CN116093358A - Graphite composite bipolar plate, preparation method thereof and fuel cell - Google Patents
Graphite composite bipolar plate, preparation method thereof and fuel cell Download PDFInfo
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- CN116093358A CN116093358A CN202310159490.9A CN202310159490A CN116093358A CN 116093358 A CN116093358 A CN 116093358A CN 202310159490 A CN202310159490 A CN 202310159490A CN 116093358 A CN116093358 A CN 116093358A
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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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Abstract
The application relates to a graphite composite bipolar plate, a preparation method thereof and a fuel cell, wherein the graphite composite bipolar plate comprises a plurality of flexible graphite plates which are arranged in a laminated mode and a resin layer arranged between any two adjacent flexible graphite plates, at least one flexible graphite plate is provided with a pore canal which penetrates through in the thickness direction, resin materials are permeated into the interior of each flexible graphite plate, resin connecting parts are embedded into the pore canal, and the resin connecting parts are connected with the adjacent resin layers. The resin layers are arranged between two adjacent flexible graphite plates, and resin materials are permeated into the flexible graphite plates, so that the density and the air tightness of the graphite composite bipolar plate can be effectively improved; through at least arranging the through hole in the thickness direction of one flexible graphite plate to embedding resin connecting portion in the hole, and control resin connecting portion and adjacent resin layer to be connected, can play the effect of similar rivet, thereby effectively improve the tensile strength of graphite composite bipolar plate.
Description
Technical Field
The application relates to the field of fuel cells, in particular to a graphite composite bipolar plate, a preparation method thereof and a fuel cell.
Background
Fuel cells are devices that convert hydrogen and oxygen into electrical energy, and stacks are the core of fuel cells. The galvanic pile is formed by alternately overlapping membrane electrodes and bipolar plates and is pressed by front and rear ends and a compensation device. The bipolar plate occupies a relatively high weight of the electric pile, is a key component of the electric pile, and plays roles of separating and introducing reaction gas, collecting and conducting current, supporting a membrane electrode, and being responsible for drainage and heat dissipation of the electric pile, and the quality of the bipolar plate determines the output power and the service life of the electric pile.
The bipolar plate is mainly divided into a metal bipolar plate, a graphite bipolar plate and a graphite composite bipolar plate, wherein the surface corrosion resistance of the metal bipolar plate is poor, the processing efficiency of the graphite bipolar plate is low, and the graphite composite bipolar plate has high production efficiency, long service life, good corrosion resistance and other performances and is widely applied. However, with the development of society, the requirements on the power density of the electric pile are higher and higher, the requirements on the weight of the bipolar plate are lower and lower, and the gas resistance performance of the bipolar plate and the supporting effect on the membrane electrode are weaker.
Disclosure of Invention
Based on the above, the application provides a graphite composite bipolar plate with higher density and tensile strength and better air tightness, a preparation method thereof and a fuel cell.
The technical scheme for solving the technical problems is as follows.
The utility model provides a graphite composite bipolar plate, includes a plurality of stacks of flexible graphite board that set up and locates arbitrary adjacent two resin layer between the flexible graphite board, at least one flexible graphite board has the pore that runs through in the thickness direction, and each flexible graphite board's inside is permeated there is the resin material, the pore embedding has the resin connecting portion, the resin connecting portion is connected with adjacent the resin layer.
In some of these embodiments, the number of flexible graphite sheets in the graphite composite bipolar plate is 3 to 6 layers.
In some of these embodiments, the graphite composite bipolar plate has a thickness of 1mm to 2mm.
In some of these embodiments, the cell is present in the flexible graphite sheet in an area ratio of 0.1% to 0.5% in the graphite composite bipolar plate.
In some of these embodiments, the flexible graphite sheet has a pore size of 0.5mm to 2mm and a pore spacing of 20mm to 40mm in the graphite composite bipolar plate.
In some of these embodiments, the channels are filled with the resin joints in the graphite composite bipolar plate.
In some of these embodiments, each of the flexible graphite sheets has the cells in a graphite composite bipolar plate.
In some of these embodiments, the resin material in the resin layer, the resin material infiltrated inside the flexible graphite sheet, and the resin material in the resin joint are each independently selected from at least one of epoxy, acrylic, and phenolic.
In some of these embodiments, the resin layer further comprises a conductive powder selected from at least one of graphite and carbon black.
The application provides a preparation method of a graphite composite bipolar plate, which comprises the following steps:
providing a plurality of flexible graphite sheets, wherein at least one flexible graphite sheet has a channel penetrating in a thickness direction;
laminating the plurality of flexible graphite plates, arranging a first resin solution between two adjacent flexible graphite plates, and performing compression molding to obtain a bipolar plate intermediate;
and (3) impregnating the bipolar plate intermediate in a second resin solution, cleaning the surface of the bipolar plate intermediate, and then performing curing treatment to obtain the graphite composite bipolar plate.
