dried coated modified carbon paper, placing the dried coated modified carbon paper into a flat-plate vulcanizing machine, pressing and molding at the curing temperature of 168 ℃ and the curing pressure of 12MPa, and then treating at the temperature of 2775 ℃ for 18 minutes to obtain the carbon material for the high-conductivity proton exchange membrane battery.
Example 3
Respectively weighing 50 parts by weight of deionized water, 15 parts by weight of 25% sulfuric acid and 2 parts by weight of potassium permanganate, placing the deionized water, 15 parts by weight of 25% sulfuric acid and 2 parts by weight of potassium permanganate in a beaker, stirring and mixing to obtain a soaking solution, taking and cutting carbon paper, soaking the cut carbon paper into the soaking solution according to the mass ratio of 1: 10, soaking for 30min, heating in a heat-preservation water bath at 85 ℃ for 3h, standing and cooling to room temperature, filtering and collecting the soaked carbon paper, washing with deionized water until a washing solution is neutral, and then carrying out vacuum drying at 50 ℃ for 2h to obtain modified carbon paper; stirring and mixing 1, 3-dioxolane and xylene according to the mass ratio of 1: 1, standing for 8 hours to obtain a dissolving solvent, adding polydimethylsiloxane into the dissolving solvent according to the mass ratio of 1: 20, stirring for dissolving, performing ultrasonic dispersion to collect a dispersion solution, adding modified carbon paper into the dispersion solution according to the mass ratio of 1: 15, stirring for mixing, soaking for 5 hours, filtering, collecting a filter cake, performing vacuum drying at 50 ℃ for 5 hours, leaching for 2 times by using a hydrofluoric acid solution with the mass fraction of 0.01%, washing with deionized water until a washing solution is neutral, and naturally drying to obtain the etching coated modified carbon paper; respectively weighing 50 parts by weight of deionized water, 2 parts by weight of manganese sulfate, 2 parts by weight of ammonium persulfate and 2 parts by weight of ammonium sulfate, adding the weighed materials into a beaker, stirring and mixing the materials, placing the mixture at 250 ℃ for heat preservation reaction for 90 hours to obtain mixed reaction liquid, filtering the mixed reaction liquid, collecting a filter cake, washing the filter cake for 5 times by using the deionized water, and drying the filter cake in vacuum to obtain a reactant; respectively weighing 50 parts by weight of deionized water, 2 parts by weight of dopamine and 2 parts by weight of reactants, placing the deionized water, the dopamine and the reactants into a beaker, stirring and mixing the mixture, dropwise adding ammonia water with the mass fraction of 1% to adjust the pH value to 8.5, stirring and mixing the mixture, placing the mixture at 80 ℃ for heat preservation reaction for 5 hours, standing and cooling the mixture to room temperature, filtering the mixture, collecting a filter cake, placing the filter cake into a tubular atmosphere furnace, introducing argon to remove air, controlling the introduction rate of the argon to be 30mL/min, drying the mixture at 110 ℃ to constant weight, heating the mixture to 850 ℃ at the temperature of 5 ℃/min, and performing heat preservation and calcination for 5 hours; respectively weighing 50 parts by weight of 1% graphene aqueous suspension, 2 parts by weight of modified composite particles and 50 parts by weight of deionized water, stirring, mixing, grinding and dispersing in a mortar, collecting dispersed slurry, and carrying out hydrothermal reaction at 150 ℃ for 12 hours to obtain a hydrothermal gel solution; respectively weighing 50 parts by weight of absolute ethyl alcohol, 2 parts by weight of polyvinyl butyral and 15 parts by weight of hydrothermal gel liquid, stirring and mixing, soaking the etched coated modified carbon paper into the hydrothermal gel liquid, soaking, drying at 60 ℃ for 8 hours, leaching for 5 times by using a phenolic resin solution with the mass fraction of 0.01%, drying at 85 ℃ for 3 hours, collecting the dried coated modified carbon paper, placing the dried coated modified carbon paper into a flat-plate vulcanizing machine, pressing and molding at the curing temperature of 170 ℃ and 15MPa, and then treating at 2800 ℃ for 20 minutes to obtain the carbon material for the high-conductivity proton exchange membrane battery with high toughness.
