CN111463447B - Laminated unipolar plate, preparation method thereof, laminated bipolar plate comprising laminated unipolar plate and application - Google Patents
Laminated unipolar plate, preparation method thereof, laminated bipolar plate comprising laminated unipolar plate and application Download PDFInfo
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- CN111463447B CN111463447B CN202010304021.8A CN202010304021A CN111463447B CN 111463447 B CN111463447 B CN 111463447B CN 202010304021 A CN202010304021 A CN 202010304021A CN 111463447 B CN111463447 B CN 111463447B
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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
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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
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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
- H01M8/0206—Metals or alloys
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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
- H01M8/0223—Composites
- H01M8/0228—Composites in the form of layered or coated products
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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 laminated unipolar plate, a preparation method thereof, a laminated bipolar plate comprising the laminated unipolar plate and application of the laminated bipolar plate, wherein the laminated unipolar plate comprises a metal layer, a composite carbon powder layer and a composite material layer. The laminated bipolar plate provided by the invention can obviously improve the conductivity of the through surface of the polar plate, solve the problem of hydrogen permeation of the carbon-based material polar plate, reduce the thickness of the polar plate and be beneficial to the improvement of the volume power density of the pile.
Description
Technical Field
The invention belongs to the technical field of fuel cells, and relates to a laminated unipolar plate, a preparation method thereof, a laminated bipolar plate containing the laminated unipolar plate and application of the laminated bipolar plate.
Background
Energy technology, one of the pillar technologies of modern civilization, is already inseparable from environmental science. The starting point of energy technology development is bound to be closely combined with environmental science to solve the global energy crisis and environmental and ecological problems together so as to adapt to the global strategy of sustainable development. Thus, it is necessary to provide a great challenge to the energy source mode of another revolution. The fuel cell, as a device for directly converting chemical energy into electric energy, has the advantages of high efficiency, high reliability, good environmental benefits and the like, and becomes a hot spot of energy research in the new century, and is a main energy conversion mode possibly replacing an internal combustion engine.
The fuel cell directly converts chemical energy into electric energy through electrochemical reaction, and no thermal kinetic energy is converted in the process, so that the conversion efficiency is high; because there is no mechanical drive unit in the fuel cell, so the noise is extremely low, and the reliability is higher; when pure hydrogen is used as fuel, the electrochemical reaction product is only water; when hydrogen-rich gas is used as fuel, the electrochemical reaction product contains a small amount of carbon dioxide; therefore, the method has little pollutant emission and is a very clean energy mode.
Proton Exchange Membrane Fuel Cells (PEMFCs) are composed of a number of single cells, each of which is composed of a membrane electrode, a diffusion layer, and a bipolar plate. The bipolar plate is an important component of PEMFC, and its cost and weight account for 45% and 80% of PEMFC, respectively, and its high cost causes the PEMFC to be expensive. Therefore, the breakthrough of the bipolar plate material and the preparation process thereof is beneficial to the industrialization of the PEMFC. The bipolar plate is used for separating gas, guiding fuel reaction gas into the fuel cell through a flow field, collecting and conducting current and supporting the membrane electrode, and simultaneously has the function of heat dissipation of the whole cell system. Therefore, to meet the functional requirements of bipolar plates, the material of the bipolar plate must have good electrical conductivity, excellent gas tightness, excellent corrosion resistance, good thermal conductivity, and easy processing.
The bipolar plate at present is mainly researched by three categories, namely a metal plate, a pure graphite plate and a composite plate. The metal bipolar plate has good electric and thermal conductivity, the air leakage problem can not occur, the gas flow channel can be formed by punching, and the mass production is easy to realize. However, the surface of the metal bipolar plate needs to be specially treated to improve the chemical stability, otherwise, the oxide film on the surface of the metal bipolar plate is thickened, the contact resistance is increased, and the battery performance is reduced. The pure graphite plate has good electrical conductivity, thermal conductivity and chemical stability, and the flow channel is generally processed by the pure graphite plate by adopting a traditional machining method, so that the processing process is long in time consumption and the production efficiency is not high; and the pure graphite plates are brittle, the internal pores are easy to cause gas leakage, and a certain thickness must be kept to ensure the gas tightness, so that the improvement of the volume ratio power and the weight ratio power of the pile is restricted. The graphite-based composite bipolar plate has the same corrosion resistance as graphite and excellent electrical conductivity and thermal conductivity, and the bipolar plate made of the material can be formed by a die pressing process, and a flow field can be formed at one time, so that the graphite-based composite bipolar plate is easy to form at one time, is suitable for large-scale production, and can reduce the production cost of the bipolar plate.