In some embodiments, the method for preparing the graphite composite bipolar plate comprises the following steps: the pressure is 3MPa to 10MPa, the temperature is 90 ℃ to 150 ℃ and the time is 60min to 120min.
In some of these embodiments, the flexible graphite sheet material has a thickness of 2mm to 4mm in the method of making the graphite composite bipolar plate.
In some of these embodiments, in the method of making a graphite composite bipolar plate, the ratio of the mass of the first resin solution to the surface area of the flexible graphite sheet is 100g/m 2 ～300g/m 2 The solid content of the first resin solution is 3% -12%.
In some of these embodiments, the method of making a graphite composite bipolar plate wherein the first resin solution is disposed between two adjacent flexible graphite sheets is selected from spray coating or infiltration.
The application provides the application of the graphite composite bipolar plate or the graphite composite bipolar plate prepared by the preparation method in preparing fuel cells.
The application provides a fuel cell, which comprises a plurality of bipolar plates which are arranged in a stacked manner and a membrane electrode which is arranged between two adjacent bipolar plates, wherein at least one bipolar plate is the graphite composite bipolar plate or the graphite composite bipolar plate manufactured by the manufacturing method.
Compared with the prior art, the graphite composite bipolar plate has the following beneficial effects:
according to the graphite composite bipolar plate, the resin layers are arranged between two adjacent flexible graphite plates, and the resin materials are permeated into the flexible graphite plates, so that the density and the air tightness of the graphite composite bipolar plate can be effectively improved; through arranging a through hole in the thickness direction of at least one flexible graphite plate, embedding a resin connecting part in the hole, controlling the resin connecting part to be connected with an adjacent resin layer, the function similar to a rivet can be achieved, and the tensile strength of the graphite composite bipolar plate is effectively improved; the characteristics of the graphite composite bipolar plate are combined, so that the density and tensile strength of the graphite composite bipolar plate are high, and the air tightness is good.
Detailed Description
The technical scheme of the present application is described in further detail below in conjunction with specific embodiments. This application may be embodied in many different forms and is not limited to the embodiments described herein. It should be understood that these embodiments are provided so that this disclosure will be thorough and complete.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this application belongs. The terminology used herein in the description of the application is for the purpose of describing particular embodiments only and is not intended to be limiting of the application.
In the description of the present application, it should be understood that the terms "first," "second," and the like are used for descriptive purposes only and are not to be construed as indicating or implying a relative importance or an implicit indication of the number of technical features being indicated. Thus, a feature defining "a first" or "a second" may explicitly or implicitly include one or more such feature. In the description of the present application, the meaning of "a plurality" is two or more, unless explicitly defined otherwise.
The weights of the relevant components mentioned in the embodiments of the present application may refer not only to specific contents of the components, but also to the proportional relationship between the weights of the components, and thus, any ratio of the contents of the relevant components according to the embodiments of the present application may be enlarged or reduced within the scope disclosed in the embodiments of the present application. Specifically, the weight described in the specification of the examples of the present application may be a mass unit known in the chemical industry such as μ g, mg, g, kg.
The utility model provides a graphite composite bipolar plate, including a plurality of flexible graphite boards that range upon range of setting and locate the resin layer between arbitrary adjacent two flexible graphite boards, at least one flexible graphite board has the pore that runs through at the thickness direction, and the inside infiltration of each flexible graphite board has resin material, and the pore embedding has resin connecting portion, and resin connecting portion is connected with adjacent resin layer.
It will be appreciated that "the interior of each flexible graphite sheet" includes, but is not limited to, cell regions and non-cell regions; the interior of a conventional flexible graphite sheet itself has many holes, and the "interior of each flexible graphite sheet" includes, but is not limited to, through-channels through which the flexible graphite sheet passes in the thickness direction and internal holes of the flexible graphite sheet itself.
It will be appreciated that the channels are embedded with resin connection portions and that the resin connection portions are connected to adjacent resin layers, which may then act like rivets.
According to the graphite composite bipolar plate, the resin layers are arranged between two adjacent flexible graphite plates, and the resin materials are permeated into the flexible graphite plates, so that the density and the air tightness of the graphite composite bipolar plate can be effectively improved; through at least arranging the through hole in the thickness direction of one flexible graphite plate to embedding resin connecting portion in the hole, and control resin connecting portion and adjacent resin layer to be connected, can play the effect of similar rivet, thereby effectively improve the tensile strength of graphite composite bipolar plate.
The characteristics of the graphite composite bipolar plate are combined, so that the density and tensile strength of the graphite composite bipolar plate are high, and the air tightness is good.
