CN113823807A - Composition, composite conductive ceramic bipolar plate thereof and preparation method - Google Patents
Composition, composite conductive ceramic bipolar plate thereof and preparation method Download PDFInfo
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Abstract
A composition and a composite conductive ceramic bipolar plate and a preparation method thereof, wherein the composition comprises the following components in percentage by mass: 20-90 parts of conductive ceramic, 5-78 parts of adhesive and 2-10 parts of reinforcing material. The invention adopts the conductive ceramic to replace the prior graphite, does not need to use a metal panel, and effectively improves the corrosion resistance. When the composition is used for preparing the bipolar plate, secondary die pressing is not needed, the production flow is effectively simplified, the production efficiency is improved, and the composition is suitable for large-scale industrial production.
Description
Technical Field
The invention relates to the field of fuel cells, in particular to a composition, a composite conductive ceramic bipolar plate and a preparation method thereof.
Background
The energy is the power for national economy development and is closely related to the survival and development of human society. Among various novel power supplies, fuel cells have been known as a fourth generation power generation technology following water power, fire power and nuclear power due to their advantages of high efficiency, low pollution, short plant construction time, wide site selection condition and the like. A fuel cell is an energy conversion device that directly and continuously converts chemical energy in a fuel and an oxidant into electrical energy. The fuel of the cell can be hydrogen, alcohol, hydrocarbon, etc., and the oxidant is generally oxygen or air. The fuel cell system does not require recharging and, as long as fuel is fed directly into the fuel cell system, the fuel cell system is able to convert the chemical energy of the fuel into electrical energy on an ongoing basis.
The bipolar plate is a key component for assembling single batteries into a battery stack in series, and the current commercialized bipolar plates are mainly non-porous graphite plates and modified metal plates. The impermeable graphite plate has excellent electric conduction and corrosion resistance, but the preparation and processing process is complex, so that the cost of the graphite bipolar plate is extremely high. The metal bipolar plate has poor corrosion resistance and cannot meet the requirement of long-term stable operation of the fuel cell. The search for graphite and metal alternative materials and new preparation and processing methods has become a research hotspot for preparing the PEMFC bipolar plate with excellent performance and low cost.
Among the alternative materials of graphite or metal bipolar plates, conductive ceramic fillers such as TiN, TiC, TiCN and the like have good conductivity, corrosion resistance and oxidation resistance, and can be used for preparing the bipolar plates.
Chinese patent "fuel cell composite bipolar plate and its manufacturing method" (publication number CN 1591941A) discloses a composite bipolar plate with sandwich structure obtained by mixing graphite and thermosetting resin and placing metal panel in the middle of the mould, which has excellent performance, but cannot realize large-scale production due to complex process, and the metal panel is easy to corrode, thus having corrosion hidden trouble. Specifically, the patent has a defect packet: 1. the bipolar plate mainly comprises thermosetting resin, filler and a stainless steel plate, the thermosetting resin and the filler are firstly added in the feeding process in a die, the stainless steel plate is placed, and then the thermosetting resin and the filler are added, so that the process complexity is increased; in addition, in order to ensure that the stainless steel plate is placed at a predetermined position, such as an intermediate position, equipment investment in the process or equipment, such as positioning or measuring device devices, must be increased, which substantially increases equipment and process time costs. 2. Metal panels are subject to corrosion and present a corrosion hazard. 3. Under the conditions of heating or physical vibration and the like, the deformation coefficient of the thermosetting resin is different from that of the metal plate, so that the thermosetting resin is easily deformed and separated from the metal plate, and the failure of the bipolar plate is caused.
Chinese patent "a composite bipolar plate of PEM fuel cell and its preparation method" (publication No. CN 103746131A) proposes a method for preparing a composite plate by blending soluble resin into organic solvent and then filling vermicular graphite. The bipolar plate prepared by the method can be formed under lower pressure, and has better bending strength and resistivity. However, the secondary mould pressing process is adopted in the experimental process, so that the process complexity in the preparation process is increased, and the production efficiency is reduced. Specifically, the patent has the following defects: 1. the preparation process comprises the processes of preparing, laying, molding, secondary molding and the like of the upper surface layer and the lower surface layer and the laminated plate unit prefabricated body, the process is extremely complex, the use of production equipment in each step is complex, the process consumes long time, and the production method cannot be used for large-scale production and industrialization at all. 2. Under the conditions of heating or physical vibration and the like, the bipolar plate with the laminated plate unit prefabricated body is easy to cause the separation of the connection parts of the upper surface layer, the lower surface layer and the laminated plate unit prefabricated body due to the different deformation coefficients of the upper surface layer, the lower surface layer and the laminated plate unit prefabricated body, thereby causing the failure of the bipolar plate.