CN101447571A discloses a method for preparing a flexible graphite composite bipolar plate of a proton exchange membrane fuel cell, which comprises the steps of preparing an anode flow field, a cathode flow field and a water plate by a flexible graphite plate, and assembling the anode flow field, the cathode flow field and the water plate, a sealing frame and a separation plate into the bipolar plate; the method comprises the steps of prepressing a low-density flexible graphite plate under vacuum to obtain a graphite plate with the density of 0.65-0.75 g/cm3The plate is dipped in a low-viscosity resin solution in vacuum, subjected to surface treatment and drying, rolled or molded under a vacuum condition to form a flow field, and cured to obtain the flow field and the water plate made of the polymer/flexible graphite composite plate. And finally, forming the bipolar plate by the flow field and the water plate which are made of the polymer/flexible graphite composite plate, the sealing frame and the separation plate. CN101593837A discloses an expanded graphite/phenolic resin composite bipolar plate and a preparation method thereof, which is prepared from expanded graphite, thermoplastic phenolic resin and hexamethylenetetramine, and the preparation method comprises the following steps: mixing the expanded graphite with the aqueous solution of the thermoplastic phenolic resin, filtering, drying filter residues, ball-milling and mixing with hexamethylenetetramine, adding into a mold for mold pressing, reducing pressure, raising temperature, keeping the temperature for mold pressing, and demolding to obtain the expanded graphite/phenolic resin composite material bipolar plate. CN103117397A discloses a manufacturing process of a bipolar plate for a fuel cell, which utilizes expanded graphite as a carbon-based material and resin powder as a binder, and carbon black and small carbon black particles are added in the preparation of the composite materialThe particles help form conductive channels between the graphite particles, and the incorporation of carbon fibers into the composite bipolar plate results in good flexural strength by increasing electrical conductivity. The composite plates provided by the above patent applications mainly increase the mechanical strength by adding resin materials and carbon fiber materials, but do not pay much attention to the problem of improving the conductivity of the through surface of the bipolar plate and the problem of air tightness of the plate.
Therefore, it is desired to develop a bipolar plate having a high through-plane conductivity and capable of solving the hydrogen leakage problem of a carbon-based material plate.
Disclosure of Invention
The invention aims to provide a laminated unipolar plate, a preparation method thereof, a laminated bipolar plate comprising the laminated unipolar plate and application of the laminated bipolar plate. The laminated bipolar plate provided by the invention can obviously improve the conductivity of the through surface of the polar plate, solve the problem of hydrogen permeation of the carbon-based material polar plate, reduce the thickness of the polar plate and be beneficial to the improvement of the volume power density of the pile.
In order to achieve the purpose, the invention adopts the following technical scheme:
in a first aspect, the present invention provides a laminated unipolar plate, which is characterized by comprising a metal layer, a composite carbon powder layer and a composite material layer.
According to the invention, by adopting the mode of laminating the metal layer, the composite carbon powder layer and the composite material layer, the conductivity of the unipolar plate can be improved, the air tightness of the substrate is increased, the problem of hydrogen permeation of the carbon-based material polar plate is avoided, the thickness of the polar plate can be reduced, and the increase of the volume power density of the pile is facilitated.
In the present invention, the stacking order of the metal layer, the composite carbon powder layer and the composite material layer is not limited, and the metal layer, the composite carbon powder layer and the composite material layer may be sequentially arranged, or the composite carbon powder layer, the metal layer and the composite material layer may be sequentially arranged, or the metal layer, the composite material layer and the composite carbon powder layer may be sequentially arranged.
It is noted that the metal layer is preferably not used as the outer surface of the flow channel for the unipolar plate hydrogen or air when the unipolar plate is applied.
In the invention, the composite carbon powder layer comprises the following components in parts by weight of 100 parts:
carbon material 70-95 parts (e.g., 72 parts, 75 parts, 78 parts, 80 parts, 82 parts, 85 parts, 88 parts, 90 parts, 92 parts, etc.), thermoplastic resin powder 5-20 parts (e.g., 6 parts, 8 parts, 10 parts, 12 parts, 14 parts, 16 parts, 18 parts, etc.) and gas grown carbon fiber (VGCF)2-10 parts (e.g., 3 parts, 4 parts, 5 parts, 6 parts, 7 parts, 8 parts, 9 parts, etc.).