It is understood that the graphite composite bipolar plate is provided with flow channels.
In some of these examples, the number of flexible graphite sheets in the graphite composite bipolar plate is 3 to 6 layers.
It is understood that the number of flexible graphite sheets includes, but is not limited to, 3, 4, 5, 6 layers.
In some of these examples, the graphite composite bipolar plate has a thickness of 1mm to 2mm.
It is understood that the thickness of the graphite composite bipolar plate includes, but is not limited to, 1mm, 1.5mm, 2mm.
In some examples, the area of the pore channels in the flexible graphite sheet is 0.1% -0.5% in the graphite composite bipolar plate.
It is understood that the area ratio of the pore channels in the flexible graphite sheet includes, but is not limited to, 0.1%, 0.2%, 0.3%, 0.4%, 0.5%.
In some of these examples, the flexible graphite sheet has a pore size of 0.5mm to 2mm and a pore spacing of 20mm to 40mm in the graphite composite bipolar plate.
It will be appreciated that the pore size of the flexible graphite sheet includes, but is not limited to, 0.5mm, 0.8mm, 1mm, 1.2mm, 1.5mm, 1.8mm, 2mm; hole spacing includes, but is not limited to, 20mm, 22mm, 25mm, 28mm, 30mm, 32mm, 35mm, 38mm, 40mm.
It will be appreciated that embedding the cells with the resin connection includes filling the entire cells with the resin connection or not filling the entire cells with the resin connection.
In some of these examples, the channels are filled with resin joints in the graphite composite bipolar plate.
It is understood that at least one flexible graphite sheet has channels extending therethrough in the thickness direction includes, but is not limited to, one flexible graphite sheet having channels extending therethrough in the thickness direction, two or more flexible graphite sheets having channels extending therethrough in the thickness direction.
In some of these examples, each flexible graphite sheet has cells in the graphite composite bipolar plate.
In some examples, the material of the resin connection portion embedded in the pore canal in the graphite composite bipolar plate comprises resin in the resin layer and resin material permeated inside the flexible graphite plate.
In some of these examples, the resin material in the resin layer, the resin material infiltrated inside the flexible graphite sheet, and the resin material in the resin joint are each independently selected from at least one of epoxy, acrylic, and phenolic.
It is understood that the material in the resin layer, the resin material and the resin connection portion may be the same or different; when the materials, the resin materials and the resin connecting parts in the resin layer are the same, the compatibility is better, so that the resin connecting parts embedded in the pore channels are stronger, and the tensile strength of the graphite composite bipolar plate is improved.
In some of these examples, the graphite composite bipolar plate further comprises a conductive powder in the resin layer.
By adding conductive powder into the resin layer, the conductive performance of the graphite composite bipolar plate is further promoted.
Further, the conductive powder is selected from at least one of graphite and carbon black.
Optionally, the conductive powder is graphite.
In some examples, the mass ratio of the resin material in the resin layer to graphite in the graphite composite bipolar plate is (2-6): 1.
It is understood that the mass ratio of resin material to graphite in the resin layer includes, but is not limited to, 2:1, 3:1, 4:1, 5:1, 6:1.
An embodiment of the present application provides a method for preparing a graphite composite bipolar plate, which includes steps S10 to S40.
It can be appreciated that the preparation method of the graphite composite bipolar plate provided by the application can prepare the graphite composite bipolar plate.
Step S10: a plurality of flexible graphite sheets are provided, wherein at least one of the flexible graphite sheets has channels extending therethrough in a thickness direction.
In some examples, in step S10, the flexible graphite sheet has a thickness of 2mm to 4mm.
It is understood that the thickness of the flexible graphite sheet material includes, but is not limited to, 2mm, 2.5mm, 3mm, 3.5mm, 4mm.
In some examples, in step S10, the flexible graphite sheet is perforated to obtain through-channels in the thickness direction of the flexible graphite sheet.
Further, a perforation tool is adopted for perforation, and the perforation tool consists of a steel plate and a steel needle.
It can be understood that the diameter of the steel needle in the perforation tool controls the diameter of the pore canal of the flexible graphite plate, namely the aperture; the distance between the steel needles controls the distance between the pore channels of the flexible graphite plate, namely the pore spacing; it is further understood that the steel needles have a diameter of 0.5mm to 2mm and a distance between the steel needles of 20mm to 40mm.
In some of these examples, step S10 includes the steps of:
and fixing the punching tool on a press, arranging the flexible graphite plate on the steel needle surface of the punching tool, and pressing to obtain the flexible graphite plate with the through hole in the thickness direction.
Step S20: and stacking a plurality of flexible graphite plates, arranging a first resin solution between two adjacent flexible graphite plates, and performing compression molding to obtain the bipolar plate intermediate.
