CN114497614A - Flow battery composite bipolar plate and preparation method thereof - Google Patents
Flow battery composite bipolar plate and preparation method thereof Download PDFInfo
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- CN114497614A CN114497614A CN202111663586.6A CN202111663586A CN114497614A CN 114497614 A CN114497614 A CN 114497614A CN 202111663586 A CN202111663586 A CN 202111663586A CN 114497614 A CN114497614 A CN 114497614A
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Classifications
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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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29D—PRODUCING PARTICULAR ARTICLES FROM PLASTICS OR FROM SUBSTANCES IN A PLASTIC STATE
- B29D7/00—Producing flat articles, e.g. films or sheets
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- Engineering & Computer Science (AREA)
- Life Sciences & Earth Sciences (AREA)
- Manufacturing & Machinery (AREA)
- Sustainable Development (AREA)
- Sustainable Energy (AREA)
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Mechanical Engineering (AREA)
- Fuel Cell (AREA)
Abstract
The invention relates to a preparation method of a flow battery composite bipolar plate, which is provided with a conductive area, an insulating area and a transition area, so that the bipolar plate has good conductivity, corrosion resistance and easy weldability, solves the technical problem that the composite bipolar plate is difficult to be in sealing connection with materials such as a diaphragm, an electrode material, a frame and the like, can effectively avoid the occurrence of the leakage phenomenon of the flow battery, prolongs the service life of the battery, reduces the leakage risk, reduces the packaging cost of the battery and has higher commercial value.
Description
Technical Field
The invention belongs to the technical field of preparation of a bipolar plate of a flow battery, and particularly relates to a high-tightness and easy-to-weld flow battery composite bipolar plate and a preparation method thereof.
Background
The bipolar plate in the flow battery structure has the function of connecting the anode and the cathode of the single battery and also has the function of separating the anode liquid and the cathode liquid of the battery, and meanwhile, the electrode reactant can be uniformly distributed to all parts of the electrode through the bipolar plate by arranging a flow channel, a flow guiding field and the like. The bipolar plates must be good conductors of low electrical resistance because higher electrical resistance tends to consume more electrical energy while generating heat. In order to effectively isolate the positive and negative reaction liquids, the short circuit between the positive and negative electrodes is placed, so that the bipolar plate has sufficient barrier property and air tightness and has no leakage to gaseous and liquid substances. Flow batteries tend to have a long life, and flow battery electrolytes often have strong acidity or strong alkalinity, so that bipolar plates are required to have high mechanical strength, aging resistance and chemical corrosion resistance.
The bipolar plates currently used in the flow battery field are mainly graphite-based bipolar plates and flexible graphite bipolar plates. The two materials have the advantages of good conductivity, small contact resistance, good stability, corrosion resistance and the like, but also have the defects of poor mechanical property, poor air tightness, high welding difficulty and the like. Therefore, the leakage of the flow battery is often generated at the joint of the bipolar plate and other materials, and the leakage is a great obstacle for restricting the development of the flow battery.
Disclosure of Invention
In order to solve the problems, the invention discloses a flow battery composite bipolar plate with good conductivity, corrosion resistance, easy weldability and high tightness and a preparation method thereof.
In order to achieve the purpose, the technical scheme of the invention is as follows:
the invention aims to provide a flow battery composite bipolar plate, wherein a conductive area is arranged in the middle of the composite bipolar plate, the edge of the composite bipolar plate is an insulating area, a transition area is arranged between the conductive area and the insulating area, the conductive area and the insulating area are connected by the transition area, and the composite bipolar plate is formed by pressing the transition area on the outer ring of the pressed conductive area and pressing the insulating area on the outer ring of the transition area.
Further, the thickness of the composite bipolar plate is 0.1-5 mm.
Further, the material of the transition region is formed by compounding the material of the conductive region and the material of the insulating region.
Further, the material of the conductive area is mainly prepared by compounding a conductive material and resin; the conductive material is one or more of artificial graphite, graphene, carbon fiber, carbon nano tube and conductive plastic particles; the resin is one or more of PE, PP, PVDF, PTFE, PA, PS, ABS, ASA, PC, PMMA, POM, PES, PEEK and PBT.
Furthermore, the insulating region is mainly made of a non-conductive high polymer material, and the non-conductive high polymer material is one or more of PE, PP, PVDF, PTFE, PA, PS, ABS, ASA, PC, PMMA, POM, PES, PEEK and PBT.