Preferably, the composite material layer comprises the following components by weight of 100 parts of the composite material layer:
60-95 parts of carbon material, 2-30 parts (for example, 5 parts, 8 parts, 10 parts, 12 parts, 15 parts, 18 parts, 20 parts, 25 parts and the like) of thermoplastic resin fiber, 1-10 parts (for example, 3 parts, 4 parts, 5 parts, 6 parts, 7 parts, 8 parts, 9 parts and the like) of gas grown carbon fiber, and 1-10 parts (for example, 3 parts, 4 parts, 5 parts, 6 parts, 7 parts, 8 parts, 9 parts and the like) of conductive carbon black (Super-P).
Preferably, the metal layer is selected from a 316 stainless steel layer, a 304 stainless steel layer or an aluminum alloy layer.
In the present invention, the carbon material is selected from artificial graphite, natural graphite, expanded graphite, activated carbon, acetylene black or carbon black.
Preferably, the thermoplastic resin powder is selected from any one of polyvinylidene fluoride (PVDF), polyethylene terephthalate (PET), or polyphenylene sulfide (PPS), or a combination of at least two thereof.
Preferably, the thermoplastic resin fiber is selected from polyethylene terephthalate fiber and/or polyphenylene sulfide fiber.
In the present invention, the carbon material has a particle size of 20 to 80 μm.
Preferably, the particle size of the thermoplastic resin powder is 20 to 80 μm.
Preferably, the gas grown carbon fiber has a diameter of 50 to 200nm and a length of 3 to 15 μm.
Preferably, the thermoplastic resin fiber has a length of 1 to 10 mm.
In the invention, the gas-grown carbon fiber is specifically selected, and in the lamination process, when the composite carbon powder layer and the composite material layer are adjacent, the composite carbon powder layer can partially permeate into the pores of the adjacent composite material layer and is bridged by the gas-grown carbon fiber in the two composite layers to form a rapid conductive path. And the composite carbon powder layer and the thermoplastic resin material in the composite material layer can well bond various materials together firmly.
The carbon material with the particle size of 20-80 μm is specifically selected, if the particle size of the carbon material is too large, the contact area of the carbon material and the thermoplastic resin material is too small, the expected mechanical strength cannot be achieved, and if the particle size of the carbon material is too small, the thermoplastic resin material coats the carbon material, the contact area between the carbon materials is reduced, and the electronic conduction is influenced.
The invention specifically selects the thermoplastic resins such as polyvinylidene fluoride, polyethylene terephthalate or polyphenylene sulfide, has higher softening temperature and excellent acid and alkali resistance and good cohesiveness, so that the finally obtained laminated unipolar plate has good temperature resistance and acid and alkali resistance and the composite layers have excellent stability.
Preferably, the metal layer has a thickness of 0.01-0.1mm, such as 0.02mm, 0.03mm, 0.04mm, 0.05mm, 0.06mm, 0.07mm, 0.08mm, 0.09mm, and the like.
Preferably, the thickness of the laminated monopole plate is 0.6-1.1mm, such as 0.7mm, 0.8mm, 0.9mm, 1.0mm, and the like.
Preferably, the laminated unipolar plate includes 2-5 metal layers, 2-5 composite carbon powder layers, and 2-5 composite material layers.
Preferably, a composite carbon powder layer and/or a composite material layer is arranged between any two adjacent metal layers, and a metal layer and/or a composite material layer is arranged between any two adjacent composite carbon powder layers; and a composite carbon powder layer and/or a metal layer is arranged between any two adjacent composite material layers.
The 2-5 layers can be 2 layers, 3 layers, 4 layers, 5 layers and the like.
The laminated unipolar plate can be a metal layer, a composite carbon powder layer, a composite material layer and a composite carbon powder layer which are arranged in sequence; or the composite carbon powder layer is sequentially arranged on the metal layer; or, for the composite carbon powder layer, the metal layer, the composite material layer, the composite carbon powder layer and the like which are sequentially arranged, because if any two adjacent composite carbon powder layers or any two composite material layers are mutually bonded, the composite carbon powder layer or the composite material layer can also be called as a composite carbon powder layer or a composite material layer, the composite carbon powder layer and/or the composite material layer is preferably arranged between any two adjacent metal layers, and the metal layer and/or the composite material layer is preferably arranged between any two adjacent composite carbon powder layers; and a composite carbon powder layer and/or a metal layer is arranged between any two adjacent composite material layers.
Fig. 1-4 are schematic structural diagrams illustrating several laminated unipolar plates according to the present invention, and as shown in fig. 1, the unipolar plate structure provided by the present invention may be a composite carbon powder layer, a composite material layer, and a metal layer that are laminated in sequence; alternatively, as shown in fig. 2, the unipolar plate structure provided by the present invention may be a composite carbon powder layer, a composite material layer, a metal layer, a composite material layer, and a composite carbon powder layer that are sequentially stacked; alternatively, as shown in fig. 3, the unipolar plate structure provided by the present invention may be a composite carbon powder layer, a composite material layer, a metal layer, and a composite material layer that are sequentially stacked; alternatively, as shown in fig. 4, the unipolar plate structure provided by the present invention may be a composite material layer, a composite carbon powder layer, a composite material layer, and a metal layer that are sequentially stacked; the structure of the unipolar plate provided by the present invention does not include only the above list.
