CN113809339A - Method for efficiently preparing integrated electrode of flow battery - Google Patents
Method for efficiently preparing integrated electrode of flow battery Download PDFInfo
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- CN113809339A CN113809339A CN202111357892.7A CN202111357892A CN113809339A CN 113809339 A CN113809339 A CN 113809339A CN 202111357892 A CN202111357892 A CN 202111357892A CN 113809339 A CN113809339 A CN 113809339A
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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
- H01M4/88—Processes of manufacture
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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
- H01M4/96—Carbon-based electrodes
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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
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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
- H01M8/0297—Arrangements for joining electrodes, reservoir layers, heat exchange units or bipolar separators to each other
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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
- H01M8/18—Regenerative fuel cells, e.g. redox flow batteries or secondary fuel cells
- H01M8/184—Regeneration by electrochemical means
- H01M8/188—Regeneration by electrochemical means by recharging of redox couples containing fluids; Redox flow type batteries
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Abstract
The invention discloses a method for efficiently preparing an integrated electrode of a flow battery, which comprises the following steps: s1: uniformly mixing the plastic, the conductive additive and the additive, and processing into a bipolar plate; s2: pretreating a graphite felt; s3: attaching a layer of volatile solvent to the surface of the bipolar plate; s4: tightly attaching two pretreated graphite felts to two sides of the bipolar plate with the surface attached with the volatile solvent to form a graphite felt/bipolar plate/graphite felt sandwich structure; s5: the graphite felt/bipolar plate/graphite felt sandwich structure is laminated and tightly attached through a tablet press, direct current or alternating current is introduced, and graphite felt carbon fibers are embedded into the bipolar plate to form an integrated electrode. The invention adopts the current mode to prepare the integrated electrode of the redox flow battery, can obviously reduce the internal resistance in the integrated electrode of the finished product, improves the efficiency of the redox flow battery, has simple preparation method, can produce a plurality of integrated electrodes at one time, has short production time and high efficiency, is energy-saving and environment-friendly, and is convenient for mass production.
Description
Technical Field
The invention relates to the technical field of redox flow batteries, in particular to a method for efficiently preparing an integrated electrode of a redox flow battery.
Background
The flow battery is an energy storage battery which realizes mutual conversion of chemical energy and electric energy through redox reaction of positive and negative reactive substances, and is mainly applied to power generation of renewable energy sources (such as wind energy, solar energy, tidal energy and the like), peak clipping and valley filling of a power system, standby power stations of important facilities and the like. The flow battery pile mainly comprises a diaphragm, an electrode, a bipolar plate, an end plate and the like. The electrode is a place where electrochemical reaction occurs, certain catalytic activity is required, and a graphite felt or a carbon felt with good electrochemical activity and reversibility is mostly adopted as the electrode; the bipolar plate plays a role in separating positive and negative electrolytes, supporting electrodes and collecting current generated by electrochemical reaction, and needs good conductivity, mechanical property, corrosion resistance and liquid resistance. When the stack is assembled, the electrode is in contact with the bipolar plate, and the contact resistance between the electrode and the bipolar plate affects the energy conversion efficiency of the flow battery, so the contact resistance is usually reduced by increasing the pressing force between the electrode and the bipolar plate, and the energy conversion efficiency of the battery is improved. However, although the contact resistance between the electrode and the bipolar plate can be reduced by applying a larger pressing force, the electrode is compressed, so that the mass transfer resistance of the electrolyte in the electrode is increased, and concentration polarization occurs, thereby affecting the performance of the battery.
For the above reasons, the integrated electrode has been researched and developed. The integrated electrode is a battery assembly formed by bonding an electrode and a bipolar plate. At present, the integrated electrode is mostly prepared by hot pressing or bonding with conductive adhesive. However, the graphite felt has poor thermal conductivity, large energy consumption and long time are needed during hot pressing, the graphite felt is easy to fall off in the using process, and the conductive adhesive has the problems of hardness, brittleness, easy falling off, long curing time, low efficiency and the like.
Disclosure of Invention
The invention aims to provide a method for efficiently preparing an integrated electrode of a flow battery, which solves the problems that the integrated electrode prepared by adopting a hot-pressing or conductive adhesive bonding mode in the prior art has poor heat conductivity, large energy consumption and long time are needed during hot pressing, a graphite felt is easy to fall off in the using process, the conductive adhesive is hard and brittle and is easy to fall off, and the long-term efficiency of curing time is low.
The technical scheme adopted by the invention is as follows:
a method for efficiently preparing an integrated electrode of a flow battery comprises the following steps:
s1: uniformly mixing a mixture consisting of 40-60wt% of plastic, 30-59wt% of conductive additive and 1-10wt% of additive, and processing to obtain a plate with the thickness of 0.6-1.4mm to obtain the bipolar plate;
s2: carrying out heat treatment or acid treatment on the graphite felt to obtain a pretreated graphite felt;
s3: soaking the bipolar plate in the S1 in a volatile solvent for 5-10min to attach a layer of volatile solvent on the surface of the bipolar plate, and then taking out the bipolar plate;
s4: tightly attaching two pretreated graphite felts in the step S2 to two sides of the bipolar plate with the surface attached with the volatile solvent in the step S3 to form a graphite felt/bipolar plate/graphite felt sandwich structure;
s5: and (3) superposing and fixing the graphite felt/bipolar plate/graphite felt sandwich structure in the S4 in a device containing a copper sheet in a multi-layer manner, tightly attaching the graphite felt/bipolar plate/graphite felt sandwich structure through a tablet press with the constant pressure of 0.02-0.10Mpa, introducing direct current or alternating current for 5-20min at the temperature of 90-200 ℃, embedding graphite felt carbon fibers into the bipolar plate, wherein the thickness of the embedded graphite felt is 0.1-0.3mm, and forming an integrated electrode.
Further, the plastic in S1 is any one or a mixture of two or more of the following: polyethylene, polypropylene, polystyrene, polyacrylonitrile, polyvinyl chloride, plexiglass, cellulose acetate, polychlorotrifluoroethylene or polyvinylidene chloride.
Further, the conductive aid in S1 is any one or a mixture of two or more of the following: conductive graphite, natural graphite, artificial graphite, acetylene black, graphene, carbon nanotubes, superconducting carbon black, or dust-free carbon black.
