CN113555577B - Composite bipolar plate and preparation method thereof - Google Patents
Composite bipolar plate and preparation method thereof Download PDFInfo
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- CN113555577B CN113555577B CN202110755075.0A CN202110755075A CN113555577B CN 113555577 B CN113555577 B CN 113555577B CN 202110755075 A CN202110755075 A CN 202110755075A CN 113555577 B CN113555577 B CN 113555577B
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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
- H01M8/023—Porous and characterised by the material
- H01M8/0234—Carbonaceous material
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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
- H01M8/023—Porous and characterised by the material
- H01M8/0241—Composites
- H01M8/0243—Composites in the form of mixtures
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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
- H01M8/22—Fuel cells in which the fuel is based on materials comprising carbon or oxygen or hydrogen and other elements; Fuel cells in which the fuel is based on materials comprising only elements other than carbon, oxygen or hydrogen
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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 application relates to the technical field of hydrogen energy fuel cells, in particular to a composite bipolar plate and a preparation method thereof. The composite bipolar plate comprises the following raw materials: 1-95 parts of expanded graphite with the particle size of D50 being 1-300 mu m; 0.1-50 parts of flake graphite with the particle size of D50 being 1-500 mu m; 1-95 parts of graphite worms with expansion multiplying power of 50-2000 mL/g; 1-50 parts of liquid resin; 0.1-20 parts of a toughening agent; 0.1-20 parts of conductive filler. The composite bipolar plate has the advantages of optimal flow channel formability, precision, mechanical property and conductivity, and good application prospect in a solid electrolyte water electrolytic cell.
Description
Technical Field
The application belongs to the technical field of hydrogen energy fuel cells, and particularly relates to a composite bipolar plate and a preparation method thereof.
Background
The technology of solid electrolyte electrolyzed water (solid electrolyte membrane water electrolysis) is used for preparing high-purity hydrogen, has high electrolysis efficiency and compact electrolytic cell structure, and is considered as a potential high-purity hydrogen preparation technology. The electrolytic tank mainly comprises a bipolar plate, a gas diffusion layer and a membrane electrode. The bipolar plate is one of the key components of solid electrolyte water electrolysis, accounts for more than 40% of the cost of the electrolytic cell, and plays a plurality of functions of cathode and anode reactant isolation and distribution, current collection, heat conduction, sealing, membrane electrode support and the like. Therefore, the bipolar plate material needs to have the characteristics of good electrical and thermal conductivity, corrosion resistance, high mechanical property, low gas permeability and the like, and the transmission and discharge of reaction gas depend on the flow channel on the bipolar plate, so the bipolar plate needs to have good flow channel forming performance, and the precision requirement is high so as to ensure smaller fluid resistance and good water and gas transmission performance.
Commonly used bipolar plates mainly include carbon plates, metal bipolar plates. Carbon-based materials are not suitable for direct contact with water at the anode because of the high electrolytic anode voltage, which can cause carbon corrosion when the carbon-based material is in direct contact with water. In the cathode of the electrolyzed water, the generation of a large amount of hydrogen easily causes the problem of hydrogen brittleness of the metal material; in the electrolytic process, a large number of micro bubbles can be attached to the metal surface of the polar plate, so that the mass transfer resistance of the electrolysis is increased.
Graphite bipolar plates have good electrical conductivity, hydrogen embrittlement resistance, and excellent acid corrosion resistance, but are poor in bending strength and gas tightness, and generally require a thick plate material to meet practical requirements. In addition, the difficulty of processing the fine flow channel structure on the surface of the bipolar plate is high, and the fine flow channel structure becomes an important factor for limiting the wide application of the graphite bipolar plate. The graphite/resin composite bipolar plate takes the polymeric material of graphite reinforced resin as a matrix, has the advantages of low price compared with metal materials, simple and convenient preparation process, light weight, good corrosion resistance and the like, but the performance of the composite bipolar plate is influenced by the graphite content, the preparation process and the like, shows larger difference in conductivity, bending strength, process performance and the like, and also has the defect of low flow channel precision.