The invention also aims to provide a preparation method of the flow battery composite bipolar plate, which comprises the following steps:
(1) adding resin and a conductive material into a diluent, stirring and mixing uniformly, removing the diluent, applying pressure to repeatedly press, and cutting an outer frame to obtain a conductive area;
(2) uniformly mixing resin, a conductive material and a non-conductive high polymer material to obtain a mixture, uniformly spreading the mixture on the outer ring of the conductive region, heating at normal temperature, applying pressure to repeatedly press the mixture until the mixture is formed, and cutting an outer frame to obtain a semi-finished bipolar plate product containing the conductive region and a transition region;
(3) and uniformly dispersing the non-conductive high polymer material on the outer ring of the semi-finished product of the bipolar plate, applying pressure to repeatedly press, and trimming burrs to obtain the composite bipolar plate.
Spraying of graphene is further included before pressure pressing is applied in the step (1), and the graphene can effectively improve the conductivity of the product and enhance the surface smoothness of the product.
The cold pressing or the hot pressing may be performed while the pressure pressing is applied, and those skilled in the art may adjust the physical properties of the resin, the conductive material, and the non-conductive polymer material.
Further, in the step (1), the weight ratio of the total weight of the resin and the conductive material to the diluent is 1:2-1: 100; the applied pressure is 0.5-50 MPa.
Further, the diluent is one or more of water, ethanol, methanol, ethylene glycol, diethyl ether, butanediol, isopropanol, n-butanol, acetonitrile, ethyl acetate, benzene and toluene.
Further, in the step (2), the mass ratio of the resin to the conductive material to the non-conductive polymer material is 1:1:1-1:10:20, and the applied pressure is 0.5-50 MPa.
Further, in the step (3), the applied pressure is 0.5 to 50 Mpa.
The invention has the beneficial effects that:
the invention relates to a flow battery composite bipolar plate, which is provided with a conductive area, an insulating area and a transition area, wherein the conductive area is used for playing the roles of conduction, isolation and drainage, the insulating area is used for welding with other high polymer materials to ensure the tightness of the battery, the material of the transition area is compounded by conductive area materials and insulating area resins, the material of the area takes the characteristics of the conductive area and the insulating area materials into consideration, after processing, the bipolar plate can be connected with the conductive area materials and also can be connected with the insulating area materials, and the transition area plays the role of bridging the conductive area and the insulating area. The existence of the three areas enables the bipolar plate to have good conductivity, corrosion resistance and easy weldability, solves the technical problem that the composite bipolar plate is difficult to be in sealing connection with materials such as a diaphragm, an electrode material and a frame, can effectively avoid the occurrence of liquid leakage of the flow battery, prolongs the service life of the battery, reduces the electric leakage risk, reduces the packaging cost of the battery, and has great commercial value.
The bipolar plate has a high conductive area with low resistance and no permeation, so that the conductivity of the battery pack can be effectively ensured; the pure resin area is arranged on the bipolar plate, so that the bipolar plate can be conveniently welded with modules such as a membrane, an electrode material, a frame and the like, the phenomena of air leakage and liquid leakage of a fuel cell, a flow battery and the like can be effectively avoided, the service life of the battery is prolonged, and the packaging cost of the battery is reduced.
The preparation method of the flow battery composite bipolar plate has the advantages of simple process flow and low cost, and is suitable for large-scale production.
Drawings
FIG. 1 is a schematic structural view of a composite bipolar plate of the present invention;
list of reference symbols:
1. a conductive region; 2. a transition zone; 3. an insulating region.
Detailed Description
The present invention will be further illustrated with reference to the accompanying drawings and specific embodiments, which are to be understood as merely illustrative of the invention and not as limiting the scope of the invention.
Example 1
300g of phenolic resin is diluted by 10kg of ethanol, 700g of expanded graphite is added, the mixture is fully stirred and uniformly mixed, and the obtained slurry-like mixture is uniformly placed in a pressure tank. And under the vacuum degree of 120Pa, removing the ethanol diluent, repeatedly pressing under the pressure of 0.5Mpa at normal temperature, heating to 155 ℃, repeatedly pressing under the pressure of 0.5Mpa again, and primarily forming the conductive plate by using the conductive plate, and cutting the outer frame. And (3) fully and uniformly mixing 30g of phenolic resin, 70g of expanded graphite and 100g of polyethylene powder, uniformly spreading on the outer ring of the conductive plate, putting the conductive plate into a press, repeatedly pressing and molding at 155 ℃ and under the pressure of 2Mpa, and trimming the outer frame to obtain a bipolar plate semi-finished product. Uniformly dispersing 100g of polyethylene powder on the outer edge of the semi-finished bipolar plate, repeatedly pressing at 165 ℃ under 10Mpa, and trimming burrs to obtain the finished bipolar plate. The test shows that the thickness of the bipolar plate is 0.5mm, the conductive area of the bipolar plate is black, and the resistance is 0.02 omega/cm2The outer frame of the bipolar plate is white, insulating and non-conductive.