Further, the auxiliary agent in S1 is one or a mixture of two or more of the following: tris [2, 4-di-tert-butylphenyl ] phosphite, polyvinyl alcohol, methyltriacetoxysilane, ethylene-vinyl acetate copolymer or ethylene-octene copolymer.
Further, the heat treatment method in S2 is to preserve the heat of the graphite felt for 4-10h in the air atmosphere of 400-600 ℃ to obtain the pretreated graphite felt.
Further, the acid treatment method in S2 is to put the graphite felt into concentrated sulfuric acid, soak the graphite felt at normal temperature for 6-8 hours, take out the graphite felt, clean the graphite felt with deionized water, and dry the graphite felt to obtain the pretreated graphite felt.
Further, the volatile solvent in S3 is any one or a mixture of two or more of the following: methanol, ethanol, acetone, butyl acetate, water, n-hexane, n-heptane or butyl acrylate.
Further, the number of stacked layers of the graphite felt/bipolar plate/graphite felt sandwich structure in the S3 is 1-50.
The invention has the beneficial effects that:
1. the integrated electrode prepared by adopting the current mode has the functions of providing a place for electrochemical reaction and collecting current, the method is simple, a plurality of integrated electrodes can be produced at one time, the mass production is convenient, the production time is short, the efficiency is high, and the energy is saved and the environment is protected.
2. When the integrated electrode prepared by adopting the current mode is electrified, the contact surface of the graphite felt electrode and the bipolar plate generates heat in a resistance mode, and the heating heat is uniform, so that the graphite felt is embedded into the bipolar plate with good effect and low contact resistance, and the efficiency of the battery can be improved.
3. The volatile solvent is added between the electrode and the bipolar plate, so that the interface resistance is increased, more heat can be generated when current is applied to the electrode, the adhesion degree of the electrode and the bipolar plate interface is increased, and the preparation time of the integrated electrode is shortened.
4. The graphite felt/bipolar plate/graphite felt sandwich structure can be overlapped in multiple layers, a plurality of integrated electrodes are prepared at one time, and the production efficiency can be improved.
5. The invention adopts the resistance electrification heating principle, shortens the preparation process of the integrated electrode and reduces the power consumption for producing the integrated electrode compared with the traditional mode of preparing the integrated electrode by hot pressing; compared with the traditional mode of preparing the integrated electrode by bonding conductive adhesive, the preparation method avoids the use of consumables such as conductive adhesive, and is more energy-saving and environment-friendly.
Drawings
FIG. 1 is a schematic view of an integrated electrode prepared by current method according to the present invention.
Description of the reference numerals
1-copper sheet, 2-graphite felt, 3-bipolar plate and 4-power supply.
Detailed Description
The following description of at least one exemplary embodiment is merely illustrative in nature and is in no way intended to limit the invention, its application, or uses. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Referring to fig. 1, a graphite felt 2/a bipolar plate 3/a graphite felt 2 form a sandwich structure, the multilayer sandwich structure is stacked and placed in a device containing a copper sheet 1 for fixation, a power supply 4 is connected, the power supply 4 is electrified by a direct current power supply or an alternating current power supply, in the electrifying process, the interface of the graphite felt 2 and the bipolar plate 3 generates a large amount of heat in a resistance mode, the surface of the bipolar plate 3 in contact with the graphite felt 2 is softened, and carbon fibers of the graphite felt 2 are embedded into the bipolar plate 3 to form an integrated electrode.
Example 1
A method for efficiently preparing an integrated electrode of a flow battery comprises the following steps:
s1: uniformly mixing 40wt% of polyethylene, 20wt% of conductive graphite, 20wt% of artificial graphite, 15wt% of carbon nano tube, 4wt% of dust-free carbon black, 0.5wt% of tris [ 2.4-di-tert-butylphenyl ] phosphite and 0.5wt% of ethylene-vinyl acetate copolymer, and processing the mixture into a plate with the thickness of 0.6mm to obtain the bipolar plate;
s2: keeping the temperature of the graphite felt at 400 ℃ in an air atmosphere for 10h to obtain a pretreated graphite felt;
s3: soaking the bipolar plate in the S1 in ethanol for 5min to attach a layer of ethanol on the surface of the bipolar plate, and taking out;
s4: tightly attaching two pretreated graphite felts in the step S2 to two sides of the bipolar plate with the surface attached with ethanol in the step S3 to form a graphite felt/bipolar plate/graphite felt sandwich structure;
s5: and (3) placing the graphite felt/bipolar plate/graphite felt sandwich structure single sheet in S4 into a device containing a copper sheet for fixing, tightly attaching the graphite felt/bipolar plate/graphite felt sandwich structure through a tablet press with the constant pressure of 0.1Mpa, introducing direct current for 5min, generating a large amount of heat at the interface of the graphite felt and the bipolar plate in a resistance mode in the electrifying process, softening the surface of the bipolar plate in contact with the graphite felt when the temperature reaches 150 ℃, embedding graphite felt carbon fibers into the bipolar plate, wherein the thickness of the embedded graphite felt is 0.1mm, and forming an integrated electrode.
Example 2
A method for efficiently preparing an integrated electrode of a flow battery comprises the following steps:
s1: uniformly mixing a mixture of 45wt% of polyethylene, 30wt% of natural graphite, 20wt% of conductive graphite, 3wt% of carbon nano tube and 2wt% of tris [ 2.4-di-tert-butylphenyl ] phosphite, and processing the mixture into a plate shape with the thickness of 1.4mm to obtain a bipolar plate;
s2: soaking the graphite felt in 98% concentrated sulfuric acid at normal temperature for 6h, taking out, washing with deionized water, and drying to obtain a pretreated graphite felt;
s3: soaking the bipolar plate in the S1 in n-hexane for 6min to attach a layer of n-hexane on the surface of the bipolar plate, and taking out the bipolar plate;
s4: tightly attaching two pretreated graphite felts in the step S2 to two sides of the bipolar plate with n-hexane attached to the surface in the step S3 to form a graphite felt/bipolar plate/graphite felt sandwich structure;
s5: and (3) superposing 5 layers of the graphite felt/bipolar plate/graphite felt sandwich structure in the S4, fixing the structure in a device containing a copper sheet, enabling the graphite felt/bipolar plate/graphite felt sandwich structure to be tightly attached through constant pressure of a tablet press with the constant pressure of 0.02Mpa, introducing alternating current for 20min, generating a large amount of heat at the interface of the graphite felt and the bipolar plate in a resistance mode in the electrifying process, softening the surface of the bipolar plate in contact with the graphite felt when the temperature reaches 160 ℃, embedding graphite felt carbon fibers into the bipolar plate, and enabling the thickness of the embedded graphite felt to be 0.3mm to form an integrated electrode.