Disclosure of Invention
The application aims to provide a composite bipolar plate and a preparation method thereof, and aims to solve the technical problem of how to improve the flow channel precision of the bipolar plate.
In order to achieve the purpose of the application, the technical scheme adopted by the application is as follows:
in a first aspect, the present application provides a composite bipolar plate, which comprises the following raw materials by weight:
1-95 parts of expanded graphite with the particle size of D50 being 1-300 mu m;
0.1-50 parts of flake graphite with the particle size of D50 being 1-500 mu m;
1-95 parts of graphite worms with expansion multiplying power of 50-2000 mL/g;
1-50 parts of liquid resin;
0.1-20 parts of a toughening agent;
0.1-20 parts of conductive filler.
The composite bipolar plate provided by the application comprises expanded graphite, crystalline flake graphite, graphite worms, resin, conductive filler and a toughening agent in certain parts by weight; the composite bipolar plate has good mechanical property and good electrical conductivity through the proportion of the resin and the conductive filler, the toughness of the composite bipolar plate can be improved by the toughening agent, and more importantly, the composite bipolar plate has good flow channel precision through the comprehensive advantages of expanded graphite, flake graphite and graphite worms; therefore, the composite bipolar plate has the advantages that the flow channel formability, the precision, the mechanical property and the conductivity of the composite bipolar plate are optimal through the synergistic effect of the components, and the composite bipolar plate has a good application prospect in a solid electrolyte water electrolytic cell.
In a second aspect, the present application provides a method for preparing a composite bipolar plate, comprising the steps of:
providing a feedstock for a composite bipolar plate as described herein;
dissolving the toughening agent and the liquid epoxy resin in a solvent to obtain a mixed solution;
mixing the expanded graphite, the flake graphite, the graphite worms and the conductive filler to obtain a mixed material;
and (3) uniformly mixing the mixed solution and the mixed material, removing the solvent, and then performing punch forming and curing treatment to obtain the composite bipolar plate.
According to the preparation method of the composite bipolar plate, the raw materials are uniformly mixed, and then the product is obtained through punch forming and curing, so that the preparation method is high in production efficiency, low in cost and high in yield, the obtained composite bipolar plate is optimal in flow channel formability and precision, and comprehensive effects of mechanical property and conductivity, and the composite bipolar plate has a good application prospect in a solid electrolyte water electrolytic cell.
Drawings
In order to more clearly illustrate the technical solutions in the embodiments of the present application, the drawings needed to be used in the description of the embodiments are briefly introduced below, and it is obvious that the drawings in the following description are only some embodiments of the present application, and it is obvious for those skilled in the art to obtain other drawings based on these drawings without creative efforts.
Fig. 1 is a schematic view illustrating a process for manufacturing a composite bipolar plate according to an embodiment of the present disclosure;
FIG. 2 is a measurement of a composite bipolar plate provided by an embodiment of the present application; a-mold surface profile, b-mold show picture, c-product surface profile, d-product show picture.
Detailed Description
In order to make the technical problems, technical solutions and beneficial effects to be solved by the present application more clearly apparent, the present application is further described in detail below with reference to the embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the present application and are not intended to limit the present application.
In this application, the term "and/or" describes an association relationship of associated objects, meaning that there may be three relationships, e.g., a and/or B, which may mean: a is present alone, A and B are present simultaneously, and B is present alone. Wherein A and B can be singular or plural. The character "/" generally indicates that the former and latter associated objects are in an "or" relationship.
In the present application, "at least one" means one or more, "plural" means two or more. "at least one of the following" or similar expressions refer to any combination of these items, including any combination of the singular or plural items. For example, "at least one (a), b, or c", or "at least one (a), b, and c", may each represent: a, b, c, a-b (i.e., a and b), a-c, b-c, or a-b-c, wherein a, b, and c may be single or plural, respectively.
It should be understood that, in various embodiments of the present application, the sequence numbers of the above-mentioned processes do not mean the execution sequence, some or all of the steps may be executed in parallel or executed sequentially, and the execution sequence of each process should be determined by its function and inherent logic, and should not constitute any limitation to the implementation process of the embodiments of the present application.