In a second aspect, the present invention provides a method of manufacturing a laminated unipolar plate according to the first aspect, the method comprising the steps of:
laminating and hot-pressing the metal layer, the composite carbon powder layer and the composite material layer to obtain the unipolar plate;
preferably, the preparation method comprises the following steps:
and (3) laminating and hot-pressing 2-5 metal layers, 2-5 composite carbon powder layers and 2-5 composite material layers to obtain the unipolar plate.
Preferably, a composite carbon powder layer and/or a composite material layer is arranged between any two adjacent metal layers, and a metal layer and/or a composite material layer is arranged between any two adjacent composite carbon powder layers; and a composite carbon powder layer and/or a metal layer is arranged between any two adjacent composite material layers.
Preferably, the hot pressing is performed in a mold with a shaped runner.
Preferably, the hot pressing temperature is 200-350 ℃, such as 220 ℃, 250 ℃, 270 ℃, 290 ℃, 300 ℃, 320 ℃ and the like, the pressure is 10-50MPa, such as 20MPa, 30MPa, 40MPa and the like, and the time is 1-10min, such as 2min, 4min, 5min, 8min and the like.
Preferably, the thickness of the composite carbon powder layer is 0.2-2mm, such as 0.3mm, 0.5mm, 0.8mm, 1mm, 1.2mm, 1.4mm, 1.6mm, 1.8mm, 2mm, etc.
Preferably, the thickness of the composite layer is 2-10mm, such as 3mm, 4mm, 5mm, 6mm, 7mm, 8mm, 9mm, and the like.
Preferably, the preparation method further comprises the steps of performing sand blasting treatment on the surface, provided with the flow channels, of the prepared laminated unipolar plate for 1-5min, such as 2min, 3min, 4min and the like, wherein the shot blasting particle size is 50-80 μm, such as 55 μm, 60 μm, 65 μm, 70 μm, 75 μm and the like, and processing excess materials at the edge and the holes of the plate.
Preferably, the preparation method of the composite material layer comprises the following steps:
(1) mixing a carbon material, thermoplastic resin fibers, gas phase grown carbon fibers, conductive carbon black and water to obtain slurry, and then draining;
(2) and draining and drying the slurry to obtain the composite material layer.
Preferably, the slurry of step (1) has a solids content of 0.5 to 5 wt%, such as 1 wt%, 2 wt%, 3 wt%, 4 wt%, etc.
Preferably, the mixing is carried out in a planetary mixer, the mixing speed is 500-3000r/min, such as 800r/min, 1000r/min, 1200r/min, 1500r/min, 1800r/min, 2000r/min, 2200r/min, 2500r/min, 2800r/min, etc., and the time is 10-120min, such as 20min, 40min, 50min, 60min, 80min, 100min, etc.
Preferably, the draining is performed by using a screen with 500 to 2000 meshes (such as 800 meshes, 1000 meshes, 1200 meshes, 1500 meshes, 1800 meshes) and providing a negative pressure of-0.1 to-0.01 MPa (such as-0.02 MPa, -0.04MPa, -0.08 MPa) at the lower end of the screen to drain the liquid water in the slurry rapidly.
Preferably, the drying method is carried out by treating at 40-80 deg.C (e.g. 50 deg.C, 60 deg.C, 70 deg.C, etc.) under vacuum degree of-0.1 to-0.08 MPa (e.g. -0.09MPa, etc.) for 10-60min (e.g. 20min, 40min, 50min, etc.), then heating to 200 deg.C 350 deg.C (e.g. 220 deg.C, 250 deg.C, 280 deg.C, 300 deg.C, 320 deg.C, etc.) for 10-60min (e.g. 20min, 40min, 50min, etc.), and finally naturally cooling to room temperature.
Preferably, the preparation method of the composite carbon powder comprises the following steps: mixing a carbon material, thermoplastic resin fibers and aerial image long carbon fibers to obtain the composite carbon powder;
preferably, the mixing is carried out in a Henschel mixer at a mixing speed of 1000-.
In a third aspect, the present invention provides a laminated bipolar plate comprising at least two laminated unipolar plates according to the first aspect bonded to each other.
Preferably, the two surface layers of the laminated bipolar plate are composite carbon powder layers and/or composite material layers.
