CN112242533A - Fuel cell bipolar plate based on carbon nanotube membrane composite material and preparation method and application thereof - Google Patents
Fuel cell bipolar plate based on carbon nanotube membrane composite material and preparation method and application thereof Download PDFInfo
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- CN112242533A CN112242533A CN201910826644.9A CN201910826644A CN112242533A CN 112242533 A CN112242533 A CN 112242533A CN 201910826644 A CN201910826644 A CN 201910826644A CN 112242533 A CN112242533 A CN 112242533A
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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
- H01M8/02—Details
- H01M8/0202—Collectors; Separators, e.g. bipolar separators; Interconnectors
- H01M8/0204—Non-porous and characterised by the material
- H01M8/0223—Composites
- H01M8/0226—Composites in the form of mixtures
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
- B29B15/00—Pretreatment of the material to be shaped, not covered by groups B29B7/00 - B29B13/00
- B29B15/08—Pretreatment of the material to be shaped, not covered by groups B29B7/00 - B29B13/00 of reinforcements or fillers
- B29B15/10—Coating or impregnating independently of the moulding or shaping step
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C43/00—Compression moulding, i.e. applying external pressure to flow the moulding material; Apparatus therefor
- B29C43/02—Compression moulding, i.e. applying external pressure to flow the moulding material; Apparatus therefor of articles of definite length, i.e. discrete articles
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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
- H01M8/02—Details
- H01M8/0202—Collectors; Separators, e.g. bipolar separators; Interconnectors
- H01M8/0204—Non-porous and characterised by the material
- H01M8/0213—Gas-impermeable carbon-containing materials
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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
- H01M8/02—Details
- H01M8/0202—Collectors; Separators, e.g. bipolar separators; Interconnectors
- H01M8/0204—Non-porous and characterised by the material
- H01M8/0221—Organic resins; Organic polymers
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29L—INDEXING SCHEME ASSOCIATED WITH SUBCLASS B29C, RELATING TO PARTICULAR ARTICLES
- B29L2007/00—Flat articles, e.g. films or sheets
- B29L2007/002—Panels; Plates; Sheets
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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
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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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Abstract
The invention provides a fuel cell bipolar plate based on a carbon nanotube membrane composite material, and a preparation method and application thereof, wherein the fuel cell bipolar plate is the carbon nanotube membrane composite material comprising a carbon nanotube membrane and a resin matrix, and the weight ratio of the carbon nanotube membrane to the resin matrix is 1.5: 1-3: 1; and wherein the conductivity of the carbon nanotube film composite material is not less than 103S/cm. The fuel cell bipolar plate of the present invention has high electricityConductivity and mechanical strength, and excellent corrosion resistance.
Description
Technical Field
The invention relates to a fuel cell bipolar plate based on a carbon nanotube membrane composite material, and a preparation method and application thereof.
Background
A Fuel Cell (Fuel Cell) is an energy conversion device capable of directly converting chemical energy into electric energy, and has the advantages of high energy conversion efficiency (40-60%), environmental friendliness, high starting speed, long service life and the like. Since the advent, fuel cells have been regarded as one of the most potential clean and efficient energy conversion technologies in the 21 st century, because of these outstanding advantages, they have received much attention from governments of various countries.
The Proton Exchange Membrane Fuel Cell (Proton Exchange Membrane Fuel Cell, abbreviated as PEMFC) uses hydrogen as Fuel and air or oxygen as oxidant, and has the common characteristics of Fuel cells (such as high energy conversion efficiency, environmental friendliness, etc.), and simultaneously has the outstanding characteristics of quick start at room temperature (working temperature is generally between 60 and 100 ℃), no electrolyte loss, easy discharge of water, long service life, high specific power and energy, and the like, and particularly, the discharge is water, so that no pollution and zero discharge are realized. The proton exchange membrane fuel cell has wide application prospect in the fields of aerospace, new energy automobiles, mobile power supplies, fixed power stations and the like.