In some examples, in step S20, the conditions of the compression molding are: the pressure is 3MPa to 10MPa, the temperature is 90 ℃ to 150 ℃ and the time is 60min to 120min.
It will be appreciated that in the conditions of compression molding, the pressure includes, but is not limited to, 3MPa, 4MPa, 5MPa, 6MPa, 7MPa, 8MPa, 9MPa, 10MPa, the temperature includes, but is not limited to, 90 ℃, 100 ℃, 110 ℃, 120 ℃, 130 ℃, 140 ℃, 150 ℃, and the time includes, but is not limited to, 60min, 70min, 80min, 90min, 100min, 110min, 120min.
It will be appreciated that in step S20, the compression molding is performed in a mold with flow channels, resulting in a bipolar plate intermediate with flow channels.
In some of these examples, in step S20, the first resin solution contains a resin material therein.
Further, in some of these examples, in step S20, the first resin solution contains a resin material and a conductive powder.
In some examples, in step S20, the ratio of the solute mass in the first resin solution to the surface area of the flexible graphite sheet is 3g/m 2 ～36g/m 2 。
It will be appreciated that in step S20, when the first resin solution is disposed between two adjacent flexible graphite sheets, a portion of the first resin solution may flow into the channels; controlling the ratio of the solute mass in the first resin solution to the surface area of the flexible graphite plate to ensure that the pore channels are not fully filled with the solute, thereby ensuring that the air is exhausted in the subsequent compression molding process; the better the exhaust in the compression molding process, the denser the structure and the higher the density of the graphite composite bipolar plate.
It is further understood that the solute in the first resin solution comprises a resin material or further comprises an electrically conductive powder.
It is also understood that the surface area of the flexible graphite sheet refers to the surface area in contact with the first resin solution, i.e., the sum of the areas of the two flexible graphite sheets in contact with the first resin solution, respectively, corresponds to the sum of the areas of the upper and lower planes of 1 flexible graphite sheet.
The ratio of the mass of resin in the first resin solution to the surface area of the flexible graphite sheet includes, but is not limited to, 3g/m 2 、5g/m 2 、8g/m 2 、10g/m 2 、12g/m 2 、15g/m 2 、18g/m 2 、20g/m 2 、22g/m 2 、25g/m 2 、28g/m 2 、30g/m 2 、32g/m 2 、35g/m 2 、36g/m 2 。
In some examples, in step S20, the solid content of the first resin solution is 3% to 12%.
It is understood that the solids content of the first resin solution includes, but is not limited to, 3%, 5%, 6%, 8%, 10%, 11%, 12%.
In some examples, in step S20, the ratio of the mass of the first resin solution to the surface area of the flexible graphite sheet is 100g/m 2 ～300g/m 2 。
It will be appreciated that the ratio of the mass of the first resin solution to the surface area of the flexible graphite sheet includes, but is not limited to, 100g/m 2 、120g/m 2 、150g/m 2 、180g/m 2 、200g/m 2 、220g/m 2 、250g/m 2 、260g/m 2 、280g/m 2 、290g/m 2 、300g/m 2 。
It is understood that the first resin in the first resin solution is selected from at least one of epoxy resin, acrylic resin, and phenolic resin.
In some examples thereof, in step S20, the solvent in the first resin solution is selected from at least one of methanol, ethanol, and acetone.
In some examples, in step S20, the first resin solution is disposed between two adjacent flexible graphite sheets in a manner selected from spray coating or infiltration.
Optionally, a first resin solution is disposed between two adjacent flexible graphite sheets by spraying.
The first resin solution is arranged between two adjacent flexible graphite plates in a spraying manner, so that the spraying amount of the first resin can be effectively controlled, and the airtight performance of the graphite composite bipolar plate is further improved.
In some examples, step S20 includes steps S21 to S23:
step S21: spraying a first resin solution on one surface of a flexible graphite plate to obtain a graphite plate with a first resin arranged on one surface;
step S22: spraying a first resin solution on both surfaces of another flexible graphite sheet material to obtain a graphite sheet material with both surfaces provided with the first resin;
step S23: and respectively laminating and placing the resin surfaces of the two graphite plates with the first resin arranged on one side and one or more resin surfaces of the graphite plates with the first resin arranged on both sides, and then performing compression molding to obtain the bipolar plate intermediate.
It can be understood that in step S23, the resin faces of the two graphite plates with the first resin disposed on one side are respectively stacked with the resin faces of one or more graphite plates with the first resin disposed on both sides, and after compression molding, the obtained bipolar plate intermediate includes a plurality of flexible graphite plates disposed in a stacked manner and a resin layer disposed between any two adjacent flexible graphite plates, and through-channels of the flexible graphite plates in the thickness direction are embedded with the first resin and connected with the adjacent resin layers.