The two surface layers of the laminated bipolar plate are composite carbon powder layers and/or composite material layers, that is, the two surfaces of the laminated bipolar plate can be both composite carbon powder layers or both composite material layers, or one surface is a composite carbon powder layer and the other surface is a composite material layer. As long as both surfaces are not metal layers.
The preparation method of the laminated bipolar plate comprises the following steps: bonding the laminated unipolar plate of the first aspect.
In a fourth aspect, the present invention provides the use of a laminated unipolar plate according to the first aspect or a laminated bipolar plate according to the third aspect in a fuel cell.
Compared with the prior art, the invention has the following beneficial effects:
the laminated bipolar plate provided by the invention can obviously improve the conductivity of the through surface of the polar plate, solve the problem of hydrogen permeation of the carbon-based material polar plate, reduce the thickness of the polar plate and be beneficial to the improvement of the volume power density of a galvanic pile; the conductivity of the through surface of the laminated composite electrode plate provided by the invention is more than 40S-cm, the highest conductivity can be more than 80S-cm, the thickness is less than 2.0mm, the optimal thickness can be less than 1.8mm, and the air tightness is good.
Drawings
Fig. 1 is a first schematic view of a laminated unipolar plate according to an exemplary embodiment of the present invention.
Fig. 2 is a second schematic structural view of a laminated unipolar plate according to an exemplary embodiment of the present invention.
Fig. 3 is a schematic diagram of a third embodiment of the present invention.
Fig. 4 is a fourth schematic structural view of an exemplary laminated unipolar plate of the present invention.
Detailed Description
The technical solution of the present invention is further explained by the following embodiments. It should be understood by those skilled in the art that the examples are only for the understanding of the present invention and should not be construed as the specific limitations of the present invention.
The materials and the reference information of the examples and comparative examples are as follows:
example 1
A laminated bipolar plate is prepared by the following steps:
(1) preparation of composite carbon powder
80 parts of artificial graphite with D90 being 70 mu m, 15 parts of polyvinylidene fluoride and 5 parts of gas phase growing carbon fiber are put into a Henschel mixer and stirred for 20min under the condition of 2000 r/min;
(2) preparation of composite Material layers
Putting 20 parts of polyethylene terephthalate fiber into a planetary mixer filled with 1000 parts of deionized water, stirring for 10min at 1500r/min, then putting 5 parts of weather-grown carbon fiber into the planetary mixer, stirring for 10min at 2000r/min, then putting 2 parts of Super-P and 73 parts of artificial stone toner with D90 of 70 mu m into the planetary mixer, continuing stirring for 30min at 2000r/min, pouring the stirred slurry into a 1000-mesh sieve, draining liquid water, then putting the slurry into a vacuum oven, vacuumizing to-0.09 MPa, heating to 50 ℃ for 30min, then increasing the temperature to 270 ℃, heating for 20min, finally naturally cooling to room temperature, and breaking vacuum to obtain a composite material layer;
(3) preparation of laminated monopolar plate
Sequentially laminating an aluminum alloy sheet with the thickness of 0.03mm, a composite material layer with the thickness of 5mm and a composite carbon powder layer with the thickness of 2mm from bottom to top, then putting the laminated layers into a mould with a forming flow channel, applying the pressure of 35MPa, and simultaneously heating to 270 ℃ for 2 min;
(4) preparation of laminated bipolar plate
And then taking out the formed unipolar plates, treating the surface of one side with the flow channel for 2min by using a sand blasting machine, removing redundant materials at the edges and holes of the polar plates, and bonding the metal layers of the two unipolar plates to obtain the laminated bipolar plate.
Example 2
A laminated bipolar plate is prepared by the following steps:
(1) preparation of composite carbon powder
70 parts of artificial graphite with D90 being 60 mu m, 20 parts of polyvinylidene fluoride and 10 parts of gas phase growing carbon fiber are put into a Henschel mixer to be mixed for 30min under the condition of 2000 r/min;
(2) preparation of composite Material layers
Same as in example 1
(3) Preparation of laminated bipolar plate
Sequentially laminating a composite material layer with the thickness of 3mm, an aluminum alloy sheet with the thickness of 0.03mm, a composite material layer with the thickness of 3mm and a composite carbon powder layer with the thickness of 2mm from bottom to top, then putting the laminated composite carbon powder layers into a mold with a molding flow channel, applying the pressure of 35MPa, heating to 270 ℃ at the same time, and keeping for 3 min;
and then taking out the formed unipolar plates, treating the surface of one side with the flow channel for 2min by using a sand blasting machine, removing redundant materials at the edges and holes of the polar plates, and bonding the metal layers of the two unipolar plates to obtain the laminated bipolar plate.