Example 3
A method for efficiently preparing an integrated electrode of a flow battery comprises the following steps:
s1: uniformly mixing a mixture of 42wt% of polypropylene, 30wt% of artificial graphite, 20wt% of conductive graphite, 5wt% of carbon nano tube, 2wt% of tris [ 2.4-di-tert-butylphenyl ] phosphite and 1wt% of ethylene-vinyl acetate copolymer, and processing the mixture into a plate with the thickness of 0.9mm to obtain a bipolar plate;
s2: keeping the temperature of the graphite felt at 450 ℃ in an air atmosphere for 8h to obtain a pretreated graphite felt;
s3: soaking the bipolar plate in the S1 in methanol for 8min to attach a layer of methanol on the surface of the bipolar plate, and taking out;
s4: tightly attaching two pretreated graphite felts in the step S2 to two sides of the bipolar plate with methanol attached to the surface in the step S3 to form a graphite felt/bipolar plate/graphite felt sandwich structure;
s5: and (3) superposing 15 layers of the graphite felt/bipolar plate/graphite felt sandwich structure in the S4, placing the laminated structure in a device containing a copper sheet for fixation, enabling the graphite felt/bipolar plate/graphite felt sandwich structure to be tightly attached through constant pressure of a tablet press with the constant pressure of 0.05Mpa, introducing direct current for 15min, generating a large amount of heat at the interface of the graphite felt and the bipolar plate in a resistance mode in the electrifying process, enabling the temperature to reach 165 ℃, softening the surface of the bipolar plate in contact with the graphite felt, embedding the graphite felt carbon fibers into the bipolar plate, and enabling the thickness of the embedded graphite felt to be 0.2mm to form an integrated electrode.
Example 4
A method for efficiently preparing an integrated electrode of a flow battery comprises the following steps:
s1: uniformly mixing 45wt% of polypropylene, 15wt% of artificial graphite, 20wt% of conductive graphite, 10wt% of dust-free carbon black, 5wt% of natural graphite, 3wt% of carbon nano tube, 1wt% of tris [ 2.4-di-tert-butylphenyl ] phosphite and 1wt% of ethylene-vinyl acetate copolymer, and processing the mixture into a plate with the thickness of 0.8mm to obtain the bipolar plate;
s2: soaking the graphite felt in 98% concentrated sulfuric acid at normal temperature for 8h, taking out, washing with deionized water, and drying to obtain a pretreated graphite felt;
s3: soaking the bipolar plate in S1 in n-heptane for 10min to attach a layer of n-heptane on the surface of the bipolar plate, and taking out;
s4: tightly attaching two pretreated graphite felts in the step S2 to two sides of the bipolar plate with n-heptane attached to the surface in the step S3 to form a graphite felt/bipolar plate/graphite felt sandwich structure;
s5: and (3) superposing 50 layers of the graphite felt/bipolar plate/graphite felt sandwich structure in the S4, placing the laminated structure in a device containing a copper sheet for fixation, enabling the graphite felt/bipolar plate/graphite felt sandwich structure to be tightly attached through constant pressure of a tablet press with the constant pressure of 0.04Mpa, introducing direct current for 15min, generating a large amount of heat at the interface of the graphite felt and the bipolar plate in a resistance mode in the electrifying process, enabling the temperature to reach 170 ℃, softening the surface of the bipolar plate in contact with the graphite felt, embedding the graphite felt carbon fibers into the bipolar plate, and enabling the thickness of the embedded graphite felt to be 0.1mm to form an integrated electrode.
Example 5
A method for efficiently preparing an integrated electrode of a flow battery comprises the following steps:
s1: uniformly mixing 60wt% of polyethylene, 8wt% of artificial graphite, 10wt% of conductive graphite, 4wt% of dust-free carbon black, 5.0wt% of natural graphite, 3wt% of carbon nano tube, 1wt% of tris [ 2.4-di-tert-butylphenyl ] phosphite and 9wt% of ethylene-vinyl acetate copolymer, and processing the mixture into a plate with the thickness of 0.7mm to obtain the bipolar plate;
s2: keeping the temperature of the graphite felt at 600 ℃ in the air atmosphere for 4h to obtain a pretreated graphite felt;
s3: soaking the bipolar plate in the S1 in ethanol for 5min to attach a layer of ethanol on the surface of the bipolar plate, and taking out;
s4: tightly attaching two pretreated graphite felts in the step S2 to two sides of the bipolar plate with the surface attached with ethanol in the step S3 to form a graphite felt/bipolar plate/graphite felt sandwich structure;
s5: and (3) superposing 20 layers of the graphite felt/bipolar plate/graphite felt sandwich structure in the S4, placing the laminated structure in a device containing a copper sheet for fixation, enabling the graphite felt/bipolar plate/graphite felt sandwich structure to be tightly attached through constant pressure of a tablet press with the constant pressure of 0.06Mpa, introducing alternating current for 20min, generating a large amount of heat at the interface of the graphite felt and the bipolar plate in a resistance mode in the electrifying process, softening the surface of the bipolar plate in contact with the graphite felt when the temperature reaches 158 ℃, embedding the graphite felt carbon fibers into the bipolar plate, and enabling the thickness of the embedded graphite felt to be 0.1mm to form an integrated electrode.