However, the high cost and low energy density of fuel cells have largely restricted it from further expanding its commercial application. The bipolar plate (also called current collecting plate) is one of the important components of the fuel cell, mainly plays the role of transporting and distributing fuel, and isolating the anode in the stack, and the performance quality of the bipolar plate directly affects the output power and the service life of the fuel cell, and the cost of the bipolar plate generally occupies more than 15% of the cost of the fuel cell, and the weight proportion is nearly 60%. Therefore, it is very important to develop a lightweight, highly conductive, and strengthened bipolar plate material.
The bipolar plate mainly comprises three systems of a nonporous graphite bipolar plate, a metal bipolar plate and a composite material bipolar plate. Among them, the nonporous graphite bipolar plate is the most mature and commercialized bipolar plate at present, and has better chemical stability and good corrosion resistance. However, the nonporous graphite bipolar plate has high cost, high brittleness, high weight, and poor strength and processability. The metal bipolar plate has the advantages of fast development, excellent mechanical property, processability, conductivity and the like, and is easy for batch production and cost reduction. Metal bipolar plates have the disadvantages of poor corrosion resistance and susceptibility to particle contamination after coating failure. The composite material bipolar plate is a research hotspot in recent years, and has the advantages of a non-porous graphite bipolar plate and a metal bipolar plate, for example, compared with the metal bipolar plate, the composite material bipolar plate can reduce weight and further realize performance regulation and control. The existing composite material bipolar plate has the main problems that the preparation cost is high, the process period is long, the conductivity and the mechanical strength are still required to be improved, and the large-scale wide popularization in the field of large-scale energy storage galvanic pile is difficult.
Disclosure of Invention
Therefore, the present invention is directed to provide a fuel cell bipolar plate based on a carbon nanotube membrane composite material, which has high electrical conductivity and mechanical strength, and excellent corrosion resistance, and a method for preparing the same.
The purpose of the invention is realized by the following technical scheme.
On one hand, the invention provides a fuel cell bipolar plate based on a carbon nanotube membrane composite material, wherein the fuel cell bipolar plate is the carbon nanotube membrane composite material comprising a carbon nanotube membrane and a resin matrix, and the weight ratio of the carbon nanotube membrane to the resin matrix is 1.5: 1-3: 1; and wherein the conductivity of the carbon nanotube film composite material is not less than 103S/cm。
In the present invention, the term "composite material" refers to a composite material in which the matrix is a thermoplastic or thermosetting resin and the reinforcement or three-dimensional skeleton is a carbon nanotube film.
In the invention, the carbon nanotube film and the resin matrix are selected to prepare the bipolar plate of the fuel cell, and the bipolar plate of the fuel cell is preparedThe content of the carbon nano tube can reach 60-75 wt%, and the electronic conductivity (the conductivity is more than or equal to 10) of the bipolar plate of the fuel cell3S/cm) can meet the requirement of heavy-current operation of the galvanic pile, and the overall strength and modulus of the bipolar plate of the fuel cell can meet the bearing requirements of severe working conditions such as vehicle-mounted working and the like. Further, the resin matrix may be impregnated into the gaps in the carbon nanotube film, thereby imparting sufficient structural compactness to the fuel cell bipolar plate while improving corrosion resistance and gas tightness of the fuel cell bipolar plate.
According to the fuel cell bipolar plate provided by the invention, the carbon nanotube film is a carbon nanotube network structure containing gaps formed by continuously growing carbon nanotubes.
The bipolar plate of the fuel cell provided by the invention has the advantages that the thickness of the carbon nanotube film is 5-20 mu m, the number of walls of carbon nanotubes in the carbon nanotube film is 3-6, and the average diameter is 7-8 nm.
According to the fuel cell bipolar plate provided by the present invention, wherein the carbon nanotube film may be prepared by any method known in the art. In some embodiments, examples of the carbon nanotube film include, but are not limited to: CVD (chemical vapor deposition) method carbon nanotube films, array method carbon nanotube films, and floating catalyst method carbon nanotube films. In some preferred embodiments, the carbon nanotube film is a floating catalyst carbon nanotube film or a CVD array carbon nanotube film.
The bipolar plate of the fuel cell provided by the invention is characterized in that the thickness of the carbon nanotube film is 10-20 μm.