Disclosure of Invention
According to a first aspect, in one embodiment, there is provided a composition comprising, by mass: 20-90 parts of conductive ceramic, 5-78 parts of adhesive and 2-10 parts of reinforcing material.
According to a second aspect, in an embodiment, there is provided a composite conductive ceramic bipolar plate comprising the composition of the first aspect.
According to a third aspect, in an embodiment, there is provided a method of making the composite conductive ceramic bipolar plate of the second aspect, comprising: mixing the raw materials, transferring the prepared mixture into a mould for mould pressing, and preparing the composite conductive ceramic bipolar plate.
According to a fourth aspect, there is provided a battery comprising the composite conductive ceramic bipolar plate of the second aspect.
According to the composition, the composite conductive ceramic bipolar plate and the preparation method thereof, the conductive ceramic is adopted to replace the existing graphite, a metal panel is not needed, the corrosion current density is obviously reduced, and the corrosion resistance is effectively improved.
In one embodiment, when the composition is used for preparing the bipolar plate, secondary die pressing is not needed, the production flow is effectively simplified, the production efficiency is improved, and the composition is suitable for large-scale industrial production.
Drawings
Fig. 1 is a schematic view of a bipolar plate manufactured in example 1.
Fig. 2 is a schematic bottom view of the bipolar plate manufactured in example 1.
Description of reference numerals: 1. a bipolar plate; 2. an airway.
Detailed Description
The present invention will be described in further detail with reference to the following embodiments. Wherein like elements in different embodiments are numbered with like associated elements. In the following description, numerous details are set forth in order to provide a better understanding of the present application. However, those skilled in the art will readily recognize that some of the features may be omitted or replaced with other elements, materials, methods in different instances. In some instances, certain operations related to the present application have not been shown or described in detail in order to avoid obscuring the core of the present application from excessive description, and it is not necessary for those skilled in the art to describe these operations in detail, so that they may be fully understood from the description in the specification and the general knowledge in the art.
Furthermore, the features, operations, or characteristics described in the specification may be combined in any suitable manner to form various embodiments. Also, the various steps or actions in the method descriptions may be transposed or transposed in order, as will be apparent to one of ordinary skill in the art. Thus, the various sequences in the specification are for the purpose of clearly describing one embodiment only and are not meant to be necessarily order unless otherwise indicated where a certain order must be followed.
The numbering of the components as such, e.g., "first", "second", etc., is used herein only to distinguish the objects as described, and does not have any sequential or technical meaning. The term "connected" and "coupled" when used in this application, unless otherwise indicated, includes both direct and indirect connections (couplings).
As used herein, "bipolar plate," also known as a collector plate, is one of the important components of a fuel cell. Has the following functions and properties: separating the fuel from the oxidant to prevent gas permeation; current is collected and conducted, and the conductivity is high; the designed and processed flow channel can uniformly distribute gas to a reaction layer of the electrode for electrode reaction; heat can be discharged, and the temperature field of the battery is kept uniform; corrosion resistance; impact and vibration resistance; the thickness is thin; the weight is light; meanwhile, the cost is low, the mechanical processing is easy, and the method is suitable for batch manufacturing and the like. The resistivity and the conductivity are in reciprocal relation, the lower the resistivity, the higher the conductivity, the better the conductivity, the smaller the current loss and the better the electrical property of the polar plate.
As used herein, "room temperature" means 20-30 ℃.
As used herein, a "fuel cell" is a chemical device that directly converts the chemical energy of a fuel into electrical energy, also known as an electrochemical generator.
According to a first aspect, in one embodiment, there is provided a composition comprising: conductive ceramic, adhesive and reinforcing material.
