CN115020720B - Vanadium redox flow battery integrated electrode and preparation method thereof - Google Patents
Vanadium redox flow battery integrated electrode and preparation method thereof Download PDFInfo
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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
- 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
- H01M4/8878—Treatment steps after deposition of the catalytic active composition or after shaping of the electrode being free-standing body
- H01M4/8896—Pressing, rolling, calendering
-
- 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
-
- 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
-
- 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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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
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- Engineering & Computer Science (AREA)
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Abstract
The invention provides a vanadium redox flow battery integrated electrode and a preparation method thereof; the preparation method comprises the following steps: a) Mixing carbon nano tube slurry, a binder and a conductive agent in a solvent to obtain a binding slurry; b) Coating a first layer of the bonding slurry on one side of the bipolar plate, then covering carbon fiber paper, coating a second layer of the bonding slurry, then covering a carbon felt, and sequentially pressing and drying to obtain a semi-finished electrode; c) And b) repeating the step b) on the other side of the bipolar plate of the semi-finished electrode to obtain the integrated electrode of the vanadium redox flow battery. Compared with the prior art, the preparation method provided by the invention has the advantages that the bipolar plate and the carbon felt are combined and integrated by adopting the specific bonding slurry, so that the vanadium redox flow battery integrated electrode is obtained, the contact resistance of the bipolar plate and the carbon felt is reduced, the compression thickness of the carbon felt in a galvanic pile is reduced, the flow resistance of the carbon felt is reduced, and the performance efficiency of the galvanic pile is further improved.
Description
Technical Field
The invention relates to the technical field of integrated electrodes, in particular to a vanadium redox flow battery integrated electrode and a preparation method thereof.
Background
According to different preparation methods, the integrated electrodes can be divided into three types: coating, electrochemical deposition and hot pressing.
(1) Coating: soaking an electrode in concentrated sulfuric acid, taking out, drying in an oven at 60-70 ℃, carrying out ultrasonic oscillation on graphene powder to be uniformly mixed into a polymer solution, standing after mixing, uniformly coating the graphene polymer solution on the surface of the treated electrode, and drying the obtained electrode under an infrared lamp; the obtained electrode is put into formaldehyde or glutaraldehyde solution with the weight percentage of 2-5 percent for crosslinking, and is put into a baking oven with the temperature of 50-70 ℃ for baking after being taken out, thus obtaining the integrated flexible electrode.
(2) Electrochemical deposition: taking a bipolar plate as a working electrode, adopting a three-electrode system, taking an aqueous solution containing graphene oxide and lithium perchlorate as a supporting electrolyte, performing first electrochemical deposition, and immersing and washing porous graphene/bipolar plate integrated electrode materials with deionized water; and (3) taking the immersed porous graphene/bipolar plate integrated electrode material as a working electrode, adopting a three-electrode system, taking a solution containing functional components as a secondary electrodeposition electrolyte solution, performing secondary electrochemical deposition, and introducing the functional components on the surface of the porous graphene to obtain the functional porous graphene integrated electrode material.
(3) Hot pressing:
① Carbon felt-graphene-carbon felt: placing the graphene film in the middle of polyacrylonitrile carbon fibers with equal thickness, and performing needling to form a felt; sequentially performing pre-oxidation treatment, carbonization treatment and high-temperature treatment on the felt body to form an integrated porous carbon felt-graphene film-carbon felt; and carrying out vacuum hot-pressing treatment, wherein the graphene film is subjected to surface wrinkling and carbon felt fiber yarn blocking of graphene pores due to the action of certain pressure to form an ultrahigh flexible graphene film, so that the integrated electrode-bipolar plate structure can be prepared.
② Resin-graphite felt-resin: soaking the electrode and the polymer resin powder in a solvent, filling the polymer resin powder in the electrode, fully mixing, putting the electrode and the polymer resin powder in an oven for drying, putting the dried electrode in a die, and hot-pressing the electrode by a hot press; and taking out, putting into a solvent to separate out surface resin, and putting into an oven to be dried, thus obtaining the integrated electrode.