According to the fuel cell bipolar plate provided by the invention, the resin matrix can be thermoplastic resin or thermosetting resin. Preferably, the resin matrix is a resin that is soluble in organic solvents such as N, N-Dimethylformamide (DMF), dimethyl sulfoxide (DMSO), and acetone, whereby the resin matrix may be formulated into a solution to wet the carbon nanotube film, thereby forming the carbon nanotube film composite.
In some embodiments, examples of suitable resin matrices include, but are not limited to: epoxy resins, bismaleimide resins, polyvinylidene fluoride (PVDF), polyethylene terephthalate (PET), Polycarbonate (PC), and polyvinyl alcohol (PVA).
According to the fuel cell bipolar plate provided by the invention, the conductivity of the carbon nanotube film composite material can be further adjusted by selecting the type of the resin matrix and/or controlling the content of the carbon nanotube film.
In some embodiments, the resin matrix is an epoxy resin or a bismaleimide resin.
Fuel cell bipolar plates are provided according to the present invention, wherein examples of suitable epoxy resins include, but are not limited to: type E51 epoxy and type 628 epoxy.
Fuel cell bipolar plates are provided according to the present invention, wherein examples of suitable bismaleimide resins include, but are not limited to: 8911 bismaleimide resin, 5428 bismaleimide resin and 4501 bismaleimide resin.
The fuel cell bipolar plate provided by the invention has the hydrogen permeability coefficient of the carbon nano tube membrane composite material at the temperature of 300K<1×10-14molH2m-1s-1Pa-0.5。
The bipolar plate of the fuel cell provided by the invention has the advantages that the thickness of the carbon nanotube film composite material is 0.01-0.05 mm, and preferably 0.02-0.03 mm.
According to the fuel cell bipolar plate provided by the invention, the carbon nanotube film composite material comprises a multilayer carbon nanotube film.
The bipolar plate of the fuel cell provided by the invention is characterized in that the density of the carbon nanotube film composite material is 1-1.2 g/cm3。
In the present invention, the density of the carbon nanotube film composite can be measured according to GB/T20042.6-2011.
According to the fuel cell bipolar plate provided by the invention, the tensile strength of the carbon nanotube film composite material is more than or equal to 1GPa, and the tensile modulus is more than or equal to 30 GPa. In some embodiments where the resin matrix is a thermoset resin, the tensile strength of the fuel cell bipolar plate is greater than or equal to 2.5GPa and the tensile modulus is greater than or equal to 80 GPa.
According to the fuel cell bipolar plate provided by the invention, the thermal conductivity of the carbon nanotube film composite material is not less than 30W/(m.K).
In another aspect, the present invention provides a method for preparing the fuel cell bipolar plate, wherein the method comprises the following steps:
(1) placing the carbon nanotube film in a diluent of a resin matrix for impregnation;
(2) taking out and drying the carbon nano tube membrane material impregnated by the resin matrix obtained in the step (1);
(3) and (3) carrying out cold pressing and hot pressing on the carbon nano tube membrane material impregnated with the dried resin matrix obtained in the step (2).
According to the preparation method provided by the invention, the concentration of the diluent of the resin matrix in the step (1) is 1-10 wt%, preferably 2-5 wt%.
According to the preparation method provided by the present invention, examples of the solvent suitable for preparing the diluent of the resin matrix include, but are not limited to: n, N-dimethylformamide, dimethyl sulfoxide and acetone.
According to the preparation method provided by the invention, in the step (1), the carbon nanotube film is immersed in the diluent of the resin matrix for 0.5-3 hours, for example, 2 hours. By immersing the carbon nanotube film in the diluent of the resin matrix for the above time, it can be effectively ensured that the resin sufficiently permeates the carbon nanotube film.
According to the preparation method provided by the invention, the drying in the step (2) is carried out under vacuum condition. In some embodiments, the drying in step (2) is performed under a vacuum of 0.2 to 0.5 KPa.
According to the preparation method provided by the invention, the drying in the step (2) is carried out at the temperature of 50-80 ℃.