The conductive ceramic is metal carbonitride and is mainly used for forming a conductive network, collecting and leading out current, and the increase of the content of the conductive ceramic can reduce the resistance of the polar plate and enhance the conductivity. The conductive ceramic can enhance the corrosion resistance of the polar plate and prolong the service life of the battery; the thermal stability of the polar plate is improved.
The adhesive (including but not limited to organic resin) is mainly used for filling the gaps of the conductive powder and improving the air tightness and bending strength of the polar plate.
The reinforcing material can be a fiber reinforcing material and is mainly used for improving the bending strength of the polar plate. After effective dispersion, the flexural strength increased as the content increased (the amount added was less than the threshold value). When the content is more than the threshold value, the bending strength is deteriorated.
The existing composite bipolar plate mainly adopts graphite and metal, in one embodiment, the invention adopts conductive ceramic as conductive filler to replace graphite and metal, and the bipolar plate is obtained by pressing, thereby providing a new idea for the development of the bipolar plate, needing no metal panel, effectively improving the corrosion resistance, and when the composition is used for preparing the bipolar plate, secondary die pressing is not needed, effectively simplifying the production flow, improving the production efficiency, and being suitable for large-scale industrial production.
In one embodiment, the high-temperature resistant ceramic phase is adopted to replace graphite, and compared with the graphite, the conductive ceramic has better hydrophobicity and is more beneficial to draining water when the polar plate is in a working state, so that the drainage performance of the battery is optimized. Meanwhile, the high-temperature performance of the conductive ceramic is good, the working state of the galvanic pile is a hydrothermal circulation state, the working state of the high-temperature ceramic polar plate is stable, and the structural deformation is less likely to occur; the conductive ceramic has high hardness and small stress deformation, so that the deformation of the pole plate in the assembling process is small, and the consistency of the shape and the size of the pole plate in the galvanic pile is ensured.
In one embodiment, the conductive ceramic of the invention has high hardness, high temperature resistance and wear resistance, and can be used in various fields such as vacuum coating, various electrode coating materials, ceramic cutting tools and dies. In the field of composite ceramic materials, the high-temperature-resistant composite material can be used as an important component of a multi-component composite material, and TiC, TiN, SiC and other materials can form the composite material to manufacture various high-temperature-resistant parts and functional parts, such as high-temperature crucibles, engine parts and the like. And is one of the best materials for manufacturing armor protection materials.
In one embodiment, the composition comprises, by mass: 20-90 parts of conductive ceramic, 5-78 parts of adhesive and 2-10 parts of reinforcing material.
In one embodiment, the parts by mass of the conductive ceramic in the composition include, but are not limited to, 20 parts, 30 parts, 40 parts, 50 parts, 60 parts, 70 parts, 80 parts, and 90 parts.
In one embodiment, the mass parts of the adhesive in the composition include, but are not limited to, 5 parts, 10 parts, 20 parts, 30 parts, 40 parts, 50 parts, 60 parts, 70 parts, and 78 parts.
In one embodiment, the mass parts of the reinforcing material in the composition include, but are not limited to, 2 parts, 3 parts, 4 parts, 5 parts, 6 parts, 7 parts, 8 parts, 9 parts, and 10 parts.
In one embodiment, the composition comprises, by mass: 70-90 parts of conductive ceramic, 10-20 parts of adhesive and 4-6 parts of reinforcing material.
In one embodiment, the composition comprises, by mass: 80 parts of conductive ceramic, 15 parts of adhesive and 5 parts of reinforcing material.
In one embodiment, the conductive ceramic includes, but is not limited to, titanium nitride (TiN), titanium carbonitride (TiCN), titanium carbide (TiC), titanium diboride (TiB)2) At least one of (1).
In one embodiment, the conductive ceramic has an average particle size of 1 to 100 nm.
In one embodiment, the conductive ceramic has an average particle size of 1 to 10 nm: conductive ceramics with an average particle size of 40-50 nm: the conductive ceramic with the average particle size of 100nm =1 (0.5-5): 0.5-5), and preferably 3:4: 3. The metal carbonitrides with different particle sizes are matched with each other, so that a more effective conductive channel can be formed, the conductivity is enhanced, and the ohmic loss of the battery is reduced.
In one embodiment, the purity of the titanium carbide is more than or equal to 99.9%.
In one embodiment, the adhesive comprises a resin. As the resin content increases, the air tightness and bending strength of the polar plate are enhanced.