The terminology used in the embodiments of the present application is for the purpose of describing particular embodiments only and is not intended to be limiting of the application. As used in the examples of this application and the appended claims, the singular forms "a", "an", and "the" are intended to include the plural forms as well, unless the context clearly indicates otherwise.
The weight of the related components mentioned in the description of the embodiments of the present application may not only refer to the specific content of each component, but also represent the proportional relationship of the weight among the components, and therefore, the content of the related components is scaled up or down within the scope disclosed in the description of the embodiments of the present application as long as it is scaled up or down according to the description of the embodiments of the present application. Specifically, the mass described in the specification of the embodiments of the present application may be a mass unit known in the chemical industry field such as μ g, mg, g, kg, etc.
The first aspect of the embodiments of the present application provides a composite bipolar plate, which comprises the following raw materials by weight:
1-95 parts of expanded graphite with the particle size of D50 being 1-300 mu m;
0.1-50 parts of flake graphite with the particle size of D50 being 1-500 mu m;
1-95 parts of graphite worms with expansion multiplying power of 50-2000 mL/g;
1-50 parts of liquid resin;
0.1-20 parts of a toughening agent;
0.1-20 parts of conductive filler.
The composite bipolar plate provided by the embodiment of the application comprises expanded graphite, crystalline flake graphite, graphite worms, resin, conductive filler and a toughening agent in certain parts by weight; the composite bipolar plate has good mechanical property and good electrical conductivity through the proportion of the resin and the conductive filler, the toughness of the composite bipolar plate can be improved by the toughening agent, and more importantly, the composite bipolar plate has good flow channel precision through the comprehensive advantages of expanded graphite, flake graphite and graphite worms; therefore, the composite bipolar plate has the advantages that the flow channel formability, the precision, the mechanical property and the conductivity of the composite bipolar plate are optimal through the synergistic effect of the components, and the composite bipolar plate has a good application prospect in a solid electrolyte water electrolytic cell.
Further, the raw materials of the composite bipolar plate comprise the following groups:
70-90 parts of expanded graphite with the D50 particle size of 1-300 mu m;
5-15 parts of flake graphite with the particle size of D50 being 1-500 mu m;
10-25 parts of graphite worms with expansion multiplying power of 50-2000 mL/g;
15-35 parts of liquid epoxy resin;
0.5-5 parts of a toughening agent;
0.5-5 parts of conductive filler.
The composite bipolar plate uses three kinds of graphite, namely expanded graphite, flake graphite and graphite worms; the Flake Graphite is also called Flake Graphite (Flake Graphite), is natural crystalline Graphite, is similar to fish phosphorus, belongs to a hexagonal system, has a layered structure and excellent physical and chemical properties, and has good heat conductivity, electric conductivity and corrosion resistance; the Expanded graphite (Expanded graphite) is loose porous graphite obtained by intercalation, washing, drying and high-temperature expansion of natural graphite flakes; the graphite worms are also called vermicular graphite (vermicular graphite), and the morphological structure of the vermicular graphite is a type of graphite between the flake graphite morphology and the spherical graphite morphology. The method comprehensively utilizes the advantages of the three types of graphite, and further uses a large amount of expanded graphite and graphite worms on the basis of the flake graphite, wherein the density of flake graphite powder is generally about 1g/cm3And the density of the graphite worm powder with the magnification of 200 is about 0.005g/cm3Because the density of the graphite worm powder is far less than that of the flake graphite powder, the plasticity is high, and the graphite worm powder and the expanded graphite cooperate to improve the flake graphite, the flow channel generated by the composite bipolar plate formed by superposing the three types of graphite is high in precision.