According to the preparation method provided by the invention, the drying in the step (2) is carried out for 0.5-1 hour.
According to the preparation method provided by the invention, the step (3) comprises the following steps:
(3a) carrying out cold pressing on the carbon nano tube membrane material impregnated by the dried resin matrix to obtain a cold-pressed carbon nano tube membrane material layer; and
(3b) and (3) carrying out hot pressing on 1, 2 or more cold-pressed carbon nanotube film material layers.
According to the preparation method provided by the invention, the cold pressing is carried out at the temperature of-10-30 ℃. In some embodiments, the cold pressing is performed at a temperature of 10 ℃ to 30 ℃.
According to the preparation method provided by the invention, the pressure of cold pressing is 5-10 MPa.
According to the preparation method provided by the invention, the cold pressing time is 0.5-3 hours.
According to the preparation method provided by the invention, the hot pressing temperature is 190-220 ℃, the pressure is 2-4 MPa, and the time is 1-2 hours.
According to the preparation method provided by the invention, the heating rate of hot pressing is 10-15 ℃/min.
According to the preparation method provided by the invention, the step (3b) comprises the following steps:
(I) laying 1, 2 or more cold-pressed carbon nanotube film material layers between two polytetrafluoroethylene films, heating to 190-220 ℃ at the speed of 10-15 ℃/min, and preserving heat for 1-2 hours;
(II) pressurizing to 2-4 MPa, and keeping the temperature and pressure for 1-2 hours; and
(III) cooling along with the furnace under the pressure of 2-4 MPa.
In yet another aspect, the invention also provides a proton exchange membrane fuel cell, which comprises an anode, a cathode and a proton exchange membrane, wherein the anode and/or the cathode comprises the fuel cell bipolar plate.
The fuel cell bipolar plate of the present invention has the following advantages:
(1) in the invention, the carbon nanotube film and the resin matrix are selected to prepare the fuel cell bipolar plate, the content of the carbon nanotubes in the fuel cell bipolar plate can reach 60-75 wt%,the fuel cell bipolar plate forms a through continuous carbon nano tube three-dimensional network, has excellent conductivity and electronic conductivity (the conductivity is more than or equal to 10)3S/cm) can meet the requirement of large-current operation of the galvanic pile. Further, the resin matrix may be impregnated into the gaps in the carbon nanotube film, thereby imparting sufficient structural compactness to the fuel cell bipolar plate while improving corrosion resistance and gas tightness of the fuel cell bipolar plate.
(2) The carbon nano tube film composite material of the invention overcomes the problem that the mechanical property of the conventional carbon nano tube reinforced composite material is reduced due to the agglomeration of the carbon nano tubes, and the mechanical property is greatly improved. Particularly, the tensile strength of the carbon nanotube film composite material is more than or equal to 1GPa, the tensile modulus is more than or equal to 30GPa, and the overall strength and modulus can meet the bearing requirements of severe working conditions such as vehicle-mounted working and the like.
(3) Compared with the conventional nonporous graphite bipolar plate, the carbon nanotube film composite material has low density of only 1-1.2 g/cm3Therefore, the weight can be greatly reduced, the weight reduction and thinning are realized, and the cost is reduced and the energy density of the fuel cell stack system is improved.
(4) The carbon nanotube film composite material is an excellent conductor, has the thermal conductivity of more than 30W/(m.K), can radiate redundant heat, and ensures the uniform temperature distribution of the battery.
(5) The conductivity of the carbon nanotube film composite material is more than or equal to 103S/cm, the generation of heat can be reduced, and the power generation efficiency of the battery is improved.
(6) Hydrogen permeability coefficient of the carbon nanotube film composite material of the present invention<1×10-14molH2m-1s-1Pa-0.5The gas barrier property is good, and the cathode reactant and the anode reactant can be strictly separated, so that the mixing of hydrogen and oxygen is avoided.
(7) In the carbon nanotube film composite material, the resin matrix such as epoxy resin and PVDF coats the carbon nanotube film, so that the carbon nanotube film composite material has good chemical stability and stable property under an acidic condition, and can ensure long-term stable operation of a fuel cell.