It will be appreciated that step S21 and step S22 are not in order.
In some examples, in step S20, after the step of disposing the first resin solution between two adjacent flexible graphite sheets, a step of drying the flexible graphite sheets disposed with the first resin solution is included before the step of compression molding.
In some examples, in step S20, the temperature of drying is 80 ℃ to 100 ℃.
It will be appreciated that drying is performed at this temperature to bring the resin film to a surface-dried state, i.e., surface-dried; it is further understood that the temperature of drying includes, but is not limited to, 80 ℃, 85 ℃, 90 ℃, 95 ℃, 100 ℃.
Step S30: and (3) impregnating the bipolar plate intermediate in a second resin solution, cleaning the surface of the bipolar plate intermediate, and then performing curing treatment to obtain the graphite composite bipolar plate.
It can be understood that, in step S20, the first resin solution disposed between two adjacent flexible graphite sheets is formed into a resin layer by compression molding, that is, the resin material in the resin layer in the graphite composite bipolar plate is derived from the first resin solution; in the step S20, when a first resin solution is disposed between two adjacent flexible graphite sheets, a part of the first resin solution flows into the channels, and in the step S30, the bipolar plate intermediate is impregnated with a second resin solution, and the second resin solution is impregnated into the channels, that is, the resin sources of the resin connection portions in which the channels of the graphite composite bipolar plate are embedded include the first resin solution in the step S20 and the second resin solution in the step S30, and the internally infiltrated resin material of each flexible graphite sheet is derived from the first resin solution in the step S20 and the second resin solution in the step S30.
According to the preparation method of the graphite composite bipolar plate, the plurality of flexible graphite plates are stacked, the first resin solution is arranged between two adjacent flexible graphite plates, after compression molding, the first resin solution forms the first resin layer in the bipolar plate intermediate, and therefore the air tightness of the graphite composite bipolar plate can be effectively improved; the flexible graphite plate with the through hole in the thickness direction is adopted, so that the flexible graphite plate is favorable for exhausting in the compression molding process, the better the exhausting is, the more compact the inside of the flexible graphite plate is, so that the density of the graphite composite bipolar plate is effectively improved, and the air tightness and the tensile strength of the graphite composite bipolar plate are further improved; impregnating the bipolar plate intermediate in a second resin solution to enable the second resin material to permeate into the flexible graphite plate, so that the porosity of the graphite composite bipolar plate is effectively reduced, and the tensile strength and the air tightness of the graphite composite bipolar plate are further improved; in the step of arranging the first resin solution between two adjacent flexible graphite plates, the first resin solution flows into the pore channels, and when the bipolar plate intermediate is impregnated in the second resin solution, the second resin is further filled in the pore channels, so that resin connection parts are formed in the pore channels, the function similar to rivets is achieved, and the tensile strength of the graphite composite bipolar plate is further improved; the steps in the preparation method of the graphite composite bipolar plate are combined to ensure that the prepared graphite composite bipolar plate has higher density and tensile strength and better air tightness.
It will be appreciated that the second resin solution may be the same as the first resin solution or may be different.
In some examples, in step S30, the impregnating means is pressure impregnation or vacuum impregnation.
It is understood that pressure infiltration is to perform infiltration treatment with a liquid medium under pressurized conditions, and vacuum infiltration is to perform infiltration treatment with a liquid medium under vacuum conditions; the second resin solution is immersed in the interior of the bipolar plate intermediate by a pressure impregnation or vacuum impregnation method.
Further, the vacuum degree is-0.1 Mpa to 0.5Mpa.
It is understood that the second resin in the second resin solution is selected from at least one of epoxy resin, acrylic resin, and phenolic resin.
In some examples thereof, in step S30, the solvent in the second resin solution is selected from at least one of methanol, ethanol, and acetone.
In some examples, in step S30, the solid content of the second resin solution is 3% to 12%.
It is understood that the solids content of the second resin solution includes, but is not limited to, 3%, 5%, 6%, 8%, 10%, 11%, 12%.
In some examples, in step S30, the temperature of the curing process is 90 ℃ to 150 ℃.
It is understood that the temperature of the curing process includes, but is not limited to, 90 ℃, 100 ℃, 110 ℃, 120 ℃, 130 ℃, 140 ℃, 150 ℃.
In some examples, in step S30, the solvent for washing is water.
It will be appreciated that in the method for manufacturing a graphite composite bipolar plate, the thickness of the finally manufactured graphite composite bipolar plate depends on the thickness and number of the raw flexible graphite plates, the spraying amount of the first resin solution, and the compression molding conditions.
The graphite composite bipolar plate prepared by the preparation method of the graphite composite bipolar plate has higher density and tensile strength and better air tightness and conductivity.