Example 3
A laminated bipolar plate is prepared by the following steps:
(1) preparation of composite carbon powder
75 parts of artificial graphite with D90 being 70 mu m, 15 parts of polyvinylidene fluoride and 10 parts of gas phase growing carbon fiber are put into a Henschel mixer to be mixed for 30min under the condition of 2000 r/min;
(2) preparation of composite Material layers
Putting 15 parts of polyethylene terephthalate fiber into a planetary mixer filled with 1000 parts of deionized water, stirring for 10min at 1500r/min, then putting 10 parts of weather-grown carbon fiber into the planetary mixer, stirring for 10min at 2000r/min, then putting 5 parts of Super-P and 70 parts of artificial stone toner with D90 being 70 mu m into the planetary mixer, continuing stirring for 30min at 2000r/min, pouring the stirred slurry into a 1000-mesh sieve, draining liquid water, then putting the slurry into a vacuum oven, vacuumizing to-0.09 MPa, heating to 50 ℃ for 30min, then increasing the temperature to 270 ℃, heating for 20min, finally naturally cooling to room temperature, and breaking vacuum to obtain a composite material layer;
(3) preparation of laminated bipolar plate
Sequentially laminating an aluminum alloy sheet with the thickness of 0.03mm, a composite material layer with the thickness of 3mm, a composite carbon powder layer with the thickness of 2mm and a composite material layer with the thickness of 3mm from bottom to top, putting the laminated layers into a mold with a molding flow channel, applying the pressure of 35MPa, heating to 270 ℃ at the same time, and keeping for 3 min;
and then taking out the formed unipolar plates, treating the surface of one side with the flow channel for 2min by using a sand blasting machine, removing redundant materials at the edges and holes of the polar plates, and bonding the metal layers of the two unipolar plates to obtain the laminated bipolar plate.
Example 4
A laminated bipolar plate is prepared by the following steps:
(1) preparation of composite carbon powder
Same as in example 3;
(2) preparation of composite Material layers
Same as in example 3;
(3) preparation of laminated bipolar plate
Sequentially laminating a 304 stainless steel sheet with the thickness of 0.03mm, a composite material layer with the thickness of 3mm, a composite carbon powder layer with the thickness of 2mm and a composite material layer with the thickness of 3mm from bottom to top, putting the laminated layers into a mold with a molding flow channel, applying the pressure of 35MPa, heating to 270 ℃ at the same time, and keeping for 3 min;
and then taking out the formed unipolar plates, treating the surface of one side with the flow channel for 2min by using a sand blasting machine, removing redundant materials at the edges and holes of the polar plates, and bonding the metal layers of the two unipolar plates to obtain the laminated bipolar plate.
Example 5
The only difference from example 1 is that in step (3) of this example, there are, in order from bottom to top, a 5mm thick composite material layer, a 0.03mm thick aluminum alloy sheet, and a 2mm thick composite carbon powder layer.
Example 6
The only difference from example 1 is that, in step (3) of this example, there are, in order from bottom to top, a 0.03mm thick aluminum alloy sheet, a 2mm thick composite carbon powder layer, and a 5mm thick composite material layer.
Example 7
The only difference from example 1 is that, in step (3) of this example, there are, in order from bottom to top, a 3mm thick composite material layer, a 2mm thick composite carbon powder layer, a 0.03mm thick 304 stainless steel sheet, a 2mm thick composite carbon powder layer, and a 3mm thick composite material layer.
Examples 8 to 11
The difference from example 1 is that in this example, the particle diameters of the artificial graphite in step (1) and step (2) were 20 μm (example 8), 80 μm (example 9), 10 μm (example 10), and 100 μm (example 11).
Comparative example 1
Opposite-label composite bipolar plate
Comparative example 2
The difference from example 1 is that the aluminum alloy sheet of 0.03mm thickness was not provided in step (3) of this comparative example.
Comparative example 3
The difference from example 1 is that in step (3) of this comparative example, a 5mm thick composite layer was not provided, while increasing the thickness of the composite carbon powder layer to 7 mm.
Comparative example 4
The difference from example 1 is that a 2mm thick composite carbon powder layer was not provided in step (3) of this comparative example, while increasing the composite layer thickness to 7 mm.