(8) The carbon nanotube film composite material has excellent mechanical property, is not easy to damage under certain assembly pressure, and can reach or even exceed 35MPa of the programmed target tensile modulus of United states DOE 2025.
(9) The carbon nanotube film composite material is formed by hot pressing, has a smooth surface, reactants can smoothly pass through the surface and are uniformly distributed, reaction products can be smoothly discharged, and adverse phenomena such as blockage, water flooding and the like are avoided.
(10) The carbon nanotube film composite material does not contain easily decomposed and dispersed substances, particularly does not contain components poisoning a proton exchange membrane, and has stable physical and chemical properties.
(11) The carbon nanotube film composite material has excellent mechanical property, meets related use conditions, meets the mechanical vibration requirement, and has good fatigue resistance.
(12) The carbon nanotube film composite bipolar plate overcomes the complex operation that the prior graphite bipolar plate needs to be cured by impregnating resin and then is subjected to carbonization process treatment and runner molding process treatment, can simply complete resin impregnation curing and runner molding by a resin diluent impregnation process and a hot-press molding process, greatly simplifies the production treatment process, shortens the period requirement and reduces the production and processing cost of the bipolar plate. In addition, in the present invention, the impregnation and hot pressing processes may be performed in batch, and may be cut after the flow channel formation to obtain a fuel cell bipolar plate of a desired formation and size.
Drawings
The accompanying drawings, which are incorporated in and constitute a part of this application, illustrate embodiments of the invention and, together with the description, serve to explain the invention and not to limit the invention. In the drawings:
fig. 1 shows a schematic view of a manufacturing process of a bipolar plate for a fuel cell of the present invention.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. The following description of at least one exemplary embodiment is merely illustrative in nature and is in no way intended to limit the invention, its application, or uses. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
SEM characterization
And performing microstructure characterization on the carbon nanotube film and the carbon nanotube film composite material by adopting a JSM-7500F cold field emission scanning electron microscope.
Tensile Strength and tensile modulus
An Instron3344 mechanical testing machine is adopted to carry out tensile test on the carbon nanotube film composite material, the sample size is 25mm multiplied by 2mm, the span is 15mm, the tensile speed is 0.5mm/min, and each test result is the average value of 5 effective tests.
Electrical conductivity of
The electrical conductivity of the carbon nanotube film composite of the present invention was measured according to the "bipolar plate material resistance test" in GB/T20042.6-2011.
Density test
The density of the carbon nanotube film composite of the present invention was measured according to "bipolar plate material density test" in GB/T20042.6-2011.
Thermal conductivity
The thermal conductivity of the carbon nanotube film composite of the present invention was measured by a laser pulse method.
Coefficient of hydrogen permeability
The hydrogen permeability coefficient was calculated by the following formula.
Wherein J is the permeation flow of hydrogen in the bipolar plate; c is the dissolved concentration of hydrogen at two ends of the bipolar plate; l is the thickness of the bipolar plate; d is a hydrogen atom in the bisDiffusion coefficient in the plate; puAnd PdThe hydrogen pressure at the near surface of the upper end and the lower end of the bipolar plate respectively; Φ — D × k is the hydrogen permeability coefficient of the bipolar plate. (J × L) and Δ P0.5There is a linear relationship between the hydrogen permeation coefficient phi and the pressure difference between the upper and lower surfaces of the bipolar plate Δ P and the permeation flux of hydrogen (J × L)0.5The slope therebetween, and measured accordingly. Further, in the present invention, the hydrogen permeability coefficient is measured at a temperature of 300K.
Example 1
This example illustrates the preparation of carbon nanotube films using a floating catalyst process.
The main devices used are as follows: the carrier gas system comprises a gas circuit and a flow controller; a carbon source/catalyst propulsion system comprising a micro-injection pump and a carbon source/catalyst mixed solution; the high-temperature tube furnace is provided with a 99 pure corundum tube, the maximum temperature is 1600 ℃, and the length of a constant-temperature area is 20 cm; and a tail gas exhaust system.
