CN110137506B - Flow battery bipolar plate, preparation method and material microspheres thereof - Google Patents

Flow battery bipolar plate, preparation method and material microspheres thereof Download PDF

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Publication number
CN110137506B
CN110137506B CN201810136269.0A CN201810136269A CN110137506B CN 110137506 B CN110137506 B CN 110137506B CN 201810136269 A CN201810136269 A CN 201810136269A CN 110137506 B CN110137506 B CN 110137506B
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microsphere
bipolar plate
flow battery
molecular polymer
high molecular
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CN110137506A (en
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周禹
杨霖霖
苏秀丽
林友斌
苏青
廖文俊
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Shanghai Electric Anhui Energy Storage Technology Co ltd
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Shanghai Electric Group Corp
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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
    • H01M4/00—Electrodes
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/88—Processes of manufacture
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/88—Processes of manufacture
    • H01M4/8875—Methods for shaping the electrode into free-standing bodies, like sheets, films or grids, e.g. moulding, hot-pressing, casting without support, extrusion without support
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30—Hydrogen technology
    • Y02E60/50—Fuel cells

Abstract

The invention discloses a flow battery bipolar plate, a preparation method and material microspheres thereof. The invention provides a material microsphere A of a flow bipolar plate, and the flow bipolar plate of a flow battery is prepared by the material microsphere A.

Description

Flow battery bipolar plate, preparation method and material microspheres thereof
Technical Field
The invention relates to a flow battery bipolar plate, a preparation method and material microspheres thereof.
Background
With the accelerated development of renewable energy, distributed micro-grids and smart energy, energy storage technologies playing an important role in improving the grid-connection rate of the renewable energy and balancing the stability of a power grid are receiving more and more attention. In a plurality of large-capacity energy storage technical routes, the all-vanadium redox flow battery is distinguished.
Compared with other energy storage technologies, the energy storage technology of the all-vanadium redox flow battery becomes one of the preferred technologies for large-scale energy storage due to the outstanding advantages of long service life, large scale, safety, reliability and the like. The bipolar plate is one of the key components of the flow battery, has the functions of transferring electrons and separating positive and negative electrolytes, and puts high requirements on good conductivity, chemical corrosion resistance and excellent mechanical properties of the bipolar plate. Therefore, the manufacturing process of the bipolar plate has also received a great deal of attention.
For example: chinese patent application CN101567452A discloses a preparation method of composite material bipolar plate of flow battery, and provides a preparation method of sequentially combining three methods of solution method mixing, tape casting and molding, thereby preparing the bipolar plate with high conductivity. However, the technical scheme adopts a large amount of organic solvent, and the solvent can volatilize into the atmosphere in the casting process, so that the environmental protection is not facilitated.
The chinese patent application CN106099121A discloses the invention patent bipolar plate and its preparation method and application, and proposes to coat conductive layers on both sides of the prepared bipolar plate body, thereby achieving the purpose of reducing the surface resistance of the bipolar plate. The surface of the bipolar plate needs to be coated with an organic solvent mixed with a conductive material, and the bipolar plate is obtained after volatilization and drying, so that a large amount of the organic solvent is evaporated in the process, and the environment protection is not facilitated; in addition, the bipolar plate of the conductive layer is not beneficial to the assembly of the battery, and the damage of the layer is easily caused, thereby affecting the performance of the battery.
The chinese patent application CN106299389A discloses an invention patent "full vanadium redox flow battery bipolar plate and a preparation method thereof", which proposes that the bipolar plate is compounded by using thermosetting resin as a matrix and using a nickel mesh as a conductive network, wherein carbon nanotubes are grafted on the surface of the nickel mesh, and the prepared bipolar plate has stable and good conductive performance. However, in the technical scheme, the metal mesh is compounded with the thermosetting resin, so that the bipolar plate can be in a strong acid environment for a long time during the operation of the actual battery, and the nickel mesh in the bipolar plate is easily corroded by a strong acid solution, so that the service life of the bipolar plate is influenced.