In one embodiment, the resin includes any one of a thermoplastic resin and a thermosetting resin.
In an embodiment, the thermoplastic resin includes, but is not limited to, at least one of phenolic resin, Polyethylene (PE), polypropylene (PP), Polycarbonate (PC), Polytetrafluoroethylene (PTFE), polyvinylidene fluoride (PVDF).
In one embodiment, the reinforcement includes, but is not limited to, at least one of carbon fibers, carbon fiber braids, carbon nanotubes, polyester fibers, and aromatic polyamide fibers (also known as aramid fibers).
In one embodiment, the diameter of the carbon fiber and the polyester fiber is 1-20 μm, the length-diameter ratio of the carbon fiber and the polyester fiber is (10-50): 1, the diameter of the carbon nanotube is 20-100 nm, and the length-diameter ratio of the carbon nanotube is (20-80): 1.
The carbon fiber is a high-strength and high-modulus fiber containing more than 90% of carbon.
According to a second aspect, in an embodiment, there is provided a composite conductive ceramic bipolar plate comprising the composition of the first aspect.
In one embodiment, the composite conductive ceramic bipolar plate is made from the composition of the first aspect.
In one embodiment, the composite conductive ceramic bipolar plate is formed by compression molding the composition of the first aspect.
According to a third aspect, in an embodiment, there is provided a method of making the composite conductive ceramic bipolar plate of the second aspect, comprising: mixing the raw materials, transferring the prepared mixture into a mould for mould pressing, and preparing the composite conductive ceramic bipolar plate.
In one embodiment, the molding temperature is 150-180 ℃, the molding pressure is 10-100 MPa, and the molding time is 10-40 min.
In one embodiment, the molding temperature includes, but is not limited to, 150 ℃, 160 ℃, 170 ℃, 180 ℃, and the like.
In an embodiment, the molding pressure includes, but is not limited to, 10MPa, 20MPa, 30MPa, 40MPa, 50MPa, 60MPa, 70MPa, 80MPa, 90MPa, 100 MPa.
In one embodiment, the molding time includes, but is not limited to, 10min, 20min, 30min, 40 min.
In one embodiment, the molding pressure is 10 to 30 MPa.
In one embodiment, the molding time is 10min to 30 min.
In one embodiment, after the die pressing is finished, cooling to 20-30 ℃, releasing the pressure and demolding to obtain the composite conductive ceramic bipolar plate.
In one embodiment, after demolding, the composite conductive ceramic bipolar plate is obtained through post-treatment. Post-processing includes, but is not limited to, flash processing. The post-processing mainly includes burr processing, and in addition, if it is not appropriate to form some hole structures in the mold, hole-forming processing may be performed after the forming.
In one embodiment, the cooling method includes, but is not limited to, at least one of circulating water cooling, hydraulic oil cooling, and the like.
In one embodiment, when mixing the components, the equipment used for mixing may include, but is not limited to, at least one of planetary mixer, ribbon mixer, rockwell mixer, henschel mixer, and tumble mixer. The mixing and stirring speed is 500-3500 r/min, and the mixing time is 10-60 min.
According to a fourth aspect, there is provided a battery comprising the composite conductive ceramic bipolar plate of the second aspect.
In one embodiment, the battery comprises a fuel cell.
In one embodiment, the conductive ceramic adopted by the invention has the characteristics of high hardness, corrosion resistance and good thermal stability, so that the prepared bipolar plate has high hardness and wear resistance and is beneficial to the assembly of a galvanic pile; the bipolar plate has good corrosion resistance and can prolong the service life of the galvanic pile. Moreover, the galvanic pile can be applied to a high-temperature galvanic pile, so that the composition and the method greatly expand the limitation of producing the polar plate only by using graphite, the polar plate has excellent performance, and the high-temperature ceramic greatly expands the production and use range of the polar plate.
In the following examples, the conductive ceramic having an average particle diameter of 1 to 10nm is satisfied by mass: conductive ceramics with an average particle size of 40-50 nm: conductive ceramic with an average particle size of 100nm =3:4: 3.