Under the protection of argon, a carbon source ethanol, thiophene and catalyst ferrocene mixed system (the molar ratio of ethanol to thiophene to ferrocene is 1:1:0.05) is injected into a 1300 ℃ high-temperature tubular furnace at the speed of 0.15ml/min by a carbon source/catalyst propulsion system. And collecting the formed carbon nanotube aerogel at the other end of the high-temperature tube furnace by using a winding device, and spraying 70% ethanol aqueous solution on line to prepare the carbon nanotube film.
And characterizing the prepared carbon nanotube film by adopting SEM. The result shows that the carbon nanotube film has a thickness of 10 μm, a wall number of 3 to 6, and an average diameter of 7 to 8 nm. Further, the surface density of the carbon nanotube film was 0.01g/cm2。
Example 2
Referring to fig. 1, a process flow for preparing a fuel cell bipolar plate is shown.
(1) Preparing N, N-dimethylformamide diluent of E51 type epoxy resin with the concentration of 5 weight percent;
(2) the carbon nanotube film prepared in example 1 was immersed in an N, N-dimethylformamide diluted solution of E51 type epoxy resin for 2 hours;
(3) taking out the carbon nanotube film, absorbing excessive diluent on two surfaces of the carbon nanotube film by using breathable tetrafluoro cloth, then placing the carbon nanotube film in a vacuum oven, and vacuumizing for 0.5 hour at 80 ℃, wherein the vacuum degree is 0.5 KPa;
(4) placing the carbon nanotube film material obtained in the step (3) between two flat polytetrafluoroethylene films, and placing the carbon nanotube film material in a press to perform cold pressing under the pressure of 5MPa to obtain a cold-pressed carbon nanotube film material layer with the thickness of about 0.01mm, wherein the cold pressing temperature is 10 ℃ and the time is 3 hours;
(5) laying 3 layers of cold-pressed carbon nanotube film material layers between two flat polytetrafluoroethylene films for hot pressing, wherein the hot pressing process comprises the following steps: the heating rate is 15 ℃/min, the temperature is kept for 1 hour after the temperature reaches 220 ℃, then the pressure is increased to 4MPa, the temperature and the pressure are kept for 2 hours, and the multi-layer carbon nano tube film composite material is obtained after furnace cooling under the pressure of 4 MPa.
Cutting the carbon nanotube film composite material into a regular shape of 50mm × 50mm, and calculating the weight ratio of the carbon nanotube film to the resin matrix according to the surface density of the carbon nanotube film and the weight of the carbon nanotube film composite material to be 3: 1.
Example 3
Referring to fig. 1, a process flow for preparing a fuel cell bipolar plate is shown.
(1) Preparing an N, N-dimethylformamide diluent of polyvinylidene fluoride with the concentration of 2 weight percent by adopting polyvinylidene fluoride which is purchased from Solef PVDF 5130 of Solewy company in America;
(2) the carbon nanotube film prepared in example 1 was immersed in an N, N-dimethylformamide diluent of polyvinylidene fluoride for 0.5 hour;
(3) taking out the carbon nanotube film, absorbing excessive diluent on two surfaces of the carbon nanotube film by using breathable tetrafluoro cloth, then placing the carbon nanotube film in a vacuum oven, and vacuumizing for 1 hour at 50 ℃, wherein the vacuum degree is 0.2 KPa;
(4) placing the carbon nanotube film material obtained in the step (3) between two flat polytetrafluoroethylene films, and placing the carbon nanotube film material in a press to perform cold pressing under the pressure of 10MPa to obtain a cold-pressed carbon nanotube film material layer with the thickness of about 0.01mm, wherein the cold pressing temperature is 30 ℃ and the time is 0.5 hour;
(5) laying 2 layers of cold-pressed carbon nanotube film material layers between two flat polytetrafluoroethylene films for hot pressing, wherein the hot pressing process comprises the following steps: the heating rate is 10 ℃/min, after the temperature reaches 190 ℃, the temperature is preserved for 2 hours, then the pressure is increased to 2MPa, the temperature and pressure are preserved for 1 hour, and the multilayer carbon nanotube film composite material is obtained after furnace cooling under the pressure of 2 MPa.