The chinese patent application CN106848346A discloses a bipolar plate for a redox flow battery and a preparation method thereof, and proposes that the bipolar plate is formed by compounding five layers of structures, including a graphite felt/carbon felt, a porous structure carbon/metal base material, a high polymer material, a porous structure carbon/metal base material, and a graphite felt/carbon felt, so that the prepared bipolar plate has excellent mechanical properties and electrical conductivity. The technical scheme is formed by compounding five layers of structures, the preparation process is very complex, each layer is extremely thin in required thickness, processing is not facilitated, and the cost is high.
It can be seen that the current preparation of bipolar plates for flow batteries has two problems: one is that the preparation process is complex or not friendly to the environment, and is not suitable for industrialization; and the other one is that the prepared bipolar plate has the conductivity and mechanical properties which cannot be obtained simultaneously. For example, the conductivity of the bipolar plate is improved and the mechanical properties are reduced, or the conductivity is improved and the conductivity is reduced, so that the comprehensive properties of the bipolar plate cannot be obviously improved.
Therefore, how to provide a flow battery bipolar plate which is suitable for industrialization and green and has both conductivity and mechanical properties is a great problem that needs to be solved urgently by those skilled in the art.
Disclosure of Invention
The invention aims to overcome the defects that the conductivity and the mechanical property of the liquid flow bipolar plate can not be considered at the same time or the preparation process is complex, the operation is difficult, the environment is not friendly or the cost is high even if the bipolar plate with good conductivity and mechanical property can be obtained in the prior art, thereby providing the liquid flow bipolar plate, the preparation method and the material microspheres thereof. The fluid flow bipolar plate prepared by the fluid flow bipolar plate material microsphere has good electrical conductivity and mechanical property, and the preparation process is simple, environment-friendly and easy for industrialization.
The invention provides a material microsphere A of a flow battery bipolar plate, which has a particle size of 5-20 microns; the microsphere comprises a microsphere B and a high molecular polymer microsphere in a mass ratio of 1: 1-1: 4; the microsphere B comprises a high molecular polymer and a conductive material in a mass ratio of 1: 1-4: 1 (such as 2:1), and the conductive material is coated on the surface of the high molecular polymer; the particle size of the microsphere B and the particle size of the high-molecular polymer microsphere are respectively and independently 5-20 microns.
In the invention, the flow battery bipolar plate material microspheres A do not contain an auxiliary agent.
The auxiliary agent refers to an auxiliary agent commonly used in the field for preparing a flow battery bipolar plate, and can be one or more of a dispersing agent, a surfactant, a reinforcing agent and a compatilizer.
In the invention, the high molecular polymer and the high molecular polymer in the high molecular polymer microsphere are high molecular polymers commonly used in the field of preparation of a bipolar plate of a flow battery.
The high molecular polymer can be thermoplastic polymer, and can be selected from one or more of Polyethylene (PE), polypropylene (PP), polyvinyl chloride (PVC), Polystyrene (PS) and acrylonitrile-butadiene-styrene copolymer (ABS); the number average molecular weight of the copolymer is 200000 to 600000.
The density of the high molecular polymer can be 0.5-1.0g/cm3E.g. 0.9g/cm3。
In the invention, the conductive material is a conductive material commonly used in the field for preparing a bipolar plate of a flow battery; the conductive material may be selected from one or more of graphite, carbon black and graphene.
In the present invention, preferably, the particle diameters of the microspheres B and the high molecular polymer microspheres are the same.
In the present invention, the particle diameters of the microspheres B and the polymeric microspheres are each independently 10 to 25 μm, for example 20 μm.
In the present invention, the microsphere B can be prepared by the following method, which comprises the following steps: the high-molecular polymer and the conductive material with the mass ratio of 1: 1-4: 1 are prepared by ball milling.
In the invention, the high molecular polymer microspheres can be prepared by ball milling the high molecular polymer.
In the ball milling preparation process of the microsphere B and the high molecular polymer microsphere:
the ball-to-feed ratio during ball milling may be from 1:1 to 5:1, for example 2: 1.
The time for ball milling can be determined according to whether the effect of crushing and uniform mixing is achieved (for example, the ball milling time can be 20min to 60min, and further for example, 30 min.
The rotational speed during ball milling can be 200-700r/min, such as 500 r/min.