The expanded graphite has a D50 particle size of 1 to 300. mu.m, specifically 10 to 280. mu.m, 20 to 250. mu.m, and 30 to 240. mu.m, and more preferably, the expanded graphite has a D50 particle size of 25 to 200. mu.m; the expanded graphite may be present in an amount of 1 to 95 parts by weight, such as 10 parts, 20 parts, 40 parts, 50 parts, 60 parts, 80 parts, 95 parts, preferably 70 to 90 parts. The particle size of D50 of the flake graphite is 1-500 μm, specifically 10-480 μm, 20-450 μm, 30-400 μm, 40-350 μm, 45-300 μm, and more preferably the particle size of D50 of the flake graphite is 25-250 μm; the weight of the crystalline flake graphite may be 0.1 to 50 parts, such as 1 part, 10 parts, 20 parts, 250 parts, 30 parts, 40 parts, 50 parts, preferably 5 to 15 parts. The expansion ratio of the graphite worms is 50-2000 mL/g, specifically 60-1500 mL/g, 70-1200 mL/g, 80-1000 mL/g, 90-800 mL/g, and more preferably 100-500 mL/g; the weight of the graphite worms may be 1 to 95 parts, such as 10 parts, 20 parts, 40 parts, 50 parts, 60 parts, 80 parts, 95 parts, preferably 10 to 25 parts. The expanded graphite, preferably D50 particle size, the flake graphite, preferably D50 particle size, and the graphite worms, preferably at an expansion ratio, interact in the preferred weight parts ranges to optimize the flow channel accuracy of the composite bipolar plate of the present application. In a preferred embodiment, the flow channel obtained by molding after adjusting the proportion of the crystalline flake graphite powder, the graphite worm powder and the expanded graphite powder has high precision, the flow channel depth deviation of the composite bipolar plate is less than +/-3 μm, and the roughness is less than 2 μm.
In one embodiment, the liquid resin is selected from any one of phenolic resin, epoxy resin, vinyl resin, urea resin, and unsaturated resin. Further, the toughening agent is selected from adhesives corresponding to liquid resins. For example, the toughening agent may be: a. the epoxy resin adhesive can be selected from carboxyl liquid nitrile rubber, carboxyl-terminated liquid nitrile rubber, polysulfide rubber, liquid silicone rubber, polyether, polysulfone, polyimide, nano calcium carbonate, nano titanium dioxide and the like; b. the phenolic resin adhesive can be selected from carboxyl nitrile rubber, liquid nitrile rubber, polyvinyl butyral, polyether sulfone and polyphenyl ether ketone, and the water-soluble phenolic resin preferably takes carboxyl nitrile latex and polyvinyl alcohol as toughening agents; c. the fast-curing acrylate structural adhesive can be selected from acrylate rubber, carboxyl nitrile rubber, chloroprene rubber, chlorosulfonated polyethylene, ABS resin and the like; d. the alpha-cyanoacrylate adhesive is preferably selected from acrylate rubber, ABS, SBS, SEBS and the like; e. the unsaturated polyester resin adhesive is selected from liquid nitrile rubber, polyvinyl butyral, polyvinyl acetate and the like; f. the urea-formaldehyde resin adhesive can be selected from polyvinyl acetate emulsion, polyvinyl alcohol and the like. The conductive filler is selected from at least one of graphene, carbon nanotubes, carbon fibers, platinum powder and conductive polymer resin.
The liquid resin may be present in an amount of 1 to 50 parts by weight, such as 10 parts, 20 parts, 30 parts, 40 parts, 50 parts, preferably 15 to 35 parts; the weight part of the toughening agent can be 0.1-20 parts, such as 1 part, 5 parts, 10 parts, 12 parts, 18 parts and 20 parts, preferably 0.5-5 parts; the conductive filler may be present in an amount of 0.1 to 20 parts by weight, such as 1 part, 5 parts, 10 parts, 12 parts, 18 parts, 20 parts, preferably 0.5 to 5 parts. The resin has poor conductivity, when the resin content is too much, the conductivity of the composite bipolar plate is poor, but the mechanical property is improved, so that the consumption of the conductive filler can be adjusted, and the performance of the bipolar plate is improved; in addition, in order to meet the assembly requirements or other requirements of the bipolar plate, the bipolar plate is required to have certain flexibility, and the toughness of the bipolar plate is changed by adjusting the using amount of the toughening agent, so that the market requirements are met. Within the above preferred ranges of the resin weight parts, the preferred conductive agent weight parts and the preferred toughening agent weight parts, the composite bipolar plate has the best comprehensive effect of electrical conductivity and mechanical properties.