Example 6
A method for efficiently preparing an integrated electrode of a flow battery comprises the following steps:
s1: uniformly mixing a mixture of 45wt% of polystyrene, 25wt% of conductive graphite, 10wt% of artificial graphite, 10wt% of carbon nano tubes, 5.0wt% of dust-free carbon black, 0.5wt% of tris [ 2.4-di-tert-butylphenyl ] phosphite and 4.5wt% of ethylene-octene copolymer, and processing the mixture into a plate with the thickness of 1.0mm to obtain the bipolar plate;
s2: keeping the temperature of the graphite felt at 600 ℃ in the air atmosphere for 4h to obtain a pretreated graphite felt;
s3: soaking the bipolar plate in the S1 in acetone for 7min to attach a layer of acetone on the surface of the bipolar plate, and taking out the bipolar plate;
s4: tightly attaching two pretreated graphite felts in the step S2 to two sides of the bipolar plate with acetone attached to the surface in the step S3 to form a graphite felt/bipolar plate/graphite felt sandwich structure;
s5: and (3) superposing 5 layers of the graphite felt/bipolar plate/graphite felt sandwich structure in the S4, fixing the structure in a device containing a copper sheet, enabling the graphite felt/bipolar plate/graphite felt sandwich structure to be tightly attached through constant pressure of a tablet press with the constant pressure of 0.1Mpa, introducing direct current for 20min, generating a large amount of heat at the interface of the graphite felt and the bipolar plate in a resistance mode in the electrifying process, softening the surface of the bipolar plate in contact with the graphite felt when the temperature reaches 100 ℃, embedding graphite felt carbon fibers into the bipolar plate, and enabling the thickness of the embedded graphite felt to be 0.1mm to form an integrated electrode.
Example 7
A method for efficiently preparing an integrated electrode of a flow battery comprises the following steps:
s1: uniformly mixing 42wt% of polyvinyl chloride, 10wt% of artificial graphite, 15wt% of conductive graphite, 10wt% of acetylene black, 10wt% of carbon nano tube, 8wt% of dust-free carbon black, 1wt% of polyvinyl alcohol and 4wt% of methyl triacetoxysilane, and processing the mixture into a plate with the thickness of 0.8mm to obtain the bipolar plate;
s2: keeping the temperature of the graphite felt at 420 ℃ in an air atmosphere for 9h to obtain a pretreated graphite felt;
s3: soaking the bipolar plate in the S1 in butyl acetate for 5min to attach a layer of butyl acetate on the surface of the bipolar plate, and taking out the bipolar plate;
s4: tightly attaching two pretreated graphite felts in the step S2 to two sides of the bipolar plate with butyl acetate attached to the surface in the step S3 to form a graphite felt/bipolar plate/graphite felt sandwich structure;
s5: and (3) superposing 15 layers of the graphite felt/bipolar plate/graphite felt sandwich structure in the S4, placing the laminated structure in a device containing a copper sheet for fixation, enabling the graphite felt/bipolar plate/graphite felt sandwich structure to be tightly attached through constant pressure of a tablet press with the constant pressure of 0.07Mpa, introducing direct current for 7min, generating a large amount of heat at the interface of the graphite felt and the bipolar plate in a resistance mode in the electrifying process, softening the surface of the bipolar plate in contact with the graphite felt when the temperature reaches 90 ℃, embedding the carbon fibers of the graphite felt into the bipolar plate, and enabling the thickness of the embedded graphite felt to be 0.1mm to form an integrated electrode.
Example 8
A method for efficiently preparing an integrated electrode of a flow battery comprises the following steps:
s1: uniformly mixing 44wt% of organic glass, 10wt% of artificial graphite, 10wt% of conductive graphite, 10wt% of acetylene black, 10wt% of carbon nano tube, 5wt% of superconducting carbon black, 10wt% of dust-free carbon black and 1wt% of methyl triacetoxysilane, and processing the mixture into a plate with the thickness of 0.6mm to obtain the bipolar plate;
s2: keeping the temperature of the graphite felt at 500 ℃ in the air atmosphere for 6h to obtain a pretreated graphite felt;
s3: soaking the bipolar plate in the S1 in a mixed solution of water and methanol for 6min to enable a layer of mixed solution of water and methanol to be attached to the surface of the bipolar plate, and then taking out the bipolar plate;
s4: tightly attaching two pretreated graphite felts in the step S2 to two sides of the bipolar plate with the surface attached with the mixed solution of water and methanol in the step S3 to form a graphite felt/bipolar plate/graphite felt sandwich structure;
s5: superposing 25 layers of the graphite felt/bipolar plate/graphite felt sandwich structure in the S4, placing the laminated structure in a device containing copper sheets for fixation, enabling the graphite felt/bipolar plate/graphite felt sandwich structure to be tightly attached through a tablet press with the constant pressure of 0.05Mpa, introducing direct current for 10min, generating a large amount of heat at the interface of the graphite felt and the bipolar plate in a resistance mode in the electrifying process, enabling the temperature to reach 140 ℃, softening the surface of the bipolar plate in contact with the graphite felt, embedding the graphite felt carbon fibers into the bipolar plate, and enabling the thickness of the embedded graphite felt to be 0.3mm to form an integrated electrode.
Example 9
A method for efficiently preparing an integrated electrode of a flow battery comprises the following steps:
s1: the bipolar plate is prepared by uniformly mixing 48wt% of polyacrylonitrile, 10wt% of natural graphite, 15wt% of acetylene black, 10wt% of graphene, 15wt% of carbon nano tube, 1wt% of tris [ 2.4-di-tert-butylphenyl ] phosphite and 1wt% of ethylene-vinyl acetate copolymer, and processing the mixture into a plate with the thickness of 0.8mm to obtain the bipolar plate;
s2: keeping the temperature of the graphite felt at 550 ℃ in an air atmosphere for 5 hours to obtain a pretreated graphite felt;
s3: soaking the bipolar plate in the S1 in n-hexane for 7min to attach a layer of n-hexane on the surface of the bipolar plate, and taking out;
s4: tightly attaching two pretreated graphite felts in the step S2 to two sides of the bipolar plate with n-hexane attached to the surface in the step S3 to form a graphite felt/bipolar plate/graphite felt sandwich structure;
s5: superposing 35 layers of the graphite felt/bipolar plate/graphite felt sandwich structure in the S4, placing the graphite felt/bipolar plate/graphite felt sandwich structure in a device containing a copper sheet for fixing, enabling the graphite felt/bipolar plate/graphite felt sandwich structure to be tightly attached through constant pressure of a tablet press with the constant pressure of 0.03Mpa, introducing direct current for 18min, generating a large amount of heat at the interface of the graphite felt and the bipolar plate in a resistance mode in the electrifying process, enabling the temperature to reach 145 ℃, softening the surface of the bipolar plate in contact with the graphite felt, embedding the graphite felt carbon fibers into the bipolar plate, and enabling the thickness of the embedded graphite felt to be 0.1mm to form an integrated electrode.