Performance testing
The bipolar plates provided in examples 1 to 11 and comparative examples 1 to 4 were subjected to performance tests as follows:
(1) and (3) testing the conductivity of the bipolar plate through surface: the single electrode plate was cut into a 30mm diameter circular piece and placed between two gold-plated copper electrodes with a gas diffusion layer (made by east-li japan) placed between the copper electrodes and the electrode plate. Applying 4900N force to the structure, and measuring the resistance R1(ii) a Removing the plate, applying the same pressure, and measuring the resistance value R2Wherein:
ρ＝(R1-R2)×A/d
rho is resistivity; a is the area of the sample wafer; d, the thickness of the sample;
(2) airtightness: performing performance test according to the 4 th test standard in GB/T20042.6;
the test results are shown in table 1:
TABLE 1
The embodiment and the performance test show that the laminated composite electrode plate provided by the invention can obviously improve the conductivity of the through surface of the electrode plate, solve the problem of hydrogen permeation of the carbon-based material electrode plate, reduce the thickness of the electrode plate and facilitate the increase of the volume power density of an electric pile, wherein the conductivity of the through surface of the laminated composite electrode plate provided by the invention is more than 40S-cm, the highest conductivity can be more than 80S-cm, the thickness is less than 2.0mm, and the air tightness is good.
As can be seen from the comparison between the embodiment 1 and the comparative example 1, the laminated composite electrode plate provided by the invention can meet the application requirements; as can be seen from the comparison between example 1 and comparative examples 2 to 4, the laminated composite electrode plate provided by the present invention includes three layers.
The applicant states that the present invention is illustrated by the above examples of the laminated unipolar plate of the present invention, the method of preparing the same, the laminated bipolar plate including the same, and the applications thereof, but the present invention is not limited to the above process steps, i.e., it is not meant that the present invention must rely on the above process steps to be implemented. It will be apparent to those skilled in the art that any modification of the present invention, equivalent substitutions of selected materials and additions of auxiliary components, selection of specific modes and the like, which are within the scope and disclosure of the present invention, are contemplated by the present invention.
Claims (27)
1. A laminated unipolar plate is characterized by comprising a metal layer, a composite carbon powder layer and a composite material layer,
the composite carbon powder layer comprises the following components in parts by weight of 100:
70-95 parts of carbon material, 5-20 parts of thermoplastic resin powder and 2-10 parts of gas-phase grown carbon fiber;
the composite material layer comprises the following components in parts by weight of 100:
60-95 parts of carbon material, 2-30 parts of thermoplastic resin fiber, 1-10 parts of gas phase growing carbon fiber and 1-10 parts of conductive carbon black, wherein the composite carbon powder layer is adjacent to the composite material layer.
2. The laminated unipolar plate of claim 1, wherein the metal layer is selected from a 316 stainless steel layer, a 304 stainless steel layer, or an aluminum alloy layer.
3. The laminated unipolar plate of claim 1, wherein the carbon material is selected from the group consisting of artificial graphite, natural graphite, expanded graphite, activated carbon, acetylene black, or carbon black.
4. The laminated unipolar plate of claim 1, wherein said thermoplastic resin powder is selected from the group consisting of any one or a combination of at least two of polyvinylidene fluoride, polyethylene terephthalate, or polyphenylene sulfide.
5. The laminated unipolar plate of claim 1, wherein the thermoplastic resin fibers are selected from the group consisting of polyethylene terephthalate fibers and/or polyphenylene sulfide fibers.
6. The laminated unipolar plate of claim 1, wherein said carbon material has a particle size of 20-80 μm.
7. The laminated unipolar plate of claim 1, wherein said thermoplastic resin powder has a particle size of 20-80 μm.
8. The laminated unipolar plate of claim 1, wherein said vapor grown carbon fibers have a diameter of 50-200nm and a length of 3-15 μ ι η.
9. The laminated unipolar plate of claim 1, wherein the thermoplastic resin fibers have a length of 1-10 mm.
10. The laminated unipolar plate of claim 1, wherein the metal layer has a thickness of 0.01-0.1 mm.
11. The laminated unipolar plate of claim 1, wherein the laminated unipolar plate has a thickness of 0.6-1.1 mm.
12. The laminated unipolar plate of claim 1, wherein the laminated unipolar plate comprises 2-5 metal layers, 2-5 composite carbon powder layers, and 2-5 composite material layers.
13. The laminated unipolar plate of claim 1, wherein a composite carbon powder layer and/or a composite material layer is disposed between any two adjacent metal layers, and a metal layer and/or a composite material layer is disposed between any two adjacent composite carbon powder layers; and a composite carbon powder layer and/or a metal layer is arranged between any two adjacent composite material layers.
14. The method of manufacturing the laminated unipolar plate of any one of claims 1-13, wherein said method of manufacturing comprises the steps of:
and laminating and hot-pressing the metal layer, the composite carbon powder layer and the composite material layer to obtain the laminated unipolar plate.