Comparative example: carbon paper from Dongguan company.
The carbon papers prepared in the examples and the comparative examples were tested, specifically as follows:
the opening rate is as follows: the standard of the test is (YB/T908-1997). The open porosity of the gas diffusion layer is the ratio of the volume of the open pores in the gas diffusion layer to the total volume of the gas diffusion layer. Therefore, the open pore ratio of the gas diffusion layer can be characterized by measuring the volume of the open pores of the gas diffusion layer and the total volume of the gas diffusion layer.
Resistivity: the surface conductivity is typically measured using a four-probe test method. The method adopts an MCP-7360 type low resistivity meter of RS-Aldrich company, selects a thickness of 0.432mm for calibration, and selects a surface resistance test program to carry out resistivity test on the prepared carbon paper sample.
The specific test results are shown in table 1.
Table 1 comparative table of property characterization
| Detecting items | Example 1 | Example 2 | Example 3 | Comparative example |
| Open cell content% | 84 | 85 | 86 | 56 |
| Resistivity/Ω · cm | 4.29×10﹣3 | 3.55×10﹣3 | 4.06×10﹣3 | 8.09×10﹣3 |
As can be seen from table 1, the carbon paper material for proton exchange membrane battery prepared by the present invention has good porosity and electrical conductivity.
Claims (10)
1. A carbon paper material for a high-toughness high-conductivity proton exchange membrane battery is characterized by comprising the following preparation steps:
(1) cutting the carbon paper, soaking the cut carbon paper into a soaking solution according to the mass ratio of 1: 10, heating in a heat-preservation water bath, standing and cooling to room temperature, filtering, collecting the soaked carbon paper, washing and drying to obtain modified carbon paper; stirring and mixing 1, 3-dioxolane and xylene according to the mass ratio of 1: 1, standing to obtain a dissolving solvent, adding polydimethylsiloxane into the dissolving solvent according to the mass ratio of 1: 20, stirring for dissolving, performing ultrasonic dispersion, collecting a dispersion dissolving solution, adding modified carbon paper into the dispersion dissolving solution according to the mass ratio of 1: 15, stirring, mixing, soaking for 3-5 hours, filtering, collecting a filter cake, performing leaching treatment and drying to obtain etched and coated modified carbon paper;
(2) respectively weighing 45-50 parts by weight of deionized water, 1-2 parts by weight of manganese sulfate, 1-2 parts by weight of ammonium persulfate and 1-2 parts by weight of ammonium sulfate, adding the weighed materials into a beaker, stirring, mixing, carrying out hydrothermal heat preservation reaction to obtain a mixed reaction liquid, filtering, collecting a filter cake, washing and drying to obtain a reactant; respectively weighing 45-50 parts by weight of deionized water, 1-2 parts by weight of dopamine and 1-2 parts by weight of reactants, placing the deionized water, the dopamine and the reactants into a beaker, stirring and mixing the mixture and adjusting the pH value to 8.5, stirring and mixing the mixture and carrying out heat preservation reaction, standing and cooling the mixture to room temperature and filtering the mixture, collecting a filter cake, placing the filter cake into a tubular atmosphere furnace, introducing argon to remove air, drying the filter cake after the introduction is finished, heating the filter cake, and carrying out heat preservation calcination to obtain modified composite particles;
(3) respectively weighing 45-50 parts by weight of graphene water suspension, 1-2 parts by weight of modified composite particles and 45-50 parts by weight of deionized water, stirring, mixing, placing in a mortar for grinding and dispersing, collecting dispersed slurry, placing in a hydrothermal reaction at 125-150 ℃ for 10-12 h to obtain a hydrothermal gel liquid; and respectively weighing 45-50 parts by weight of absolute ethyl alcohol, 1-2 parts by weight of polyvinyl butyral and 10-15 parts by weight of hydrothermal gel liquid, stirring and mixing, soaking the etched coated modified carbon paper into the hydrothermal gel liquid, soaking, drying, washing with a phenolic resin solution, drying, collecting to obtain dried coated modified carbon paper, placing the dried coated modified carbon paper into a flat vulcanizing machine, performing compression molding, and performing high-temperature treatment to obtain the carbon paper material for the high-toughness high-conductivity proton exchange membrane battery.