Example 10
A method for efficiently preparing an integrated electrode of a flow battery comprises the following steps:
s1: uniformly mixing a mixture of 52wt% of cellulose acetate, 10wt% of natural graphite, 15wt% of graphene, 10wt% of superconducting carbon black, 10wt% of dust-free carbon black, 1wt% of tris [ 2.4-di-tert-butylphenyl ] phosphite and 2wt% of ethylene-vinyl acetate copolymer, and processing the mixture into a plate with the thickness of 1.0mm to obtain the bipolar plate;
s2: keeping the temperature of the graphite felt at 550 ℃ in an air atmosphere for 5 hours to obtain a pretreated graphite felt;
s3: soaking the bipolar plate in S1 in n-heptane for 8min to attach a layer of n-heptane on the surface of the bipolar plate, and taking out;
s4: tightly attaching two pretreated graphite felts in the step S2 to two sides of the bipolar plate with n-heptane attached to the surface in the step S3 to form a graphite felt/bipolar plate/graphite felt sandwich structure;
s5: and (3) superposing 45 layers of the graphite felt/bipolar plate/graphite felt sandwich structure in the S4, fixing the graphite felt/bipolar plate/graphite felt sandwich structure in a device containing a copper sheet, enabling the graphite felt/bipolar plate/graphite felt sandwich structure to be tightly attached through constant pressure of a tablet press with the constant pressure of 0.04Mpa, introducing alternating current for 5min, generating a large amount of heat at the interface of the graphite felt and the bipolar plate in a resistance mode in the electrifying process, softening the surface of the bipolar plate in contact with the graphite felt when the temperature reaches 150 ℃, embedding the graphite felt carbon fibers into the bipolar plate, and enabling the thickness of the embedded graphite felt to be 0.1mm to form an integrated electrode.
Example 11
A method for efficiently preparing an integrated electrode of a flow battery comprises the following steps:
s1: the bipolar plate is prepared by uniformly mixing 55wt% of polychlorotrifluoroethylene, 10wt% of natural graphite, 15wt% of graphene, 10wt% of superconducting carbon black, 5wt% of dust-free carbon black, 1wt% of tris [ 2.4-di-tert-butylphenyl ] phosphite and 4wt% of ethylene-vinyl acetate copolymer, and processing the mixture into a plate with the thickness of 1.2mm to obtain the bipolar plate;
s2: keeping the temperature of the graphite felt at 500 ℃ in the air atmosphere for 6h to obtain a pretreated graphite felt;
s3: soaking the bipolar plate in the S1 in a mixed solution of water and ethanol for 9min to attach a layer of mixed solution of water and ethanol on the surface of the bipolar plate, and taking out the bipolar plate;
s4: tightly attaching two pretreated graphite felts in the step S2 to two sides of the bipolar plate with the surface attached with the mixed solution of water and ethanol in the step S3 to form a graphite felt/bipolar plate/graphite felt sandwich structure;
s5: and (3) superposing 10 layers of the graphite felt/bipolar plate/graphite felt sandwich structure in the S4, fixing the structure in a device containing a copper sheet, enabling the graphite felt/bipolar plate/graphite felt sandwich structure to be tightly attached through constant pressure of a tablet press with the constant pressure of 0.06Mpa, introducing alternating current for 9min, generating a large amount of heat at the interface of the graphite felt and the bipolar plate in a resistance mode in the electrifying process, softening the surface of the bipolar plate in contact with the graphite felt when the temperature reaches 200 ℃, embedding graphite felt carbon fibers into the bipolar plate, and enabling the thickness of the embedded graphite felt to be 0.2mm to form an integrated electrode.
Example 12
A method for efficiently preparing an integrated electrode of a flow battery comprises the following steps:
s1: uniformly mixing a mixture of 57wt% of polyvinylidene chloride, 5wt% of artificial graphite, 15wt% of carbon nano tube, 10wt% of graphene, 10wt% of superconducting carbon black, 1wt% of tris [ 2.4-di-tert-butylphenyl ] phosphite and 2wt% of ethylene-vinyl acetate copolymer, and processing the mixture into a plate with the thickness of 1.4mm to obtain a bipolar plate;
s2: keeping the temperature of the graphite felt at 450 ℃ in an air atmosphere for 8h to obtain a pretreated graphite felt;
s3: soaking the bipolar plate in the S1 in acetone for 10min to attach a layer of acetone on the surface of the bipolar plate, and taking out the bipolar plate;
s4: tightly attaching two pretreated graphite felts in the step S2 to two sides of the bipolar plate with acetone attached to the surface in the step S3 to form a graphite felt/bipolar plate/graphite felt sandwich structure;
s5: and (3) superposing 20 layers of the graphite felt/bipolar plate/graphite felt sandwich structure in the S4, placing the graphite felt/bipolar plate/graphite felt sandwich structure in a device containing a copper sheet for fixing, enabling the graphite felt/bipolar plate/graphite felt sandwich structure to be tightly attached through constant pressure of a tablet press with the constant pressure of 0.08Mpa, introducing alternating current for 13min, generating a large amount of heat at the interface of the graphite felt and the bipolar plate in a resistance mode in the electrifying process, enabling the temperature to reach 130 ℃, softening the surface of the bipolar plate in contact with the graphite felt, embedding the graphite felt carbon fibers into the bipolar plate, and enabling the thickness of the embedded graphite felt to be 0.1mm to form an integrated electrode.