The invention also provides a preparation method of the bipolar plate material microsphere A for the flow battery, which comprises the following steps of stirring the microsphere B and the high-molecular polymer microsphere to prepare the microsphere A.
The stirring can be carried out by a high-speed stirrer, the rotating speed can be 500r/min, and the stirring time in the high-speed stirrer is 20 min.
The invention also provides a preparation method of the flow battery bipolar plate, which comprises the following steps: and carrying out hot pressing on the bipolar plate material microspheres A of the flow battery on the substrate.
In the present invention, the preparation process may be carried out in the absence of an organic solvent.
In the present invention, the hot pressing may refer to apparatuses and parameters in the art for hot pressing when preparing a bipolar plate of a flow battery, for example, a flat vulcanizing machine is used as the hot pressing apparatus.
Wherein the hot pressing temperature can be 170-230 ℃, for example 190-200 ℃.
Wherein the hot pressing pressure may be 2-15MPa, e.g., 10 MPa.
Wherein the hot pressing time may be 2-20min, for example, 3 min.
The invention provides a bipolar plate of a flow battery prepared by the method.
The thickness of the bipolar plate of the flow battery can be 0.5-5mm (such as 0.5-3.0mm, and further such as 1mm), the resistivity can be 1-100 omega-cm (such as 16-40 omega-cm), the mechanical property tensile strength can be 10-50MPa (such as 17-22 MPa), and the breaking elongation can be 7-14%.
The above preferred conditions can be arbitrarily combined to obtain preferred embodiments of the present invention without departing from the common general knowledge in the art.
The reagents and starting materials used in the present invention are commercially available.
The positive progress effects of the invention are as follows:
(1) the bipolar plate of the flow battery provided by the invention has good electrical and mechanical properties;
(2) the bipolar plate of the flow battery provided by the invention can be prepared under the action of no organic solvent, and is environment-friendly;
(3) the bipolar plate of the redox flow battery provided by the invention is assembled in a 5KW all-vanadium redox flow battery pile at 40mA/cm2The current efficiency under the current density of the transformer reaches over 84 percent, the voltage efficiency can reach over 76 percent, and the energy efficiency can reach over 64 percent.
(4) The method does not add any auxiliary agent such as a reinforcing agent and the like in the process of mixing the high molecular polymer material and the conductive material.
Drawings
Fig. 1 is a flow chart of a method for preparing a bipolar plate of a flow battery in example 1.
Detailed Description
The invention is further illustrated by the following examples, which are not intended to limit the scope of the invention. The experimental methods without specifying specific conditions in the following examples were selected according to the conventional methods and conditions, or according to the commercial instructions.
In the following examples:
PE from catal petrochemicals;
the HDPE is 5000S of Daqing petrochemical;
PP is T30S made by land refining;
the carbon black is EC-300J of Keqin;
the ball mill is PM-0.2A for the future;
the high-speed mixer is a 10L mixer of a Leizhou Zelin chemical mechanical plant;
the vulcanizer is XLB-1 of Detai hydraulic electromechanical equipment factory of Yuyao;
example 1
1. Mixing Polyethylene (PE) particles and carbon black at a mass ratio of 2:1 (wherein the mass of PE is 200g, the mass of carbon black is 100g, and the density of PE is 0.5 g/cm)3) The mixture is added into a ball mill for ball milling, and the density of PE particles is 0.9g/cm3The specific surface area of the carbon black was 200m2The ball-material ratio is 2:1, the ball milling time is 30min, the rotating speed is 500r/min, the mixture of PE and carbon black is prepared, and the particle size of the prepared microsphere (namely microsphere B) is 5 microns.
2. Adding the PE particles into a ball mill for ball milling, wherein the density of the PE particles is 0.9g/cm3The ball-material ratio is 2:1, the ball milling time is 30min, the rotating speed is 500r/min, PE powder is prepared, and the particle size of the prepared microspheres is 5 microns.
3. The mixture of PE and carbon black and the PE powder in the mass ratio of 1:1 are stirred in a high-speed stirrer at the rotating speed of 500r/min for 20min to obtain a PE-carbon black mixture, and the particle size of the prepared microsphere (namely microsphere A) is 10 microns.