Cutting the carbon nanotube film composite material into a regular shape of 50mm × 50mm, and calculating the weight ratio of the carbon nanotube film to the resin matrix according to the surface density of the carbon nanotube film and the weight of the carbon nanotube film composite material to be 1.5: 1.
Example 4
Referring to fig. 1, a process flow for preparing a fuel cell bipolar plate is shown.
(1) Preparing an 8911 bismaleimide resin N, N-dimethylformamide diluent with the concentration of 3 weight percent;
(2) the carbon nanotube film prepared in example 1 was immersed in an N, N-dimethylformamide diluted solution of 8911 bismaleimide resin for 1.5 hours;
(3) taking out the carbon nanotube film, absorbing excessive diluent on two surfaces of the carbon nanotube film by using breathable tetrafluoro cloth, then placing the carbon nanotube film in a vacuum oven, and vacuumizing for 0.5 hour at 80 ℃, wherein the vacuum degree is 0.5 KPa;
(4) placing the carbon nanotube film material obtained in the step (3) between two flat polytetrafluoroethylene films, and placing the carbon nanotube film material in a press to perform cold pressing under the pressure of 5MPa to obtain a cold-pressed carbon nanotube film material layer with the thickness of about 0.01mm, wherein the cold pressing temperature is 10 ℃ and the time is 3 hours;
(5) laying 5 layers of cold-pressed carbon nanotube film material layers between two flat polytetrafluoroethylene films for hot pressing, wherein the hot pressing process comprises the following steps: the heating rate is 15 ℃/min, the temperature is kept for 1 hour after the temperature reaches 220 ℃, then the pressure is increased to 4MPa, the temperature and the pressure are kept for 2 hours, and the multi-layer carbon nano tube film composite material is obtained after furnace cooling under the pressure of 4 MPa.
Cutting the carbon nanotube film composite material into a regular shape of 50mm multiplied by 50mm, and calculating the weight ratio of the carbon nanotube film to the resin matrix according to the surface density of the carbon nanotube film and the weight of the carbon nanotube film composite material, wherein the weight ratio is 3: 1.
The properties of the carbon nanotube film composites prepared in examples 2-4 are shown in tables 1 and 2.
TABLE 1 Properties of carbon nanotube film composites
| Density of | Thickness of | Electrical conductivity of | Thermal conductivity | |
| Example 2 | 1.10g/cm3 | 0.02mm | 2.03×103S/cm | 30W/(m·K) |
| Example 3 | 1.06g/cm3 | 0.02mm | 1.01×103S/cm | 31W/(m·K) |
| Example 4 | 1.15g/cm3 | 0.03mm | 2.37×103S/cm | 35W/(m·K) |
TABLE 2 hydrogen permeation coefficient and mechanical Properties of carbon nanotube film composites
| Coefficient of hydrogen permeability | Tensile strength | Tensile modulus | |
| Example 2 | 0.92×10-14molH2m-1s-1Pa-0.5 | 2.5GPa | 80GPa |
| Example 3 | 0.87×10-14molH2m-1s-1Pa-0.5 | 1.1GPa | 30GPa |
| Example 4 | 0.93×10-14molH2m-1s-1Pa-0.5 | 2.7GPa | 96GPa |
The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention, and various modifications and changes may be made by those skilled in the art. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. A fuel cell bipolar plate based on a carbon nanotube membrane composite material is disclosed, wherein the fuel cell bipolar plate is the carbon nanotube membrane composite material comprising a carbon nanotube membrane and a resin matrix, and the weight ratio of the carbon nanotube membrane to the resin matrix is 1.5: 1-3: 1; and wherein the conductivity of the carbon nanotube film composite material is not less than 103S/cm。
2. The fuel cell bipolar plate according to claim 1, wherein the carbon nanotube film has a thickness of 5 to 20 μm, a wall number of carbon nanotubes in the carbon nanotube film is 3 to 6, and an average diameter of 7 to 8 nm;
preferably, the carbon nanotube film is a CVD method carbon nanotube film, an array method carbon nanotube film or a floating catalysis method carbon nanotube film, preferably a floating catalysis method carbon nanotube film or a CVD array method carbon nanotube film;
preferably, the thickness of the carbon nanotube film is 10-20 μm;
preferably, the resin matrix is epoxy resin, bismaleimide resin, polyvinylidene fluoride, polyethylene terephthalate, polycarbonate or polyvinyl alcohol, and preferably is epoxy resin or bismaleimide resin;
preferably, the resin matrix is an E51 type epoxy resin, a 628 type epoxy resin, a 911 bismaleimide resin, a 5428 bismaleimide resin or a 4501 bismaleimide resin.