In the following examples, part 6 of a PEM fuel cell was prepared according to GB/T20042.6-2011: the method for testing the characteristics of the bipolar plate comprises the steps of testing the corresponding performances by using a method for testing the conductivity, the bending strength, the corrosion current density and the air permeability. The specific method comprises the following steps: the resistivity of a bipolar plate material is measured at room temperature, a four-probe method is usually adopted, four probes are attached to the surface of a sample in a certain load pressing mode, when current passes through the probes, each point in the sample has potential difference, and the two probes are used for measuring the potential difference of contact points of the probes. The resistivity of the sample can be calculated according to the current passing between the probes, the potential difference between the probes and the distance between the probes.
In the following examples, the flexural strength of the composite material was tested by a three-point bending method.
In the following examples, the corrosion resistance of the composite plate was determined by a polarization curve test of the composite plate in a simulated fuel cell environment using a potential sweep method. The scan rate for the polarization curve test was 1 mV. s-1The potential scanning range is-1-1.5V, the reference electrode is a saturated calomel electrode, the auxiliary electrode is a platinum electrode, and the working electrode is a composite plate.
In the following examples, when the bipolar plate is soaked in the ethylene glycol aqueous solution, the mass ratio of ethylene glycol to water in the ethylene glycol aqueous solution may be (0.5-2): 1, and specifically, 1 in the following examples: 1.
example 1
150g of phenolic resin, 800g of titanium carbonitride powder and 50g of carbon fiber (the diameter is 5 mu m, the length-diameter ratio is 20: 1) are respectively weighed and added into a planetary mixing stirrer, the stirring temperature is room temperature (25 ℃), the stirring speed is 1000r/min, and the ball milling time is 40 min. And transferring the uniformly mixed materials into a mold with a flow field, wherein the mold pressing temperature is 150 ℃, the mold pressing pressure is 20MPa, and the mold pressing time is 20 min. And finally, cooling the temperature of the die to 30 ℃ (the cooling time is about 5-60 min, in the embodiment, 10-20 min) by adopting a circulating water cooling mode, releasing the pressure, demolding, and processing burrs to obtain the composite conductive ceramic bipolar plate, wherein the length and width of the bipolar plate are 5cm x 5cm, the thickness of the bipolar plate is 0.6mm, the depth of an air field air passage is 0.3mm, and the length and width of the bipolar plate, the thickness of the bipolar plate and the depth of the air field air passage in the subsequent embodiments are the same as those in the embodiment.
Before the soaking in the ethylene glycol aqueous solution, the corrosion current density and the nitrogen gas permeability of the bipolar plate are tested. The measured corrosion current density was 0.308. mu.A.cm-2Nitrogen gas permeability of 5.8X 10-18 cm3 /（s·cm2）。
Before the soaking in the ethylene glycol aqueous solution, the conductivity of the composite conductive ceramic bipolar plate prepared in the embodiment is 82S/cm, the bending strength is 35MPa, and after the composite conductive ceramic bipolar plate is soaked in the ethylene glycol aqueous solution at 125 ℃ for 2000 hours, the conductivity is reduced by 2.0-3.0%, and the bending strength is reduced by 2.5-4.0%.
Fig. 1 and 2 are schematic structural diagrams of a bipolar plate, wherein one side of the bipolar plate 1 is provided with a plurality of parallel gas channels 2, and the gas channels 2 are in a concave structure.
Example 2
150g of phenolic resin, 800g of titanium nitride powder and 50g of carbon fiber (the diameter is 5 mu m, the length-diameter ratio is 20: 1) are respectively weighed and added into a planetary mixing stirrer, the stirring temperature is room temperature (25 ℃), the stirring speed is 1000r/min, and the ball milling time is 40 min. And transferring the uniformly mixed materials into a mold with a flow field, wherein the mold pressing temperature is 150 ℃, the mold pressing pressure is 20MPa, and the mold pressing time is 20 min. And finally, cooling the mold to 30 ℃ by adopting a circulating water cooling mode, releasing the pressure, demolding and processing burrs to obtain the composite conductive ceramic bipolar plate.