4. Putting the PE-carbon black mixture (microspheres A) into a flat vulcanizing machine for hot pressing at 190 ℃ under 10MPa for 3min to obtain the conductive bipolar plate with the thickness of 1 mm.
Example 2
1. The mixture of PE particles and carbon black was mixed at a mass ratio of 2:1 (wherein the mass of PE was 200g, the mass of carbon black was 100g, and the density of PE was 1.0 g/cm)3) The mixture is added into a ball mill for ball milling, and the density of PE particles is 0.9g/cm3The specific surface area of the carbon black was 200m2The ball-material ratio is 2:1, the ball milling time is 30min, the rotating speed is 500r/min, the mixture of PE and carbon black is prepared, and the particle size of the prepared microspheres is 10 microns.
2. Adding the PE particles into a ball mill for ball milling, wherein the density of the PE particles is 0.9g/cm3The ball-material ratio is 3:1, the ball milling time is 30min, the rotating speed is 500r/min, PE powder is prepared, and the particle size of the prepared microspheres is 10 microns.
3. And (3) stirring the mixture of the PE and the carbon black and the PE powder in a mass ratio of 1:1 in a high-speed stirrer for 20min at a rotating speed of 500r/min to obtain a PE-carbon black mixture, wherein the particle size of the prepared microspheres is 10 microns.
4. And putting the PE-carbon black mixture into a flat vulcanizing machine for hot pressing, wherein the hot pressing temperature is 200 ℃, the pressure is 10MPa, and the time is 3min, so that the conductive bipolar plate with the thickness of 1mm is obtained.
Example 3
1. The mixture of PE particles and carbon black was mixed at a mass ratio of 2:1 (wherein the mass of PE was 200g, the mass of carbon black was 100g, and the density of PE was 0.9 g/cm)3) Adding into a ball mill for ball milling, wherein the density of the PE particles is 0.9g/cm3The specific surface area of the carbon black was 200m2The ball-material ratio is 2:1, the ball milling time is 30min, the rotating speed is 500r/min, the mixture of PE and carbon black is prepared, and the particle size of the prepared microspheres is 10 microns.
2. Adding the PE particles into a ball mill for ball milling, wherein the density of the PE particles is 0.9g/cm3, the ball-to-material ratio is 2:1, the ball milling time is 15min, the rotating speed is 500r/min, PE powder is prepared, and the particle size of the prepared microspheres is 25 microns.
3. And (3) stirring the mixture of the PE and the carbon black and the PE powder in a mass ratio of 1:1 in a high-speed stirrer for 20min at a rotating speed of 500r/min to obtain a PE-carbon black mixture, wherein the particle size of the prepared microspheres is different from 10-25 microns.
4. And putting the PE-carbon black mixture into a flat vulcanizing machine for hot pressing, wherein the hot pressing temperature is 200 ℃, the pressure is 10MPa, and the time is 3min, so that the conductive bipolar plate with the thickness of 1mm is obtained.
Example 4
1. The mixture of PE particles and carbon black was mixed at a mass ratio of 2:1 (wherein the mass of PE was 200g, the mass of carbon black was 100g, and the density of PE was 0.9 g/cm)3) The mixture is added into a ball mill for ball milling, and the density of PE particles is 0.9g/cm3The specific surface area of the carbon black was 200m2The ball-material ratio is 2:1, the ball milling time is 30min, the rotating speed is 500r/min, the mixture of PE and carbon black is prepared, and the particle size of the prepared microspheres is 10 microns.
2. Adding PP particles into a ball mill for ball milling, wherein the density of the PP particles is 0.9g/cm3The ball-material ratio is 2:1, the ball milling time is 30min, the rotating speed is 500r/min, PP powder is prepared, and the particle size of the prepared microspheres is 10 microns.
3. And (3) stirring the mixture of the PE and the carbon black and the PP powder in a mass ratio of 1:1 in a high-speed stirrer for 20min at a rotating speed of 500r/min to obtain a PE-PP-carbon black mixture, wherein the particle size of the prepared microsphere is 10 microns.