3. The fuel cell bipolar plate of claim 1 or 2, wherein the carbon nanotube membrane composite has a hydrogen permeability coefficient at a temperature of 300K<1×10-14molH2m-1s-1Pa-0.5；
Preferably, the thickness of the carbon nanotube film composite material is 0.01-0.05 mm, and preferably 0.02-0.03 mm.
4. The fuel cell bipolar plate of any one of claims 1 to 3, wherein the carbon nanotube film composite comprises a multilayer carbon nanotube film;
preferably, the density of the carbon nanotube film composite material is 1-1.2 g/cm3。
5. The method for manufacturing a fuel cell bipolar plate according to any one of claims 1 to 4, wherein the manufacturing method comprises the steps of:
(1) placing the carbon nanotube film in a diluent of a resin matrix for impregnation;
(2) taking out and drying the carbon nano tube membrane material impregnated by the resin matrix obtained in the step (1);
(3) and (3) carrying out cold pressing and hot pressing on the carbon nano tube membrane material impregnated with the dried resin matrix obtained in the step (2).
6. The method according to claim 5, wherein the concentration of the diluted resin matrix solution in the step (1) is 1 to 10 wt%, preferably 2 to 5 wt%;
preferably, the solvent of the dilution liquid of the resin matrix is one selected from the group consisting of N, N-dimethylformamide, dimethyl sulfoxide and acetone.
7. The production method according to claim 5 or 6, wherein the carbon nanotube film is immersed in the diluted solution of the resin matrix for 0.5 to 3 hours, for example, 2 hours in step (1);
preferably, the drying in step (2) is performed under vacuum;
more preferably, the drying in the step (2) is carried out under the vacuum degree of 0.2-0.5 KPa;
more preferably, the drying in the step (2) is carried out at a temperature of 50-80 ℃;
more preferably, the drying in step (2) is performed for 0.5 to 1 hour.
8. The production method according to any one of claims 5 to 7, wherein the step (3) includes the steps of:
(3a) carrying out cold pressing on the carbon nano tube membrane material impregnated by the dried resin matrix to obtain a cold-pressed carbon nano tube membrane material layer;
(3b) hot-pressing 1, 2 or more cold-pressed carbon nanotube film material layers;
preferably, the cold pressing is carried out at a temperature of-10 ℃ to 30 ℃, such as 10 ℃ to 30 ℃;
preferably, the pressure of the cold pressing is 5-10 MPa;
preferably, the cold pressing time is 0.5-3 hours;
preferably, the hot pressing temperature is 190-220 ℃, the pressure is 2-4 MPa, and the time is 1-2 hours;
preferably, the heating rate of the hot pressing is 10-15 ℃/min.
9. The production method according to any one of claims 5 to 8, wherein the step (3b) includes the steps of:
(I) laying 1, 2 or more cold-pressed carbon nanotube film material layers between two polytetrafluoroethylene films, heating to 190-220 ℃ at the speed of 10-15 ℃/min, and preserving heat for 1-2 hours;
(II) pressurizing to 2-4 MPa, and keeping the temperature and pressure for 1-2 hours;
(III) cooling along with the furnace under the pressure of 2-4 MPa.
10. A proton exchange membrane fuel cell comprising an anode, a cathode and a proton exchange membrane, the anode and/or the cathode comprising a fuel cell bipolar plate according to any one of claims 1 to 4.
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