Before the soaking in the ethylene glycol aqueous solution, the corrosion current density and the nitrogen gas permeability of the bipolar plate are tested. The measured corrosion current density was 0.312. mu.A.cm-2Nitrogen gas permeability of 6.1X 10-18 cm3 /（s·cm2）。
Before the soaking in the ethylene glycol aqueous solution, the conductivity of the composite conductive ceramic bipolar plate prepared in the embodiment is 90S/cm, the bending strength is 34.5MPa, and after the composite conductive ceramic bipolar plate is soaked in the ethylene glycol aqueous solution at the temperature of 125 ℃ for 2000 hours, the conductivity is reduced by 1.5-3.0%, and the bending strength is reduced by 2.0-4.2%.
Example 3
150g of phenolic resin, 800g of titanium carbide powder and 50g of carbon fiber (the diameter is 5 mu m, the length-diameter ratio is 20: 1) are respectively weighed and added into a planetary mixing stirrer, the stirring temperature is room temperature (25 ℃), the stirring speed is 1000r/min, and the ball milling time is 40 min. And transferring the uniformly mixed materials into a mold with a flow field, wherein the mold pressing temperature is 150 ℃, the mold pressing pressure is 20MPa, and the mold pressing time is 20 min. And finally, cooling the mold to 30 ℃ by adopting a circulating water cooling mode, releasing the pressure, demolding and processing burrs to obtain the composite conductive ceramic bipolar plate.
Before the soaking in the ethylene glycol aqueous solution, the corrosion current density and the nitrogen gas permeability of the bipolar plate are tested. The measured corrosion current density was 0.298. mu.A.cm-2Nitrogen gas permeability of 4.6X 10-18 cm3 /（s·cm2）。
Before the soaking in the ethylene glycol aqueous solution, the conductivity of the composite conductive ceramic bipolar plate prepared in the embodiment is 88S/cm, the bending strength is 35.5MPa, and after the composite conductive ceramic bipolar plate is soaked in the ethylene glycol aqueous solution at the temperature of 125 ℃ for 2000 hours, the conductivity is reduced by 2.4-3.2%, and the bending strength is reduced by 2.2-3.9%.
The present invention has been described in terms of specific examples, which are provided to aid understanding of the invention and are not intended to be limiting. For a person skilled in the art to which the invention pertains, several simple deductions, modifications or substitutions may be made according to the idea of the invention.
Claims (10)
1. A composition characterized in that it comprises, by mass: 20-90 parts of conductive ceramic, 5-78 parts of adhesive and 2-10 parts of reinforcing material.
2. The composition according to claim 1, wherein the composition comprises, by mass: 70-90 parts of conductive ceramic, 10-20 parts of adhesive and 4-6 parts of reinforcing material.
3. The composition according to claim 1, wherein the composition comprises, by mass: 80 parts of conductive ceramic, 15 parts of adhesive and 5 parts of reinforcing material;
the conductive ceramic is selected from at least one of titanium nitride, titanium carbonitride, titanium carbide and titanium diboride;
the average particle size of the conductive ceramic is 1-100 nm;
among the conductive ceramics, the conductive ceramics with the average particle size of 1-10 nm by mass: conductive ceramics with an average particle size of 40-50 nm: conductive ceramic with an average particle size of 100nm =1 (0.5-5) and (0.5-5).
4. The composition according to claim 1, wherein the conductive ceramic has an average particle size of 1 to 100 nm;
among the conductive ceramics, the conductive ceramics with the average particle size of 1-10 nm by mass: conductive ceramics with an average particle size of 40-50 nm: conductive ceramic with average particle size of 100nm =3:4: 3;
the adhesive comprises a resin;
the resin is selected from any one of thermoplastic resin and thermosetting resin;
the thermoplastic resin is selected from at least one of phenolic resin, polyethylene, polypropylene, polycarbonate, polytetrafluoroethylene and polyvinylidene fluoride;
the reinforcing material is selected from at least one of carbon fiber, carbon fiber braided fabric, carbon nano tube, polyester fiber and aromatic polyamide fiber;
the diameter of the carbon fiber and the polyester fiber is 1-20 mu m, the length-diameter ratio of the carbon fiber and the polyester fiber is (10-50): 1, the diameter of the carbon nano tube is 20-100 nm, and the length-diameter ratio of the carbon nano tube is (20-80): 1.
5. A composite conductive ceramic bipolar plate comprising the composition of any one of claims 1 to 4.
6. The composite conductive ceramic bipolar plate of claim 5, wherein the composite conductive ceramic bipolar plate is prepared from the composition of any one of claims 1 to 4.