Example 2
Fully mixing 100g of PVDF and 400g of expanded graphite, adding 1100g of ethanol, continuously stirring and uniformly mixing to obtain a slightly wet pasty solid, uniformly distributing the slightly wet pasty solid in a pressure tank, uniformly spraying 20g of graphene on the surface of the slightly wet pasty solid, gradually heating to 200 ℃, and drying for 20 min. Repeatedly pressing the conductive plate at 200 deg.C and 50Mpa to make the conductive plate be preliminarily formed, and cutting out the outer frame. And (3) fully and uniformly mixing 20g of PVDF resin, 80g of expanded graphite and 100g of PP powder, uniformly spreading the mixture on the outer ring of the conductive plate, repeatedly pressing and molding the mixture in a press at 180 ℃ and under 50Mpa, and trimming the outer frame to obtain a semi-finished product of the bipolar plate. Uniformly dispersing 100g of PP powder on the outer edge of the semi-finished bipolar plate, repeatedly pressing the semi-finished bipolar plate at 180 ℃ and 50Mpa, and trimming burrs to obtain a finished bipolar plate. The test shows that the thickness of the bipolar plate is 0.38mm, the black resistance of the conductive area of the bipolar plate is 0.008 omega/cm2The outer frame of the bipolar plate is milky white, insulating and non-conducting.
Example 3
Uniformly spreading carbon fiber cloth, fully mixing 150g of PE powder and 400g of graphite powder, uniformly dispersing on two sides of the carbon fiber cloth, slightly flattening, spraying 600g of benzene on the surface of a sample to soak the liquid, flattening again, standing for 1 hour, gradually heating to 90 ℃, and trapping gas under slight negative pressure. Repeatedly pressing the conductive plate at 90 deg.C and 50Mpa, and trapping gas at micro-negative pressure. And cutting the outer frame of the crude product of the current-conducting plate. Fully and uniformly mixing 120g of PE resin and 80g of graphite powder, uniformly spreading the mixture on the outer ring of the conductive plate, repeatedly pressing and molding the mixture in a press at 80 ℃ and 50Mpa, trapping gas at a slight negative pressure in the process, and trimming the outer frame to obtain a bipolar plate semi-finished product. Uniformly dispersing 100g of PE powder on the outer edge of the semi-finished bipolar plate, repeatedly pressing the semi-finished bipolar plate at 80 ℃ and 50Mpa, and trimming burrs to obtain a finished bipolar plate. The test shows that the thickness of the bipolar plate is 0.4mm, the conductive area of the bipolar plate is black, and the resistance is 0.022 omega/cm2The outer frame of the bipolar plate is milky white, insulating and non-conducting.
Performance testing
A white PP plate frame with a thickness of mm was cut out, and tightly welded to the outer frame of the bipolar plate obtained in example 2 using a carbon dioxide laser (40 w) at a welding speed of 0.8 m/min. Repeatedly beating, the bipolar plate is closely connected with the PP plate frame. And (4) performing a tensile test on a universal tensile testing machine, and measuring the maximum tensile strength 343N of the welding seam.
It should be noted that the above-mentioned contents only illustrate the technical idea of the present invention, and the protection scope of the present invention is not limited thereby, and it is obvious to those skilled in the art that several modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations fall within the protection scope of the claims of the present invention.
Claims (9)
1. The composite bipolar plate of the flow battery is characterized in that a conductive area is arranged in the middle of the composite bipolar plate, the edge of the composite bipolar plate is an insulating area, a transition area is arranged between the conductive area and the insulating area, and the conductive area and the insulating area are connected through the transition area; the composite bipolar plate is formed by pressing a transition area on the outer ring of a pressed conductive area and pressing an insulating area on the outer ring of the transition area.
2. The flow battery composite bipolar plate according to claim 1, wherein the thickness of the composite bipolar plate is 0.1-5 mm.
3. The flow battery composite bipolar plate as claimed in claim 1, wherein the material of the transition region is formed by compounding the material of the conductive region and the material of the insulating region.