An embodiment of the application provides an application of the graphite composite bipolar plate or the graphite composite bipolar plate prepared by the preparation method in preparing a fuel cell.
Another embodiment of the present application provides a fuel cell, including a plurality of bipolar plates stacked and disposed and a membrane electrode disposed between adjacent bipolar plates, at least one of the bipolar plates being the graphite composite bipolar plate or the graphite composite bipolar plate manufactured by the above manufacturing method.
It is understood that the stack of the fuel cell contains a plurality of bipolar plates.
In some examples, the bipolar plates in the fuel cell are all graphite composite bipolar plates as described above.
In other examples, the bipolar plates in the fuel cell may include other bipolar plates in addition to the graphite composite bipolar plates described above.
The following examples of the graphite composite bipolar plate, the preparation method and the application thereof and the fuel cell according to the present application, it is understood that the graphite composite bipolar plate, the preparation method and the fuel cell according to the present application are not limited to the following examples.
Example 1
(1) Fixing a punching tool (the diameter of steel needles is 0.5mm, the distance between the steel needles is 20 mm) on a press, pushing in a flexible graphite plate with the thickness of 2mm, and pressing to obtain a flexible graphite plate with a through hole in the thickness direction;
(2) Preparing epoxy resin and graphite powder into a first resin solution with 3% of solid content according to the mass ratio of 4:1 and ethanol, and thenThe ratio of the mass of the first resin solution to the surface area of the flexible graphite sheet was 100g/m 2 Spraying the first resin solution on one surface and two surfaces of different flexible graphite plates respectively by adopting spraying equipment, and drying at 80 ℃ until the surfaces are dry to obtain the flexible graphite plates with the first resin on one side and the flexible graphite plates with the first resin on both sides respectively;
(3) Placing a mold with a runner in the order of 1 flexible graphite plate with first resin on one side, 4 flexible graphite plates with first resin on two sides and 1 flexible graphite plate with first resin on one side, attaching the surface without the first resin to the mold, and performing compression molding under the conditions of 3MPa of pressure, 120 ℃ of temperature and 120min of time to obtain the flexible graphite plate with the runner;
(4) Preparing epoxy resin and ethanol to obtain a second resin solution with 3% of solid content, then carrying out vacuum infiltration on the flexible graphite plate with the runner in the second resin solution under the vacuum condition of-0.1 Mpa to enable the resin to be immersed into the flexible graphite plate, taking out after the infiltration is finished, scraping off the resin solution on the surface, cleaning the surface by adopting water, and curing at 120 ℃ to obtain the graphite composite bipolar plate, wherein the total thickness of the graphite composite bipolar plate is 2mm.
Example 2
(1) Fixing a punching tool (the diameter of steel needles is 2mm, the distance between the steel needles is 40 mm) on a press, pushing in a flexible graphite plate with the thickness of 3mm, and pressing to obtain the flexible graphite plate with a through hole in the thickness direction;
(2) Preparing phenolic resin and graphite powder into a first resin solution with solid content of 5% according to the mass ratio of 6:1 and acetone, and then preparing the first resin solution into a flexible graphite plate with the mass ratio of 200g/m according to the mass of the first resin solution and the surface area of the flexible graphite plate 2 Spraying the first resin on one surface and two surfaces of different flexible graphite plates respectively by adopting spraying equipment, and drying at 80 ℃ until the surfaces are dry to obtain the flexible graphite plates with the first resin on one side and the flexible graphite plates with the first resin on both sides respectively;
(3) Placing a mold with a runner in the sequence of 1 flexible graphite plate with first resin on one side, 2 flexible graphite plates with first resin on two sides and 1 flexible graphite plate with first resin on one side, attaching the flexible graphite plate without the first resin to the mold, and performing compression molding under the conditions of 10MPa of pressure, 150 ℃ of temperature and 90min of time to obtain the flexible graphite plate with the runner;
(4) Preparing phenolic resin and acetone to obtain a second resin solution with 5% of solid content, then carrying out vacuum infiltration on the flexible graphite plate in the second resin solution under the vacuum condition of-0.1 Mpa to enable the resin to be immersed into the flexible graphite plate, taking out the infiltrated flexible graphite plate after the infiltration is finished, scraping the resin solution on the surface, adopting water to clean the surface, and curing at 150 ℃ to obtain the graphite composite bipolar plate, wherein the total thickness of the graphite composite bipolar plate is 1mm.