Example 13
A method for efficiently preparing an integrated electrode of a flow battery comprises the following steps:
s1: uniformly mixing a mixture of 30wt% of polyethylene, 15wt% of polypropylene, 25wt% of conductive graphite, 10wt% of artificial graphite, 10wt% of carbon nano tube, 5wt% of dust-free carbon black, 0.5wt% of tris [ 2.4-di-tert-butylphenyl ] phosphite and 4.5wt% of ethylene-octene copolymer, and processing the mixture into a plate shape with the thickness of 1.2mm to obtain the bipolar plate;
s2: keeping the temperature of the graphite felt at 420 ℃ in an air atmosphere for 9h to obtain a pretreated graphite felt;
s3: soaking the bipolar plate in the S1 in n-hexane for 5min to attach a layer of n-hexane on the surface of the bipolar plate, and taking out the bipolar plate;
s4: tightly attaching two pretreated graphite felts in the step S2 to two sides of the bipolar plate with n-hexane attached to the surface in the step S3 to form a graphite felt/bipolar plate/graphite felt sandwich structure;
s5: and (3) superposing 30 layers of the graphite felt/bipolar plate/graphite felt sandwich structure in the S4, placing the laminated structure in a device containing a copper sheet for fixation, enabling the graphite felt/bipolar plate/graphite felt sandwich structure to be tightly attached through constant pressure of a tablet press with the constant pressure of 0.1Mpa, introducing alternating current for 17min, generating a large amount of heat at the interface of the graphite felt and the bipolar plate in a resistance mode in the electrifying process, enabling the temperature to reach 160 ℃, softening the surface of the bipolar plate in contact with the graphite felt, embedding the graphite felt carbon fibers into the bipolar plate, and enabling the thickness of the embedded graphite felt to be 0.1mm to form an integrated electrode.
Example 14
A method for efficiently preparing an integrated electrode of a flow battery comprises the following steps:
s1: uniformly mixing a mixture of 46wt% of polyacrylonitrile, 25wt% of conductive graphite, 10wt% of artificial graphite, 10wt% of carbon nano tube, 5wt% of dust-free carbon black, 0.5wt% of tris [ 2.4-di-tert-butylphenyl ] phosphite and 3.5wt% of ethylene-octene copolymer, and processing the mixture into a plate with the thickness of 1.0mm to obtain the bipolar plate;
s2: keeping the temperature of the graphite felt at 400 ℃ in an air atmosphere for 10h to obtain a pretreated graphite felt;
s3: soaking the bipolar plate in S1 in n-heptane for 6min to attach a layer of n-heptane on the surface of the bipolar plate, and taking out;
s4: tightly attaching two pretreated graphite felts in the step S2 to two sides of the bipolar plate with n-heptane attached to the surface in the step S3 to form a graphite felt/bipolar plate/graphite felt sandwich structure;
s5: and (3) superposing 40 layers of the graphite felt/bipolar plate/graphite felt sandwich structure in the S4, fixing the graphite felt/bipolar plate/graphite felt sandwich structure in a device containing a copper sheet, enabling the graphite felt/bipolar plate/graphite felt sandwich structure to be tightly attached through constant pressure of a tablet press with the constant pressure of 0.09Mpa, introducing alternating current for 15min, generating a large amount of heat at the interface of the graphite felt and the bipolar plate in a resistance mode in the electrifying process, softening the surface of the bipolar plate in contact with the graphite felt when the temperature reaches 140 ℃, embedding the carbon fibers of the graphite felt into the bipolar plate, and enabling the thickness of the embedded graphite felt to be 0.2mm to form an integrated electrode.
Example 15
A method for efficiently preparing an integrated electrode of a flow battery comprises the following steps:
s1: uniformly mixing 40wt% of polyethylene, 5wt% of polyacrylonitrile, 20wt% of conductive graphite, 20wt% of artificial graphite, 10wt% of carbon nano tube, 4wt% of dust-free carbon black, 0.5wt% of tris [ 2.4-di-tert-butylphenyl ] phosphite and 0.5wt% of ethylene-vinyl acetate copolymer, and processing the mixture into a plate with the thickness of 0.8mm to obtain the bipolar plate;
s2: soaking the graphite felt in 98% concentrated sulfuric acid at normal temperature for 7h, taking out, washing with deionized water, and drying to obtain a pretreated graphite felt;
s3: soaking the bipolar plate in the S1 in a mixed solution of methanol and ethanol for 7min, so that a layer of mixed solution of methanol and ethanol is attached to the surface of the bipolar plate, and then taking out the bipolar plate;
s4: tightly attaching two pretreated graphite felts in the step S2 to two sides of the bipolar plate with the surface attached with the mixed solution of methanol and ethanol in the step S3 to form a graphite felt/bipolar plate/graphite felt sandwich structure;
s5: and (3) superposing 6 layers of the graphite felt/bipolar plate/graphite felt sandwich structure in the S4, placing the laminated structure in a device containing a copper sheet for fixation, enabling the graphite felt/bipolar plate/graphite felt sandwich structure to be tightly attached through constant pressure of a tablet press with the constant pressure of 0.08Mpa, introducing direct current for 5min, generating a large amount of heat at the interface of the graphite felt and the bipolar plate in a resistance mode in the electrifying process, enabling the temperature to reach 150 ℃, softening the surface of the bipolar plate in contact with the graphite felt, embedding the graphite felt carbon fibers into the bipolar plate, and enabling the thickness of the embedded graphite felt to be 0.1mm to form an integrated electrode.
Example 16
A method for efficiently preparing an integrated electrode of a flow battery comprises the following steps:
s1: uniformly mixing a mixture of 35wt% of polypropylene, 10wt% of polyacrylonitrile, 25wt% of conductive graphite, 10wt% of artificial graphite, 10wt% of graphene, 5wt% of dust-free carbon black, 0.5wt% of tris [ 2.4-di-tert-butylphenyl ] phosphite and 4.5wt% of ethylene-octene copolymer, and processing the mixture into a plate with the thickness of 0.6mm to obtain the bipolar plate;
s2: soaking the graphite felt in 98% concentrated sulfuric acid at normal temperature for 6h, taking out, washing with deionized water, and drying to obtain a pretreated graphite felt;
s3: soaking the bipolar plate in the S1 in a mixed solution of n-hexane and n-heptane for 5min, so that a layer of mixed solution of n-hexane and n-heptane is attached to the surface of the bipolar plate, and then taking out the bipolar plate;
s4: tightly attaching two pretreated graphite felts in the step S2 to two sides of the bipolar plate with the surface attached with the mixed solution of normal hexane and normal heptane in the step S3 to form a graphite felt/bipolar plate/graphite felt sandwich structure;
s5: and (3) superposing 18 layers of the graphite felt/bipolar plate/graphite felt sandwich structure in the S4, placing the laminated structure in a device containing a copper sheet for fixation, enabling the graphite felt/bipolar plate/graphite felt sandwich structure to be tightly attached through constant pressure of a tablet press with the constant pressure of 0.04Mpa, introducing direct current for 20min, generating a large amount of heat at the interface of the graphite felt and the bipolar plate in a resistance mode in the electrifying process, enabling the temperature to reach 170 ℃, softening the surface of the bipolar plate in contact with the graphite felt, embedding the graphite felt carbon fibers into the bipolar plate, and enabling the thickness of the embedded graphite felt to be 0.3mm to form an integrated electrode.