The composite bipolar plate of the present application may be used in fuel cells, such as hydrogen energy dye cells.
A second aspect of the embodiments of the present application provides a method for manufacturing a composite bipolar plate, including the steps of:
s01: providing raw materials of the composite bipolar plate of the embodiment of the application;
s02: dissolving a toughening agent and liquid epoxy resin in a solvent to obtain a mixed solution;
s03: mixing expanded graphite, flake graphite, graphite worms and a conductive filler to obtain a mixed material;
s04: and (3) uniformly mixing the mixed solution and the mixed material, removing the solvent, and then performing punch forming and curing treatment to obtain the composite bipolar plate.
According to the preparation method of the composite bipolar plate, the raw materials are uniformly mixed, and then the product is obtained through punch forming and curing, so that the preparation method is high in production efficiency, low in cost and high in yield, the obtained composite bipolar plate is optimal in flow channel formability, precision, mechanical property and conductivity, and has a good application prospect in a solid electrolyte water electrolytic cell.
In the step of punch forming, the punching pressure is 50-200 Mpa, and the punching time is 1-5 min; the stamping effect under the stamping condition is better. Furthermore, before the step of stamping forming, the method further comprises the step of pre-pressing the prefabricated plate into a prefabricated plate with the thickness of 1-5 mm, namely, pre-pressing the prefabricated plate into a pre-pressed plate, and then stamping. Further, the temperature of the curing treatment is 25-500 ℃, and the time is 5-120 min.
As shown in fig. 1, the production process mainly comprises three steps, namely, in the first step (fig. 1a), preparing a mixed base material (i.e., a base material formed by uniformly mixing the mixed solution and the mixed material and then removing a solvent), or prepressing the mixed base material to prepare a prepressing plate with a certain thickness; secondly (figure 1b), putting the mixed base material into a die to be directly punched and molded or to be molded by a punching pre-pressing plate; and thirdly (figure 1c), placing the punched composite bipolar plate into an oven for curing to obtain a product.
The reinforcing material uses the expanded graphite with higher compression ratio, so that the resin is easily absorbed, and a flow channel is formed; the forming process adopts stamping and rapid forming, and the forming efficiency is high; the mixed base material can be directly formed or pre-pressed into a prefabricated plate, the prefabricated plate can be separately stamped, and different bipolar plate products can be obtained according to different dies. In the preparation raw material formula, the expanded graphite material accounts for the main component, so that the air permeability of the composite bipolar plate can be reduced, the flexibility of the composite bipolar plate is improved, internal gas in the process of forming the bipolar plate can be effectively discharged by adopting a punch forming process, the internal defects of the composite bipolar plate are reduced, and in addition, the die can be vacuumized, so that the yield is improved.
When graphite and liquid resin are mixed, an appropriate amount of solvent is used to dilute the resin to obtain a resin solution (a toughening agent is further added), and then the resin solution is mixed with a mixed material formed by expanded graphite, flake graphite, graphite worms and conductive fillers, the resin solution is ensured to completely soak graphite powder during mixing, the solution is not too much or too little, and then the solvent is removed, and the solvent is a carrier for dispersing resin in the whole mixing process. The amount of the solvent used needs to be controlled during the mixing process, when the amount of the solvent is too large, the concentration of the solution increases during the solvent removal process, resulting in uneven mixing of graphite/resin, and when the amount of the solvent is too small, the graphite cannot be completely impregnated, so that part of the graphite surface is free from resin, resulting in uneven mixing of graphite/resin. The weight part of the solvent can be 200-700 parts; the solvent can be one or more of water, benzene, toluene, xylene, ethylbenzene, styrene, cyclohexane, cyclohexanone, chlorobenzene, dichloromethane, carbon tetrachloride, gasoline, kerosene, methanol, ethanol, ethyl acetate, butyl acetate, acetone, butanone, dimethylacetamide and carbon disulfide, and the proper solvent is selected according to different resin types. The resin matrix is liquid resin, and graphite worms are easier to adsorb after being diluted by a solvent, so that the effect of uniform mixing can be achieved.