4. And putting the PE-PP-carbon black mixture into a flat vulcanizing machine for hot pressing, wherein the hot pressing temperature is 200 ℃, the pressure is 10MPa, and the time is 3min, so that the conductive bipolar plate with the thickness of 1mm is obtained.
Example 5
1. The mixture of PE particles and carbon black was mixed at a mass ratio of 1:1 (wherein the mass of PE was 100g, the mass of carbon black was 100g, and the density of PE was 0.9 g/cm)3) The mixture is added into a ball mill for ball milling, and the density of PE particles is 0.9g/cm3The specific surface area of the carbon black was 200m2The ball-material ratio is 2:1, the ball milling time is 30min, the rotating speed is 500r/min, the mixture of PE and carbon black is prepared, and the particle size of the prepared microspheres is 20 microns.
2. Adding the PE particles into a ball mill for ball milling, wherein the density of the PE particles is 0.9g/cm3The ball-material ratio is 2:1, ball milling time is 30min, rotating speed is 500r/min, PE powder is prepared, and the particle size of the prepared microspheres is 20 microns.
3. And (3) stirring the mixture of the PE and the carbon black and the PE powder in a mass ratio of 1:4 in a high-speed stirrer for 20min at a rotating speed of 500r/min to obtain a PE-carbon black mixture, wherein the particle size of the prepared microspheres is 20 microns.
4. And putting the PE-carbon black mixture into a flat vulcanizing machine for hot pressing, wherein the hot pressing temperature is 200 ℃, the pressure is 10MPa, and the time is 3min, so that the conductive bipolar plate with the thickness of 1mm is obtained.
Example 6
1. The mixture of PE particles and carbon black was mixed in a mass ratio of 4:1 (wherein the mass of PE was 400g, the mass of carbon black was 100g, and the density of PE was 0.9 g/cm)3) The mixture is added into a ball mill for ball milling, and the density of PE particles is 0.9g/cm3The specific surface area of the carbon black was 200m2The ball-material ratio is 3:1, the ball milling time is 30min, the rotating speed is 500r/min, the mixture of PE and carbon black is prepared, and the particle size of the prepared microspheres is 10 microns.
2. Adding the PE particles into a ball mill for ball milling, wherein the density of the PE particles is 0.9g/cm3The ball-material ratio is 2:1, the ball milling time is 30min, the rotating speed is 500r/min, PE powder is prepared, and the particle size of the prepared microspheres is 10 microns.
3. And (3) stirring the mixture of the PE and the carbon black and the PE powder in a mass ratio of 1:1 in a high-speed stirrer for 20min to obtain a PE-carbon black mixture, wherein the particle size of the prepared microspheres is 10 microns.
4. And putting the PE-carbon black mixture into a flat vulcanizing machine for hot pressing, wherein the hot pressing temperature is 200 ℃, the pressure is 10MPa, and the time is 3min, so that the conductive bipolar plate with the thickness of 1mm is obtained.
Comparative example 1
1. Mixing the mixture of PE particles and carbon black at a high speed of 500r/min and a density of 0.9g/cm at a mass ratio of 2:13The specific surface area of the carbon black was 200m2And/g, preparing a mixture of PE and carbon black, wherein the particle size of the prepared powder is 20-50 microns.
2. And putting the PE-carbon black mixture into a flat vulcanizing machine for hot pressing, wherein the hot pressing temperature is 190 ℃, the pressure is 10MPa, and the time is 3min, so that the conductive bipolar plate is obtained.
Comparative example 2
1. The mixture of PE particles and carbon black was mixed at a mass ratio of 2:1 (wherein the mass of PE was 200g, the mass of carbon black was 100g, and the density of PE was 0.9 g/cm)3) The mixture is added into a ball mill for ball milling, and the density of PE particles is 0.9g/cm3The specific surface area of the carbon black was 200m2The ball-material ratio is 2:1, the ball milling time is 30min, the rotating speed is 500r/min, the mixture of PE and carbon black is prepared, and the particle size of the prepared microspheres is 10 microns.
2. And putting the mixture obtained after the PE-carbon black is mixed at a high speed into a flat vulcanizing machine for hot pressing, wherein the hot pressing temperature is 190 ℃, the pressure is 10MPa, and the time is 3min, so that the conductive bipolar plate is obtained.