Example 3
(1) Fixing a punching tool (the diameter of steel needles is 1mm, the distance between the steel needles is 20 mm) on a press, pushing in a flexible graphite plate with the thickness of 4mm, and pressing to obtain the flexible graphite plate with a through hole in the thickness direction;
(2) Preparing acrylic resin and graphite powder into a first resin solution with a solid content of 12% according to a mass ratio of 4:1 and methanol, and then preparing a flexible graphite plate with a mass ratio of 300g/m according to the mass of the first resin solution and the surface area of the flexible graphite plate 2 Spraying the first resin solution on one surface and two surfaces of different flexible graphite plates respectively by adopting spraying equipment, and drying at 80 ℃ until the surfaces are dry to obtain the flexible graphite plates with the first resin on one side and the flexible graphite plates with the first resin on both sides respectively;
(3) Placing a mold with a runner in the sequence of 1 flexible graphite plate with first resin on one side, and 1 flexible graphite plate with first resin on one side, wherein the flexible graphite plate without first resin is attached to the mold, and performing compression molding under the conditions of pressure of 6MPa, temperature of 90 ℃ and time of 60min to obtain the flexible graphite plate with the runner;
(4) Preparing acrylic resin and methanol to obtain a second resin solution with a solid content of 12%, then carrying out vacuum infiltration on the flexible graphite plate in the second resin solution under the vacuum condition of-0.1 Mpa to enable the resin to be immersed into the flexible graphite plate, taking out the infiltrated flexible graphite plate after the infiltration is finished, scraping the resin solution on the surface, adopting water to clean the surface, and curing at 90 ℃ to obtain the graphite composite bipolar plate, wherein the total thickness of the graphite composite bipolar plate is 2mm.
Example 4
The same as in example 1 was followed except that in the punching tool, the steel needles had a diameter of 1mm and a pitch of 30mm.
Example 5
Substantially the same as in example 1, except that in the punching tool, the steel needle diameter was 2mm and the steel needle diameter was 40mm.
Example 6
Substantially the same as in example 1, except that in step (2), the flexible graphite sheet was impregnated with the first resin solution, and after the impregnation was completed, the resin solution on one surface of 2 flexible graphite sheets was removed, and the surface was washed with water and baked at 80 ℃ to dryness, to finally obtain a flexible graphite sheet having the first resin on one side and a flexible graphite sheet having the first resin on both sides.
Comparative example 1
(1) Carrying out compression molding on a flexible graphite plate with the thickness of 12mm under the conditions of the pressure of 3MPa, the temperature of 120 ℃ and the time of 120min to obtain a graphite plate with a flow channel;
(2) And (3) carrying out vacuum infiltration on the graphite plate in an epoxy resin-ethanol solution with 3% of solid content under the vacuum condition of-0.1 Mpa, immersing the epoxy resin into the graphite plate, taking out the impregnated graphite plate after the infiltration is finished, scraping off the resin solution on the surface, cleaning the surface with water, and curing at 120 ℃ to obtain the graphite composite bipolar plate, wherein the total thickness of the graphite composite bipolar plate is 2mm.
Comparative example 2
Substantially the same as in example 1, except that step (1) in example 1 was omitted, the first resin solution was directly sprayed on one surface and both surfaces of different flexible graphite sheets (having no through-channels in the thickness direction), respectively.
Comparative example 3
(1) Fixing a punching tool (the diameter of steel needles is 0.5mm, the distance between the steel needles is 20 mm) on a press, pushing in a flexible graphite plate with the thickness of 12mm, and pressing to obtain the flexible graphite plate with through holes in the thickness direction;
(2) Preparing epoxy resin and graphite powder according to a mass ratio of 4:1 and ethanol to obtain a first resin solution with 3% of solid content, carrying out vacuum infiltration on the flexible graphite plate with the through-channels in the thickness direction obtained in the step (1) in the first resin solution under the vacuum condition of-0.1 Mpa, taking out the flexible graphite plate after the infiltration is finished, scraping off the resin solution on the surface, cleaning the surface by adopting water, carrying out semi-curing treatment on the cleaned flexible graphite plate, and carrying out compression molding under the conditions of the pressure of 3MPa, the temperature of 120 ℃ and the time of 120min to obtain the flexible graphite plate with the flow channels;
(4) Preparing epoxy resin and ethanol to obtain a second resin solution with 3% of solid content, vacuum impregnating the flexible graphite plate with the runner in the second resin solution under the vacuum condition of-0.1 Mpa, taking out after the impregnation is finished, scraping off the resin solution on the surface, cleaning the surface with water, and curing at 120 ℃ to obtain the graphite composite bipolar plate, wherein the total thickness of the graphite composite bipolar plate is 2mm.
The density (GB/T20042.6-2011), tensile strength (JB/T9141.2-1999) and air permeability (GB/T20042.6-2011) of the graphite composite bipolar plates prepared in each example and comparative example were tested, and the conductivity was measured by using a four-probe conductivity meter, and the results are shown in Table 1.