③ Graphite felt-bipolar plate-graphite felt: mixing high polymer resin or fluoroplastic dispersion liquid, a conductive agent and an auxiliary agent, pre-pressing into a sheet, cooling to obtain a bipolar plate, and then modifying to improve the surface hydrophilicity or increase the surface free radical; carrying out heat treatment, acid treatment and impregnation treatment on the surface of the graphite felt; and (3) placing the graphite felt and the bipolar plate in a mould for fixation, enabling the impregnated side of the graphite felt to be in contact with the bipolar plate, performing hot-pressing bonding molding, and cooling to room temperature.
④ Carbon felt-bipolar plate (TiO 2) -carbon felt: uniformly mixing nano titanium dioxide particles with a core-shell structure into the curable resin, and uniformly mixing a curing agent; curing the curable resin in a mold to form a matrix; and respectively covering the activated carbon fiber felt on one surface and the other surface of the matrix, which are opposite to each other, and carrying out integrated composite treatment on the carbon fiber felt and the matrix to obtain the double electrode of the all-vanadium redox flow battery.
However, the above preparation method has the following defects and disadvantages: (1) high cost: the integrated electrode technology uses graphene, titanium dioxide and the like as materials, and is high in price; (2) complex process: the electrochemical deposition, hot pressing and other methods have higher requirements on equipment conditions, extremely accurate flow operation is needed, and the large-scale implementation has higher difficulty; (3) the addition of new materials has a large influence on the battery: some of the methods involve the addition of materials such as titanium dioxide, resin materials, dispersants, which may adversely affect the performance of the battery.
Disclosure of Invention
In view of the above, the invention aims to provide an integrated electrode of a vanadium redox flow battery and a preparation method thereof, and the integrated electrode of the vanadium redox flow battery reduces the contact resistance of a bipolar plate and a carbon felt by compounding and integrating the bipolar plate and the carbon felt, reduces the compression thickness of the carbon felt in a galvanic pile, reduces the flow resistance of the carbon felt, and further improves the performance efficiency of the galvanic pile.
The invention provides a preparation method of an integrated electrode of a vanadium redox flow battery, which comprises the following steps:
a) Mixing carbon nano tube slurry, a binder and a conductive agent in a solvent to obtain a binding slurry;
b) Coating a first layer of the bonding slurry on one side of the bipolar plate, then covering carbon fiber paper, coating a second layer of the bonding slurry, then covering a carbon felt, and sequentially pressing and drying to obtain a semi-finished electrode;
c) And b) repeating the step b) on the other side of the bipolar plate of the semi-finished electrode to obtain the integrated electrode of the vanadium redox flow battery.
Preferably, the carbon nanotube slurry in step a) has a carbon nanotube content of 1wt% to 10wt%.
Preferably, the binder in step a) is selected from polyvinyl alcohol, polytetrafluoroethylene, carboxymethyl cellulose or polyvinylidene fluoride.
Preferably, the conductive agent in step a) is selected from one or more of conductive carbon black, ketjen black, acetylene black, conductive graphite, carbon fiber and graphene.
Preferably, the mass ratio of the carbon nanotube slurry, the binder and the conductive agent in the step a) is 1: (1.2-2): (0.5-1).
Preferably, the mixing process in step a) is specifically:
Taking carbon nano tube slurry in a beaker, adding a solvent, and magnetically stirring for 20-40 min at 15-25 ℃ and 1000-3000 r/min; simultaneously, taking the binder and the conductive agent to be ground in a mortar for 20-40 min to obtain a mixture; then the mixture is put into the beaker, then solvent is added, and magnetic stirring is continued for 10 to 15 hours at 15 to 25 ℃ and 1000 to 3000r/min, thus obtaining the bonding slurry.
Preferably, the process of applying the first layer of the bonding slurry to one side of the bipolar plate in the step b) specifically includes:
Cutting the bipolar plate into a size of (22-30) cm x (15-25) cm, horizontally placing the bipolar plate on a glass plate, and cleaning the surface of the bipolar plate with alcohol; drawing a rectangular area with the length of (17-21) cm multiplied by (9-14) cm on the center of the pen; and then placing the first layer of the bonding slurry in a rectangular area, adjusting the thickness of a scraper to be 0.1-1 mm, and carrying out scraping coating from left to right.
Preferably, the pressing pressure in step b) is from 0.5N to 5N.