Comparative example 3
1. The mixture of PE particles and carbon black was mixed at a mass ratio of 2:1 (wherein the mass of PE was 200g, the mass of carbon black was 100g, and the density of PE was 0.9 g/cm)3) The mixture is added into a ball mill for ball milling, and the density of PE particles is 0.9g/cm3The specific surface area of the carbon black was 200m2The ball-material ratio is 2:1, the ball milling time is 30min, the rotating speed is 500r/min, the mixture of PE and carbon black is prepared, and the particle size of the prepared microspheres is 10 microns.
2. And stirring the mixture of the PE and the carbon black for 20min in a high-speed stirrer at a speed of 500r/min to obtain a PE-carbon black mixture, wherein the particle size of the prepared microspheres is 10 microns.
3. And putting the mixture obtained after the PE-carbon black is mixed at a high speed into a flat vulcanizing machine for hot pressing, wherein the hot pressing temperature is 190 ℃, the pressure is 10MPa, and the time is 3min, so that the conductive bipolar plate is obtained.
Effect example 1
The conductive properties and mechanical properties of the bipolar plates prepared in examples 1 to 6 and comparative examples 1 to 3 were tested.
Numbering Resistance (omega) Tensile strength (20Mpa) Elongation at break
Example 1 28 20 10％
Example 2 23 22 11％
Example 3 20 18 8.50％
Example 4 19 17 8％
Example 5 16 19 7％
Example 6 40 25 14％
Comparative example 1 120 22 15％
Comparative example 2 108 15 7.8％
Comparative example 3 38 14 7.5％
Effect example 2
The bipolar plates prepared in the above examples 1-6 and comparative examples 1-3 were assembled in a 5KW all-vanadium redox flow battery stack at 40mA/cm2The current efficiency, voltage efficiency, energy efficiency and electrolyte utilization rate of the battery are tested under the current density.
Current efficiency, voltage efficiency, and energy efficiency were all tested using electrochemical tester 5V6A from New Wille electronics, Shenzhen, Inc., with the results shown in the following table.
Current efficiency Efficiency of voltage Energy efficiency
Example 1 90％ 80％ 72％
Example 2 91％ 83％ 76％
Example 3 88％ 78％ 69％
Example 4 87％ 78％ 68％
Example 5 85％ 76％ 65％
Example 6 84％ 76％ 64％
Comparative example 1 78％ 75％ 59％
Comparative example 2 80％ 76％ 61％
Comparative example 3 82％ 74％ 61％

Claims (14)

1. The material microsphere A for the bipolar plate of the flow battery is characterized in that the particle size of the material microsphere A for the bipolar plate of the flow battery is 5-20 μm; the microsphere comprises a microsphere B and a high molecular polymer microsphere in a mass ratio of 1: 1-1: 4; the microsphere B comprises a high molecular polymer and a conductive material in a mass ratio of 1: 1-4: 1, and the conductive material is coated on the surface of the high molecular polymer; the particle size of the microsphere B and the particle size of the high-molecular polymer microsphere are respectively and independently 5-20 microns.
2. The flow battery bipolar plate material microsphere A as claimed in claim 1, wherein the flow battery bipolar plate material microsphere A does not contain an auxiliary agent;
and/or the high molecular polymer is a thermoplastic polymer;
and/or the conductive material is selected from one or more of graphite, carbon black and graphene.
3. The flow battery bipolar plate material microsphere A as claimed in claim 1, wherein the flow battery bipolar plate material microsphere A does not contain an auxiliary agent, and the auxiliary agent is selected from one or more of a dispersing agent, a surfactant, a reinforcing agent and a compatilizer;
and/or the high molecular polymer is selected from one or more of polyethylene, polypropylene, polyvinyl chloride, polystyrene and acrylonitrile-butadiene-styrene copolymer; the number average molecular weight of the copolymer is 200000 to 600000.