Example 17
A method for efficiently preparing an integrated electrode of a flow battery comprises the following steps:
s1: uniformly mixing a mixture of 45wt% of polystyrene, 25wt% of conductive graphite, 10wt% of artificial graphite, 10wt% of carbon nano tubes, 5wt% of dust-free carbon black, 0.5wt% of tris [ 2.4-di-tert-butylphenyl ] phosphite and 4.5wt% of ethylene-octene copolymer, and processing the mixture into a plate with the thickness of 0.7mm to obtain the bipolar plate;
s2: soaking the graphite felt in 98% concentrated sulfuric acid at normal temperature for 8h, taking out, washing with deionized water, and drying to obtain a pretreated graphite felt;
s3: soaking the bipolar plate in the S1 in acetone for 6min to attach a layer of acetone on the surface of the bipolar plate, and taking out the bipolar plate;
s4: tightly attaching two pretreated graphite felts in the step S2 to two sides of the bipolar plate with acetone attached to the surface in the step S3 to form a graphite felt/bipolar plate/graphite felt sandwich structure;
s5: and (3) superposing 24 layers of the graphite felt/bipolar plate/graphite felt sandwich structure in the S4, placing the laminated structure in a device containing a copper sheet for fixation, enabling the graphite felt/bipolar plate/graphite felt sandwich structure to be tightly attached through constant pressure of a tablet press with the constant pressure of 0.03Mpa, introducing alternating current for 5min, generating a large amount of heat at the interface of the graphite felt and the bipolar plate in a resistance mode in the electrifying process, softening the surface of the bipolar plate in contact with the graphite felt when the temperature reaches 100 ℃, embedding the carbon fibers of the graphite felt into the bipolar plate, and enabling the thickness of the embedded graphite felt to be 0.1mm to form an integrated electrode.
Example 18
A method for efficiently preparing an integrated electrode of a flow battery comprises the following steps:
s1: uniformly mixing a mixture of 45wt% of cellulose acetate, 25wt% of conductive graphite, 10wt% of artificial graphite, 10wt% of carbon nano tubes, 5wt% of superconducting carbon black, 0.5wt% of tris [ 2.4-di-tert-butylphenyl ] phosphite and 4.5wt% of ethylene-octene copolymer, and processing the mixture into a plate shape with the thickness of 0.9mm to obtain the bipolar plate;
s2: soaking the graphite felt in 98% concentrated sulfuric acid at normal temperature for 7h, taking out, washing with deionized water, and drying to obtain a pretreated graphite felt;
s3: soaking the bipolar plate in the S1 in butyl acrylate for 7min, and taking out the bipolar plate after a layer of butyl acrylate is attached to the surface of the bipolar plate;
s4: tightly attaching two pretreated graphite felts in the step S2 to two sides of the bipolar plate with butyl acrylate attached to the surface in the step S3 to form a graphite felt/bipolar plate/graphite felt sandwich structure;
s5: and (3) superposing 36 layers of the graphite felt/bipolar plate/graphite felt sandwich structure in the S4, placing the laminated structure in a device containing a copper sheet for fixation, enabling the graphite felt/bipolar plate/graphite felt sandwich structure to be tightly attached through constant pressure of a tablet press with the constant pressure of 0.03Mpa, introducing alternating current for 15min, generating a large amount of heat at the interface of the graphite felt and the bipolar plate in a resistance mode in the electrifying process, enabling the temperature to reach 155 ℃, softening the surface of the bipolar plate in contact with the graphite felt, embedding the graphite felt carbon fibers into the bipolar plate, and enabling the thickness of the embedded graphite felt to be 0.1mm to form an integrated electrode.
Comparative example 1
A method for efficiently preparing an integrated electrode of a flow battery comprises the following steps:
s1: uniformly mixing 42wt% of polypropylene, 30wt% of artificial graphite, 20wt% of conductive graphite, 5wt% of carbon nano tube, 2wt% of antioxidant and 1% of toughening agent, and processing into a plate shape with the thickness of 0.9mm to obtain the bipolar plate;
s2: keeping the temperature of the graphite felt at 450 ℃ in an air atmosphere for 8h to obtain a pretreated graphite felt;
s3: tightly attaching two pretreated graphite felts in the step S2 to two sides of the bipolar plate to form a graphite felt/bipolar plate/graphite felt sandwich structure;
s4: and (3) superposing 15 layers of the graphite felt/bipolar plate/graphite felt sandwich structure in the S3, placing the laminated structure in a device containing a copper sheet for fixation, enabling the graphite felt/bipolar plate/graphite felt sandwich structure to be tightly attached through a constant pressure of 0.05Mpa of a tablet press, introducing direct current for 30min, generating a large amount of heat at the interface of the graphite felt and the bipolar plate in a resistance mode in the electrifying process, softening the surface of the bipolar plate in contact with the graphite felt when the temperature reaches 165 ℃, embedding graphite felt carbon fibers into the bipolar plate, and enabling the thickness of the embedded graphite felt to be 0.2mm to form an integrated electrode.
Comparative example 2
A vanadium battery integrated electrode is prepared by the following steps:
and (3) keeping the temperature of the graphite felt at 500 ℃ in the air atmosphere for 10h, placing the graphite felt on two sides of the conductive plastic bipolar plate after cooling, setting the temperature of a hot press to 170 ℃, hot-pressing the graphite felt and the bipolar plate for 15min, and cold-pressing for 10min to obtain an integrated bipolar plate, wherein the thickness of the embedded graphite felt is 0.1 mm.