4. The flow battery composite bipolar plate as claimed in claim 3, wherein the material of the conductive region is mainly prepared by compounding a conductive material and a resin; the conductive material is one or more of artificial graphite, graphene, carbon fiber, carbon nano tube and conductive plastic particles; the resin is one or more of PE, PP, PVDF, PTFE, PA, PS, ABS, ASA, PC, PMMA, POM, PES, PEEK and PBT.
5. The flow battery composite bipolar plate according to claim 3, wherein the material of the insulating region is mainly prepared from a non-conductive polymer material, and the non-conductive polymer material is one or more of PE, PP, PVDF, PTFE, PA, PS, ABS, ASA, PC, PMMA, POM, PES, PEEK and PBT.
6. A method for preparing a composite bipolar plate for a flow battery as claimed in any one of claims 1 to 5, comprising the steps of:
(1) adding resin and a conductive material into a diluent, stirring and mixing uniformly, removing the diluent, applying pressure to repeatedly press, and cutting an outer frame to obtain a conductive area;
(2) uniformly mixing resin, a conductive material and a non-conductive high polymer material to obtain a mixture, uniformly spreading the mixture on the outer ring of the conductive region, applying pressure to repeatedly press the mixture to form, and cutting an outer frame to obtain a semi-finished bipolar plate product containing the conductive region and a transition region;
(3) and uniformly dispersing the non-conductive high polymer material on the outer ring of the semi-finished product of the bipolar plate, applying pressure to repeatedly press, and trimming burrs to obtain the composite bipolar plate.
7. The method for preparing a flow battery composite bipolar plate according to claim 6, wherein in the step (1), the weight ratio of the total weight of the resin and the conductive material to the diluent is 1:2-1: 100.
8. The method for preparing a flow battery composite bipolar plate according to claim 7, wherein the diluent is one or more of water, ethanol, methanol, ethylene glycol, diethyl ether, butanediol, isopropanol, n-butanol, acetonitrile, ethyl acetate, benzene and toluene.
9. The method for preparing the composite bipolar plate of the flow battery as claimed in claim 6, wherein in the step (2), the mass ratio of the resin to the conductive material to the non-conductive polymer material is 1:1:1-1:10: 20.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
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| CN202111663586.6A CN114497614A (en) | 2021-12-31 | 2021-12-31 | Flow battery composite bipolar plate and preparation method thereof |
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| Application Number | Priority Date | Filing Date | Title |
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| CN202111663586.6A CN114497614A (en) | 2021-12-31 | 2021-12-31 | Flow battery composite bipolar plate and preparation method thereof |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115548363A (en) * | 2022-11-29 | 2022-12-30 | 山东海化集团有限公司 | Weldable bipolar plate for flow battery and preparation method and application thereof |
| 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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|---|---|---|---|---|
| US20040058214A1 (en) * | 2002-09-19 | 2004-03-25 | Christof Mehler | Bipolar plate for PEM fuel cells |
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| CN101335357A (en) * | 2007-06-26 | 2008-12-31 | 通用汽车环球科技运作公司 | Low electrical resistance bipolar plate-diffusion media assembly |
| DE102011120802A1 (en) * | 2011-12-10 | 2013-06-13 | Daimler Ag | Plastic bipolar plate for fuel cell, has inner region formed from electrically conductive material, and peripheral region formed from electrically insulating material such as thermoplastic resin |
| KR101462497B1 (en) * | 2013-08-01 | 2014-11-19 | 한국생산기술연구원 | Thin type composite bipolar plate having high conductivity and the manufacturing method thereof |
| CN206322784U (en) * | 2016-12-08 | 2017-07-11 | 新源动力股份有限公司 | It is a kind of to prevent the bipolar plates of battery pile short circuit |
| CN108963294A (en) * | 2018-07-20 | 2018-12-07 | 大连交通大学 | A kind of proton exchange membrane fuel cell metal graphite composite bipolar plate preparation method |
| TWM588892U (en) * | 2019-05-29 | 2020-01-01 | 盛英股份有限公司 | Structure of thin dual polar plates |
| CN112264708A (en) * | 2020-10-26 | 2021-01-26 | 乐山晟嘉电气股份有限公司 | Flow battery unit forming process |
| CN113555578A (en) * | 2021-07-22 | 2021-10-26 | 浙江华熔科技有限公司 | Composite graphite material for fuel cell bipolar plate and preparation method thereof |
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| CN115548363A (en) * | 2022-11-29 | 2022-12-30 | 山东海化集团有限公司 | Weldable bipolar plate for flow battery and preparation method and application thereof |
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