4. The flow battery bipolar plate material microsphere A as claimed in claim 1, wherein the particle size of the microsphere B is the same as that of the high molecular polymer microsphere;
and/or the particle size of the microsphere B and the particle size of the high molecular polymer microsphere are respectively and independently 10-25 μm;
and/or the microspheres B comprise a high molecular polymer and a conductive material in a mass ratio of 2: 1;
and/or the density of the high molecular polymer is 0.5-1.0g/cm3。
5. The flow battery bipolar plate material microsphere A as claimed in claim 4, wherein the particle size of the microsphere B and the particle size of the high molecular polymer microsphere are 20 μm independently;
and/or the density of the high molecular polymer is 0.9g/cm3。
6. The flow battery bipolar plate material microsphere A as claimed in claim 1, wherein the microsphere B is prepared by the following method, which comprises the following steps: the high molecular polymer and the conductive material with the mass ratio of 1: 1-4: 1 are subjected to ball milling to prepare the conductive material;
and/or the high molecular polymer microspheres are prepared by ball milling the high molecular polymer.
7. The flow battery bipolar plate material microsphere A as claimed in claim 6, wherein in the ball milling preparation process of the microsphere B and the high molecular polymer microsphere:
the ball-material ratio during ball milling is 1:1-5: 1;
and/or the ball milling time is 20min-60 min;
and/or the rotating speed during ball milling is 200-700 r/min.
8. The flow battery bipolar plate material microsphere A as claimed in claim 7, wherein during the ball milling preparation process of the microsphere B and the high molecular polymer microsphere:
the ball-material ratio during ball milling is 2: 1;
and/or the ball milling time is 30 min;
and/or the rotating speed during ball milling is 500 r/min.
9. The preparation method of the microspheres A of the bipolar plate material for the flow battery as described in any one of claims 1 to 8, comprising the following steps of stirring the microspheres B and the high molecular polymer microspheres to obtain microspheres.
10. The preparation method of the microspheres A of the bipolar plate material of the flow battery as claimed in claim 9, wherein a high-speed stirrer is adopted during stirring, and the stirring time of the high-speed stirrer is 20 min.
11. The preparation method of the flow battery bipolar plate is characterized by comprising the following steps: the flow battery bipolar plate material microspheres A as defined in any one of claims 1-8 are hot-pressed on a substrate.
12. The method of making a bipolar plate for a flow battery of claim 11, wherein the method is performed in the absence of an organic solvent;
and/or a flat vulcanizing machine is adopted during hot pressing;
and/or the hot pressing temperature is 170-230 ℃;
and/or the hot pressing pressure is 2-15 MPa;
and/or the hot pressing time is 2-20 min.
13. The method for preparing a bipolar plate of a flow battery as claimed in claim 12, wherein the hot pressing temperature is 190-200 ℃;
and/or the hot pressing pressure is 10 MPa;
and/or the hot pressing time is 3 min.
14. A bipolar plate of a flow battery prepared by the preparation method of any one of claims 11 to 13.
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CN1776944A (en) * 2005-09-27 2006-05-24 武汉理工大学 Method for improving conductivity of bipolar plate of high-conducting composite material
CN101308924A (en) * 2007-05-18 2008-11-19 中国科学院大连化学物理研究所 Flexibility enhanced bipolar plate for liquid energy-storing battery and manufacture thereof
CN101567452A (en) * 2009-04-20 2009-10-28 清华大学 Preparation method of liquid flow battery composite material bipolar plate
CN104332641A (en) * 2014-08-28 2015-02-04 清华大学 Preparation method of composite bipolar plate

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Publication number Priority date Publication date Assignee Title
JP2011228059A (en) * 2010-04-16 2011-11-10 Sumitomo Electric Ind Ltd Dipole plate for redox flow battery

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1776944A (en) * 2005-09-27 2006-05-24 武汉理工大学 Method for improving conductivity of bipolar plate of high-conducting composite material
CN101308924A (en) * 2007-05-18 2008-11-19 中国科学院大连化学物理研究所 Flexibility enhanced bipolar plate for liquid energy-storing battery and manufacture thereof
CN101567452A (en) * 2009-04-20 2009-10-28 清华大学 Preparation method of liquid flow battery composite material bipolar plate
CN104332641A (en) * 2014-08-28 2015-02-04 清华大学 Preparation method of composite bipolar plate

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