7. The composite conductive ceramic bipolar plate of claim 5, wherein the composite conductive ceramic bipolar plate is formed by compression molding the composition of any one of claims 1 to 4.
8. A method for preparing the composite conductive ceramic bipolar plate as claimed in any one of claims 5 to 7, comprising: mixing the raw materials, transferring the prepared mixture into a mould for mould pressing, and preparing the composite conductive ceramic bipolar plate.
9. The method of claim 8, wherein the molding temperature is 150 to 180 ℃;
the mould pressing pressure is 10-100 MPa;
the mould pressing time is 10-40 min;
and after the molding is finished, cooling to 20-30 ℃, releasing the pressure and demolding to obtain the composite conductive ceramic bipolar plate.
10. A battery comprising the composite conductive ceramic bipolar plate according to any one of claims 5 to 7.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114464833A (en) * | 2021-12-22 | 2022-05-10 | 萍乡市慧成精密机电有限公司 | Ceramic fuel cell bipolar plate and manufacturing method thereof |
Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6083641A (en) * | 1998-05-08 | 2000-07-04 | The United States Of America As Represented By The United States Department Of Energy | Titanium carbide bipolar plate for electrochemical devices |
| CN1595697A (en) * | 2004-06-24 | 2005-03-16 | 武汉理工大学 | A bipolar plate for fuel cell with proton exchange membrane and preparation method thereof |
| CN1919916A (en) * | 2006-07-03 | 2007-02-28 | 中山大学 | Composite material, preparation method thereof and application in fuel cell double polar plate |
| CN1964113A (en) * | 2006-11-29 | 2007-05-16 | 武汉理工大学 | A bipolar plate for conductive ceramics/graphite proton exchange membrane fuel cell and its manufacture method |
| CN108232226A (en) * | 2018-01-03 | 2018-06-29 | 湖南省银峰新能源有限公司 | A kind of preparation method of vanadium cell ceramic composite bipolar plates |
| CN109081671A (en) * | 2018-08-16 | 2018-12-25 | 成都新柯力化工科技有限公司 | A kind of ceramic base fuel battery pole board and preparation method |
| CN112786909A (en) * | 2020-12-18 | 2021-05-11 | 国科微城市智能科技(南京)有限责任公司 | Ceramic composite bipolar plate for hydrogen fuel cell |
| CN113594487A (en) * | 2021-07-30 | 2021-11-02 | 全球能源互联网欧洲研究院 | Bipolar plate and preparation method thereof |
-
2021
- 2021-11-25 CN CN202111409492.6A patent/CN113823807A/en active Pending
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6083641A (en) * | 1998-05-08 | 2000-07-04 | The United States Of America As Represented By The United States Department Of Energy | Titanium carbide bipolar plate for electrochemical devices |
| CN1595697A (en) * | 2004-06-24 | 2005-03-16 | 武汉理工大学 | A bipolar plate for fuel cell with proton exchange membrane and preparation method thereof |
| CN1919916A (en) * | 2006-07-03 | 2007-02-28 | 中山大学 | Composite material, preparation method thereof and application in fuel cell double polar plate |
| CN1964113A (en) * | 2006-11-29 | 2007-05-16 | 武汉理工大学 | A bipolar plate for conductive ceramics/graphite proton exchange membrane fuel cell and its manufacture method |
| CN108232226A (en) * | 2018-01-03 | 2018-06-29 | 湖南省银峰新能源有限公司 | A kind of preparation method of vanadium cell ceramic composite bipolar plates |
| CN109081671A (en) * | 2018-08-16 | 2018-12-25 | 成都新柯力化工科技有限公司 | A kind of ceramic base fuel battery pole board and preparation method |
| CN112786909A (en) * | 2020-12-18 | 2021-05-11 | 国科微城市智能科技(南京)有限责任公司 | Ceramic composite bipolar plate for hydrogen fuel cell |
| CN113594487A (en) * | 2021-07-30 | 2021-11-02 | 全球能源互联网欧洲研究院 | Bipolar plate and preparation method thereof |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114464833A (en) * | 2021-12-22 | 2022-05-10 | 萍乡市慧成精密机电有限公司 | Ceramic fuel cell bipolar plate and manufacturing method thereof |
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