TABLE 1
Wherein, the thickness refers to the thickness of the graphite composite bipolar plate.
As can be seen from table 1, compared with the comparative example, the graphite composite bipolar plate prepared in the example has higher density and tensile strength, lower air permeability, i.e. better air tightness; and the conductivity still meets the requirement of more than 100S/cm.
The technical features of the above-described embodiments may be arbitrarily combined, and all possible combinations of the technical features in the above-described embodiments are not described for brevity of description, however, as long as there is no contradiction between the combinations of the technical features, they should be considered as the scope of the description.
The above examples merely represent a few embodiments of the present application, which facilitate a specific and detailed understanding of the technical solutions of the present application, but are not to be construed as limiting the scope of the invention. It should be noted that it would be apparent to those skilled in the art that various modifications and improvements could be made without departing from the spirit of the present application, which would be within the scope of the present application. It should be understood that those skilled in the art, based on the technical solutions provided in the present application, can obtain technical solutions through logical analysis, reasoning or limited experiments, all fall within the protection scope of the claims attached in the present application. The scope of the patent application is therefore intended to be indicated by the appended claims, and the description may be used to interpret the contents of the claims.
Claims (14)
1. The utility model provides a graphite composite bipolar plate which characterized in that includes a plurality of stacks of flexible graphite board that set up and locates arbitrary adjacent two resin layer between the flexible graphite board, at least one flexible graphite board has the pore that runs through in the thickness direction, and each the inside of flexible graphite board is permeated with resin material, the pore has embedded resin connecting portion, resin connecting portion is connected with adjacent resin layer.
2. The graphite composite bipolar plate of claim 1 wherein the number of flexible graphite sheets is 3 to 6 layers.
3. The graphite composite bipolar plate of claim 1 wherein said graphite composite bipolar plate has a thickness of 1mm to 2mm.
4. A graphite composite bipolar plate as claimed in any one of claims 1 to 3 wherein said cells have a pore diameter of 0.5mm to 2mm and a pore spacing of 20mm to 40mm.
5. A graphite composite bipolar plate as claimed in any one of claims 1 to 3 wherein said cells occupy an area of 0.1% to 0.5% of said flexible graphite sheet.
6. A graphite composite bipolar plate as claimed in any one of claims 1 to 3, wherein said cells are filled with said resin joints.
7. A graphite composite bipolar plate as claimed in any one of claims 1 to 3 wherein each of said flexible graphite sheets has said cells.
8. The graphite composite bipolar plate as recited in any one of claims 1 to 3, wherein the resin material in said resin layer, the resin material permeated inside said flexible graphite sheet and the resin material in said resin joint are each independently selected from at least one of epoxy resin, acrylic resin and phenolic resin.
9. The graphite composite bipolar plate of any one of claims 1 through 3 wherein said resin layer further comprises a conductive powder selected from at least one of graphite and carbon black.
10. The method of manufacturing a graphite composite bipolar plate according to any one of claims 1 to 9, comprising the steps of:
providing a plurality of flexible graphite sheets, wherein at least one flexible graphite sheet has a channel penetrating in a thickness direction;
laminating the plurality of flexible graphite plates, arranging a first resin solution between two adjacent flexible graphite plates, and performing compression molding to obtain a bipolar plate intermediate;
and (3) impregnating the bipolar plate intermediate in a second resin solution, cleaning the surface of the bipolar plate intermediate, and then performing curing treatment to obtain the graphite composite bipolar plate.
11. The method of preparing a graphite composite bipolar plate as recited in claim 10, wherein said compression molding conditions are: the pressure is 3MPa to 10MPa, the temperature is 90 ℃ to 150 ℃ and the time is 60min to 120min.
12. The method of manufacturing a graphite composite bipolar plate as claimed in claim 10, wherein the flexible graphite sheet has a thickness of 2mm to 4mm.
13. The method of preparing a graphite composite bipolar plate as claimed in claim 10, wherein a ratio of a mass of said first resin solution to a surface area of said flexible graphite sheet is 100g/m 2 ～300g/m 2 The solid content of the first resin solution is 3% -12%.
14. A fuel cell comprising a plurality of bipolar plates arranged in a stacked manner and a membrane electrode provided between two adjacent bipolar plates, at least one of the bipolar plates being a graphite composite bipolar plate according to any one of claims 1 to 9 or a graphite composite bipolar plate produced by the production method according to any one of claims 10 to 13.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN116914175A (en) * | 2023-09-13 | 2023-10-20 | 北京普能世纪科技有限公司 | Flow battery bipolar plate and current collecting plate |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN116914175A (en) * | 2023-09-13 | 2023-10-20 | 北京普能世纪科技有限公司 | Flow battery bipolar plate and current collecting plate |
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