In the preparation method, the toughening agent is selected from an adhesive corresponding to liquid resin, a solid resin adhesive or other liquid resin adhesives can be selected, the liquid resin can be phenolic resin, epoxy resin, vinyl resin, unsaturated resin and the like, and the liquid resin and the toughening agent are dissolved in a solvent to form viscous liquid which is mixed into a solid mixed material in a molecular level; when the material is molded at a certain temperature, the material appears in a liquid state and is not solidified; and then the curing treatment process is carried out. The application can adopt a horizontal stirrer to stir and mix the graphite, and can also use other mixing methods to replace the graphite, but the graphite worms and the expanded graphite structure cannot be seriously damaged in the mixing process.
Further, the flake graphite, the expanded graphite, the graphite worms and the conductive filler can be mixed after pretreatment, and the pretreatment process comprises surface functionalization, surface grafting, powder sizing treatment and the like to obtain a mixed material. The pretreated mixed material and the mixed solution containing the resin and the toughening agent are mixed, the surface of the mixed graphite is uniformly covered with the liquid resin adhesive, a certain amount of resin adhesive is adsorbed in the graphite material, and after the solvent is removed (such as heating and solvent removal), the graphite material can be directly subjected to punch forming by using a bipolar plate die, or a base material is pre-pressed to prepare a flat plate with a certain thickness and then subjected to punch forming, and a bipolar plate product is obtained after curing.
The composite bipolar plate base material can be directly formed in a mold with a flow channel through a punching machine in a cold pressing mode, a 1-5 mm prefabricated plate can be prepared through flattening and pre-pressing forming firstly, then the composite bipolar plate base material is formed in the mold with the flow channel through the cold pressing forming of a press machine in the direct cold pressing mode, and during forming, the composite bipolar plate base material is formedThe time is less than or equal to 5 minutes, the composite bipolar plate can be vacuumized, the punch forming pressure is 50-300 MPa, the mold temperature is-10-100 ℃, the forming thickness is more than or equal to 0.6mm, the thinnest part of the die-pressing composite bipolar plate is 0.2mm, and the composite bipolar plate formed by cold pressing has initial strength and can be easily demoulded. The molded composite bipolar plate can be put into an oven for curing in batches, and the curing temperature is 25-500 ℃. The electrical conductivity of the cured composite bipolar plate is more than or equal to 100S/cm, and the contact resistance is less than or equal to 30m omega cm2Flatness is less than or equal to 10um, bending strength is more than or equal to 25MPa, and gas transmission coefficient is less than or equal to 2 multiplied by 10-14Std cm3/(sec cm2Pa) @80 deg.C, 3atm, 100% RH. The preparation method reduces production cost and improves production efficiency.
The following description is given with reference to specific examples.
Example 1
A preparation method of a composite bipolar plate comprises the following steps:
(1) providing raw materials:
80 parts of expanded graphite powder with D50 particle size of 25-200 microns
8 parts of flake graphite powder with D50 particle size of 25-250 microns
18 parts of graphite worms with expansion factor of 300mL/g
30 parts of liquid epoxy resin
Carboxyl liquid nitrile rubber 1 part
1 part of graphene conductive filler
And 500 parts of dichloromethane solvent.
(2) The molding process comprises the following steps: dissolving carboxyl liquid nitrile rubber and liquid epoxy resin in dichloromethane to obtain a mixed solution, mechanically stirring and uniformly mixing expanded graphite, crystalline flake graphite, graphite worms and conductive filler with strong force, uniformly mixing the mixed solution and powder, removing a solvent to obtain a base material of the composite bipolar plate, putting the base material into a punch forming die, punching for 5min at a punching pressure of 100MPa, and heating and curing for 100min after forming to obtain the composite bipolar plate.
Example 2
A preparation method of a composite bipolar plate comprises the following steps:
(1) providing raw materials:
74 parts of expanded graphite powder with D50 particle size of 25-200 microns
6 parts of flake graphite powder with the particle size of 25-250 micrometers of D50
15 parts of graphite worms with expansion multiple of 200mL/g
25 parts of liquid epoxy resin
0.5 part of carboxyl liquid nitrile rubber
0.5 part of graphene conductive filler
450 parts of dichloromethane solvent.