2. The carbon paper material for the high-toughness high-conductivity proton exchange membrane battery according to claim 1, wherein: the preparation method of the soaking solution comprises the steps of weighing 45-50 parts by weight of deionized water, 10-15 parts by weight of 25% sulfuric acid and 1-2 parts by weight of potassium permanganate respectively, placing the materials in a beaker, and stirring and mixing the materials to obtain the soaking solution.
3. The carbon paper material for the high-toughness high-conductivity proton exchange membrane battery according to claim 1, wherein: and the leaching treatment is to leach 1-2 times by using hydrofluoric acid solution with the mass fraction of 0.01%.
4. The carbon paper material for the high-toughness high-conductivity proton exchange membrane battery according to claim 1, wherein: the hydrothermal heat preservation reaction is a heat preservation reaction at 200-250 ℃ for 80-90 h.
5. The carbon paper material for the high-toughness high-conductivity proton exchange membrane battery according to claim 1, wherein: the pH value is adjusted to 8.5 by adopting 1% ammonia water by mass fraction.
6. The carbon paper material for the high-toughness high-conductivity proton exchange membrane battery according to claim 1, wherein: the argon gas introducing speed is 20-30 mL/min.
7. The carbon paper material for the high-toughness high-conductivity proton exchange membrane battery according to claim 1, wherein: the drying treatment, temperature rise heating and heat preservation calcining are drying at 100-110 ℃ to constant weight, then raising the temperature to 750-850 ℃ at 5 ℃/min, and carrying out heat preservation calcining for 3-5 h.
8. The carbon paper material for the high-toughness high-conductivity proton exchange membrane battery according to claim 1, wherein: the concentration of the graphene aqueous suspension is 1% by mass.
9. The carbon paper material for the high-toughness high-conductivity proton exchange membrane battery according to claim 1, wherein: the compression molding is performed at the curing temperature of 165-170 ℃ and under 10-15 MPa.
10. The carbon paper material for the high-toughness high-conductivity proton exchange membrane battery according to claim 1, wherein: the high-temperature treatment is carried out at 2750-2800 ℃ for 15-20 min.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111979774A (en) * | 2020-07-07 | 2020-11-24 | 广西大学 | Aminated graphene modified polyacrylonitrile active fiber and preparation method and application thereof |
| CN113161561A (en) * | 2021-04-26 | 2021-07-23 | 昆明理工大学 | Carbon cloth modified with MOFs-derived Fe2O3, and preparation method and application thereof |
| CN113422074A (en) * | 2021-06-24 | 2021-09-21 | 焦作大学 | Pretreatment method of carbon-based electrode material of electrochemical system |
| CN114597428A (en) * | 2022-03-10 | 2022-06-07 | 湖南金博氢能科技有限公司 | Flexible carbon paper, preparation method thereof, gas diffusion layer and fuel cell |
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2019
- 2019-12-24 CN CN201911346111.7A patent/CN111129555A/en not_active Withdrawn
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111979774A (en) * | 2020-07-07 | 2020-11-24 | 广西大学 | Aminated graphene modified polyacrylonitrile active fiber and preparation method and application thereof |
| CN113161561A (en) * | 2021-04-26 | 2021-07-23 | 昆明理工大学 | Carbon cloth modified with MOFs-derived Fe2O3, and preparation method and application thereof |
| CN113422074A (en) * | 2021-06-24 | 2021-09-21 | 焦作大学 | Pretreatment method of carbon-based electrode material of electrochemical system |
| CN114597428A (en) * | 2022-03-10 | 2022-06-07 | 湖南金博氢能科技有限公司 | Flexible carbon paper, preparation method thereof, gas diffusion layer and fuel cell |
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Application publication date: 20200508 |