15. The method of making the laminated unipolar plate of claim 14, wherein said method of making comprises the steps of:
and (3) laminating and hot-pressing 2-5 metal layers, 2-5 composite carbon powder layers and 2-5 composite material layers to obtain the laminated unipolar plate.
16. The method for manufacturing a laminated unipolar plate according to claim 14, wherein a composite carbon powder layer and/or a composite material layer is disposed between any two adjacent metal layers, and a metal layer and/or a composite material layer is disposed between any two adjacent composite carbon powder layers; and a composite carbon powder layer and/or a metal layer is arranged between any two adjacent composite material layers.
17. The method of preparing the laminated unipolar plate of claim 14, wherein the hot pressing is performed at a temperature of 200 ℃ to 350 ℃, a pressure of 10 to 50MPa, and a time of 1 to 10 min.
18. The method of making a laminated unipolar plate of claim 14, wherein said composite carbon powder layer has a thickness of 0.2-2 mm.
19. The method of making a laminated unipolar plate of claim 14, wherein said composite material layer has a thickness of 2-10 mm.
20. The method of manufacturing a laminated unipolar plate as claimed in claim 14, further comprising sand blasting the surface of the laminated unipolar plate with the flow channels.
21. The method of manufacturing a laminated unipolar plate of claim 20, wherein said grit blasting is performed for a period of 1 to 5min and a shot size is 50 to 80 μm.
22. The method of making a laminated unipolar plate of claim 14, wherein said method of making a composite material layer comprises:
(1) mixing a carbon material, thermoplastic resin fibers, gas phase grown carbon fibers, conductive carbon black and water to obtain slurry, and then draining;
(2) and draining and drying the slurry to obtain the composite material layer.
23. The method of preparing a laminated unipolar plate of claim 22, wherein said slurry of step (1) has a solids content of 0.5 to 5 wt%.
24. The method for preparing the laminated unipolar plate as claimed in claim 22, wherein the drying is performed by treating at 40-80 ℃ and a vacuum degree of-0.1-0.08 MPa for 10-60min, then heating to 200-350 ℃ for 10-60min, and finally naturally cooling to room temperature.
25. A laminated bipolar plate comprising at least two laminated unipolar plates according to any one of claims 1 to 13 bonded to each other.
26. The laminated bipolar plate of claim 25 wherein both surface layers of the laminated bipolar plate are layers of composite carbon powder and/or composite material.
27. Use of a laminated unipolar plate according to any one of claims 1 to 13 or of a laminated bipolar plate according to claim 25 or 26 in a fuel cell.
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| CN1851964A (en) * | 2005-04-22 | 2006-10-25 | 鸿富锦精密工业（深圳）有限公司 | Double-polar board, its preparing method and fuel cell having said double-polar board |
| CN109921053A (en) * | 2017-12-13 | 2019-06-21 | 中国科学院大连化学物理研究所 | A kind of preparation method and applications of bipolar plates |
| CN110137524A (en) * | 2019-04-26 | 2019-08-16 | 张家港市乐青新材料科技有限公司 | A kind of metal-based compound bipolar plates substrate and preparation method thereof |
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| US20020064701A1 (en) * | 2000-09-11 | 2002-05-30 | Hand Doris I. | Conductive liquid crystalline polymer film and method of manufacture thereof |
| CN1248344C (en) * | 2001-09-11 | 2006-03-29 | 石油大学(北京) | Composite carbon fibre paper used for diffusion layer of electrode in ion-exchange membrane fuel battery and its preparing process |
| TWI336538B (en) * | 2006-03-22 | 2011-01-21 | Ind Tech Res Inst | Electrically conductive composite |
| US20100279177A1 (en) * | 2008-01-03 | 2010-11-04 | Hsiharng Yang | Carbon fiber conductive sheet and manufacturing method thereof |
| CN109486144A (en) * | 2018-10-30 | 2019-03-19 | 三明共聚塑胶有限公司 | A kind of fibre reinforced composites with three-dimensional conductive network structure |
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| CN1851964A (en) * | 2005-04-22 | 2006-10-25 | 鸿富锦精密工业（深圳）有限公司 | Double-polar board, its preparing method and fuel cell having said double-polar board |
| CN109921053A (en) * | 2017-12-13 | 2019-06-21 | 中国科学院大连化学物理研究所 | A kind of preparation method and applications of bipolar plates |
| CN110137524A (en) * | 2019-04-26 | 2019-08-16 | 张家港市乐青新材料科技有限公司 | A kind of metal-based compound bipolar plates substrate and preparation method thereof |
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