The integrated electrodes prepared in each example and comparative example were cut to a size of 3cm × 3cm, then both ends were covered with copper plates, and a constant 25N pressure was applied, and the contact resistance was tested by a universal meter; the integrated electrodes in the comparative example and each example were assembled into a stack as electrodes and tested at a test current density of 80mA/cm2Coulombic efficiency, voltage efficiency and energy efficiency were recorded. The test results are shown in table 1:
table 1: battery performance test meter adopting integrated motor to assemble electric pile
Therefore, in the embodiment of the invention, the number of the integrated electrodes produced each time is large, the processing time is short, and the efficiency is higher. The surface of the bipolar plate in the comparative example 1 has no solvent, the processing time is longest, and the addition of the solvent is proved to increase the resistance between the bipolar plate and the graphite felt, accelerate heat generation and be beneficial to improving the production efficiency. The integrated electrode obtained by adopting the traditional hot-pressing mode has the advantages of maximum internal resistance, low production efficiency, high production energy consumption due to the fact that heat is transferred through the graphite felt with poor heat conductivity in the hot-pressing process, and the current mode adopted by the invention enables the graphite felt electrode and the bipolar plate to release heat through the contact resistance so as to achieve local heating of key parts, is uniform in heat and low in energy consumption, has a good effect of embedding the graphite felt electrode into the bipolar plate, is low in contact resistance, and can improve the battery efficiency.
In addition, the embodiment of the invention has lower integrated electrode internal resistance, higher voltage efficiency and energy efficiency, and shows that the method for preparing the integrated bipolar plate of the redox flow battery by adopting the current mode has the advantages of simple process, mass production and high efficiency, can obviously reduce the internal resistance of the integrated electrode, improves the efficiency of the redox flow battery, and has the advantages of high efficiency, low cost, energy conservation and environmental protection.
The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention, and various modifications and changes may be made by those skilled in the art. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (8)
1. A method for efficiently preparing an integrated electrode of a flow battery is characterized by comprising the following steps:
s1: uniformly mixing a mixture consisting of 40-60wt% of plastic, 30-59wt% of conductive additive and 1-10wt% of additive, and processing to obtain a plate with the thickness of 0.6-1.4mm to obtain the bipolar plate;
s2: carrying out heat treatment or acid treatment on the graphite felt to obtain a pretreated graphite felt;
s3: soaking the bipolar plate in the S1 in a volatile solvent for 5-10min to attach a layer of volatile solvent on the surface of the bipolar plate, and then taking out the bipolar plate;
s4: tightly attaching two pretreated graphite felts in the step S2 to two sides of the bipolar plate with the surface attached with the volatile solvent in the step S3 to form a graphite felt/bipolar plate/graphite felt sandwich structure;
s5: and (3) superposing and fixing the graphite felt/bipolar plate/graphite felt sandwich structure in the S4 in a device containing a copper sheet in a multi-layer manner, tightly attaching the graphite felt/bipolar plate/graphite felt sandwich structure through a tablet press with the constant pressure of 0.02-0.10Mpa, introducing direct current or alternating current for 5-20min at the temperature of 90-200 ℃, embedding graphite felt carbon fibers into the bipolar plate, wherein the thickness of the embedded graphite felt is 0.1-0.3mm, and forming an integrated electrode.
2. The method for efficiently preparing the integrated electrode of the flow battery as claimed in claim 1, wherein the plastic in S1 is any one or a mixture of two or more of the following: polyethylene, polypropylene, polystyrene, polyacrylonitrile, polyvinyl chloride, plexiglass, cellulose acetate, polychlorotrifluoroethylene or polyvinylidene chloride.
3. The method for efficiently preparing the integrated electrode of the flow battery as claimed in claim 1, wherein the conductive aid in S1 is any one or a mixture of two or more of the following: conductive graphite, natural graphite, artificial graphite, acetylene black, graphene, carbon nanotubes, superconducting carbon black, or dust-free carbon black.
4. The method for efficiently preparing the integrated electrode of the flow battery as claimed in claim 1, wherein the assistant in S1 is one or a mixture of two or more of the following: tris [2, 4-di-tert-butylphenyl ] phosphite, polyvinyl alcohol, methyltriacetoxysilane, ethylene-vinyl acetate copolymer or ethylene-octene copolymer.
5. The method for efficiently preparing the integrated electrode of the flow battery as claimed in claim 1, wherein the heat treatment in S2 is performed by keeping the graphite felt at 400-600 ℃ for 4-10h to obtain the pretreated graphite felt.
6. The method for efficiently preparing the integrated electrode of the flow battery as claimed in claim 1, wherein the acid treatment in S2 is to put the graphite felt into concentrated sulfuric acid, soak the graphite felt at normal temperature for 6-8h, take out the graphite felt, wash the graphite felt with deionized water, and dry the graphite felt to obtain the pretreated graphite felt.
7. The method for efficiently preparing the integrated electrode of the flow battery as claimed in claim 1, wherein the volatile solvent in S3 is any one or a mixture of two or more of the following: methanol, ethanol, acetone, butyl acetate, water, n-hexane, n-heptane or butyl acrylate.
8. The method for efficiently preparing the integrated electrode of the flow battery as claimed in claim 1, wherein the number of stacked graphite felt/bipolar plate/graphite felt "sandwich" structure in S3 is 1-50.
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| CN114256476A (en) * | 2022-03-01 | 2022-03-29 | 杭州德海艾科能源科技有限公司 | Conductive polymer bipolar plate for flow battery and preparation method thereof |
| CN114566666A (en) * | 2022-03-02 | 2022-05-31 | 保定市正念复合材料科技有限公司 | Composite bipolar plate for flow battery, preparation tool and preparation method |
| CN114824314A (en) * | 2022-04-29 | 2022-07-29 | 四川星明能源环保科技有限公司 | Electrochemical modification method of vanadium battery electrode based on silane hydrolysate |
| CN116505049A (en) * | 2023-06-27 | 2023-07-28 | 杭州德海艾科能源科技有限公司 | Integrated battery cell for flow battery and manufacturing method thereof |
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