(2) The molding process comprises the following steps: dissolving carboxyl liquid nitrile rubber and liquid epoxy resin in dichloromethane to obtain a mixed solution, mechanically stirring and uniformly mixing expanded graphite, crystalline flake graphite, graphite worms and conductive filler with strong force, uniformly mixing the mixed solution and powder, removing a solvent to obtain a base material of the composite bipolar plate, putting the base material into a punch forming die, punching for 4min at a punching pressure of 120MPa, and heating and curing for 80min after forming to obtain the composite bipolar plate.
Example 3
A preparation method of a composite bipolar plate comprises the following steps:
(1) providing raw materials:
90 parts of expanded graphite powder with D50 particle size of 25-200 microns
15 parts of flake graphite powder with D50 particle size of 25-250 microns
24 parts of graphite worms with expansion multiple of 450mL/g
35 parts of liquid epoxy resin
4 portions of carboxyl liquid nitrile rubber
4 parts of graphene conductive filler
And 600 parts of dichloromethane solvent.
(2) The molding process comprises the following steps: dissolving carboxyl liquid nitrile rubber and liquid epoxy resin in dichloromethane to obtain a mixed solution, mechanically stirring and uniformly mixing expanded graphite, crystalline flake graphite, graphite worms and conductive filler with strong force, uniformly mixing the mixed solution and powder, removing a solvent to obtain a base material of the composite bipolar plate, putting the base material into a punch forming die, punching for 5min at a punching pressure of 200MPa, and heating and curing for 120min after forming to obtain the composite bipolar plate.
Comparative example 1
A preparation method of a composite bipolar plate comprises the following steps:
(1) providing raw materials:
88 parts of expanded graphite powder with the particle size of 25-200 microns of D50;
18 parts of graphite worms with expansion factor of 300mL/g
30 parts of liquid epoxy resin
Carboxyl liquid nitrile rubber 1 part
1 part of graphene conductive filler
And 500 parts of dichloromethane solvent.
(2) The molding process comprises the following steps: same as in example 1.
Comparative example 2
A preparation method of a composite bipolar plate comprises the following steps:
(1) providing raw materials:
80 parts of flake graphite powder with D50 particle size of 25-250 microns
15 parts of graphite worms with expansion multiple of 200mL/g
25 parts of liquid epoxy resin
0.5 part of carboxyl liquid nitrile rubber
0.5 part of graphene conductive filler
450 parts of dichloromethane solvent.
(2) The molding process comprises the following steps: same as in example 2.
Comparative example 3
A preparation method of a composite bipolar plate comprises the following steps:
(1) providing raw materials:
129 parts of expanded graphite powder with the particle size of 25-200 microns of D50;
35 parts of liquid epoxy resin
4 portions of carboxyl liquid nitrile rubber
4 parts of graphene conductive filler
And 600 parts of dichloromethane solvent.
(2) The molding process comprises the following steps: same as in example 3.
Performance testing
(1) The measurement of the composite bipolar plate of example 1 is shown in fig. 2, and the results show that the composite bipolar plate has high channel accuracy.
(2) The mold and product runner depth and roughness measurements for examples 1-3 are shown in table 1 and the mold and product runner depth and roughness measurements for comparative examples 1-3 are shown in table 2. The data show that the composite bipolar plates of examples 1-3 of the present application have better flow channel accuracy.
TABLE 1
TABLE 2
The above description is only exemplary of the present application and should not be taken as limiting the present application, as any modification, equivalent replacement, or improvement made within the spirit and principle of the present application should be included in the protection scope of the present application.
Claims (10)
1. The composite bipolar plate is characterized in that the raw materials of the composite bipolar plate comprise the following components in parts by weight:
70-90 parts of expanded graphite with the D50 particle size of 1-300 mu m;
5-15 parts of flake graphite with the particle size of D50 being 1-500 mu m;
10-25 parts of graphite worms with expansion multiplying power of 50-2000 mL/g;
15-35 parts of liquid resin;
0.5-5 parts of a toughening agent;
0.5-5 parts of conductive filler.
2. The composite bipolar plate of claim 1, wherein said expanded graphite has a D50 particle size of 25 to 200 μm; and/or the presence of a gas in the gas,
the particle size of D50 of the flake graphite is 25-250 mu m; and/or the presence of a gas in the gas,
the expansion ratio of the graphite worms is 100-500 mL/g.
3. The composite bipolar plate of claim 1 wherein said liquid resin is selected from the group consisting of unsaturated resins.
4. The composite bipolar plate of claim 1, wherein said liquid resin is selected from any one of phenol formaldehyde, epoxy, vinyl, urea formaldehyde.
5. The composite bipolar plate of claim 4, wherein said toughening agent is selected from the group consisting of adhesives corresponding to said liquid resin.
6. The composite bipolar plate of claim 1, wherein said conductive filler is selected from at least one of graphene, carbon nanotubes, carbon fibers, platinum powder, and conductive polymer resin.
7. The preparation method of the composite bipolar plate is characterized by comprising the following steps:
providing a feedstock for a composite bipolar plate according to any one of claims 1 to 6;
dissolving the toughening agent and the liquid resin in a solvent to obtain a mixed solution;
mixing the expanded graphite, the flake graphite, the graphite worms and the conductive filler to obtain a mixed material;
and (3) uniformly mixing the mixed solution and the mixed material, removing the solvent, and then performing punch forming and curing treatment to obtain the composite bipolar plate.
8. The preparation method of claim 7, wherein in the step of stamping and forming, the stamping pressure is 50-200 Mpa, and the stamping time is 1-5 min.
9. The preparation method according to claim 8, wherein the step of stamping forming further comprises pre-pressing a prefabricated plate with a thickness of 1-5 mm.
10. The method according to any one of claims 7 to 9, wherein the curing treatment is carried out at a temperature of 25 to 500 ℃ for 5 to 120 min.
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| CN114759210B (en) * | 2022-06-13 | 2022-09-02 | 湖南耕驰新能源科技有限公司 | Preparation method of bipolar plate |
| CN115322516A (en) * | 2022-08-18 | 2022-11-11 | 厦门泰启力飞科技有限公司 | High-performance fuel cell bipolar plate base material and preparation method thereof |
| CN115490459A (en) * | 2022-09-23 | 2022-12-20 | 北京吉拓创能科技有限公司 | Graphite polar plate and preparation method thereof, alkaline electrolytic cell and water electrolysis hydrogen production equipment |
| CN115472858B (en) * | 2022-10-28 | 2023-03-24 | 江苏金亚隆科技有限公司 | Manufacturing method of enhanced composite graphite polar plate |
| CN115995572B (en) * | 2023-02-14 | 2023-08-29 | 温州锌时代能源有限公司 | Composite bipolar plate for zinc-bromine flow battery, preparation method and application thereof |
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| CN101101994A (en) * | 2007-07-17 | 2008-01-09 | 武汉理工大学 | Expansion graphite base compound material dual-pole board and its making method |
| CN111916782A (en) * | 2020-06-29 | 2020-11-10 | 惠州市杜科新材料有限公司 | Ultrathin graphite composite bipolar plate base material capable of being rapidly cold-pressed and formed and preparation method thereof |
| CN112290040A (en) * | 2020-10-30 | 2021-01-29 | 江苏清能新能源技术股份有限公司 | Preparation method of composite graphite bipolar plate |
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| US20030104257A1 (en) * | 2001-12-03 | 2003-06-05 | Jeremy Chervinko | Method for bipolar plate manufacturing |
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| CN101101994A (en) * | 2007-07-17 | 2008-01-09 | 武汉理工大学 | Expansion graphite base compound material dual-pole board and its making method |
| CN111916782A (en) * | 2020-06-29 | 2020-11-10 | 惠州市杜科新材料有限公司 | Ultrathin graphite composite bipolar plate base material capable of being rapidly cold-pressed and formed and preparation method thereof |
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