Preferably, the drying in step b) is carried out at a temperature of 100 to 150℃for a period of 10 to 15 hours.
The invention also provides an integrated electrode of the vanadium redox flow battery, which is prepared by adopting the preparation method of the technical scheme.
The invention provides a vanadium redox flow battery integrated electrode and a preparation method thereof; the preparation method comprises the following steps: a) Mixing carbon nano tube slurry, a binder and a conductive agent in a solvent to obtain a binding slurry; b) Coating a first layer of the bonding slurry on one side of the bipolar plate, then covering carbon fiber paper, coating a second layer of the bonding slurry, then covering a carbon felt, and sequentially pressing and drying to obtain a semi-finished electrode; c) And b) repeating the step b) on the other side of the bipolar plate of the semi-finished electrode to obtain the integrated electrode of the vanadium redox flow battery. Compared with the prior art, the preparation method provided by the invention has the advantages that the bipolar plate and the carbon felt are combined and integrated by adopting the specific bonding slurry, so that the vanadium redox flow battery integrated electrode is obtained, the contact resistance of the bipolar plate and the carbon felt is reduced, the compression thickness of the carbon felt in a galvanic pile is reduced, the flow resistance of the carbon felt is reduced, and the performance efficiency of the galvanic pile is further improved; meanwhile, the preparation method provided by the invention has the advantages of simple process, low raw material cost, easiness in operation, good product stability and wide application prospect.
Drawings
FIG. 1 is a schematic structural diagram of a finished integrated electrode obtained by the preparation method according to the embodiment of the invention;
FIG. 2 is a graph showing the change in contact resistance before and after compounding the integrated electrode prepared in example 1;
FIG. 3 is a plot of integrated electrode resistance versus bond line carbon content;
FIG. 4 is a graph showing the flow rate as a function of pressure before and after compounding in example 1;
fig. 5 shows the pile performance of example 1.
Detailed Description
The technical solutions of the present invention will be clearly and completely described in conjunction with the embodiments of the present invention, and it is apparent that the described embodiments are only some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
The invention provides a preparation method of an integrated electrode of a vanadium redox flow battery, which comprises the following steps:
a) Mixing carbon nano tube slurry, a binder and a conductive agent in a solvent to obtain a binding slurry;
b) Coating a first layer of the bonding slurry on one side of the bipolar plate, then covering carbon fiber paper, coating a second layer of the bonding slurry, then covering a carbon felt, and sequentially pressing and drying to obtain a semi-finished electrode;
c) And b) repeating the step b) on the other side of the bipolar plate of the semi-finished electrode to obtain the integrated electrode of the vanadium redox flow battery.
Firstly, mixing carbon nano tube slurry, a binder and a conductive agent in a solvent to obtain the binding slurry.
In the present invention, the Carbon Nanotube (CNT) content in the Carbon Nanotube (CNT) paste is preferably 1wt% to 10wt%, more preferably 5wt%. The source of the carbon nanotubes is not particularly limited, and commercially available products known to those skilled in the art may be used.
In the present invention, the binder is preferably selected from polyvinyl alcohol (PVA), polytetrafluoroethylene (PTFE), carboxymethyl cellulose (CMC) or polyvinylidene fluoride (PVDF), more preferably polyvinylidene fluoride (PVDF). The source of the binder is not particularly limited in the present invention, and commercially available products known to those skilled in the art may be used.
In the present invention, the conductive agent is preferably one or more selected from conductive carbon black, ketjen black, acetylene black, conductive graphite, carbon fiber, and graphene, more preferably conductive carbon black (SP). The source of the conductive agent is not particularly limited in the present invention, and commercially available products known to those skilled in the art may be used.
In the present invention, the mass ratio of the carbon nanotube paste, the binder and the conductive agent is preferably 1: (1.2-2): (0.5 to 1), more preferably 1: (1.5-1.75): (0.7-0.95).
In the present invention, the solvent is preferably determined according to the kind of the binder, for example, when polyvinyl alcohol (PVA), polytetrafluoroethylene (PTFE), and carboxymethyl cellulose (CMC) are used as the binder, water may be used as the solvent; and when polyvinylidene fluoride (PVDF) is used as a binder, N-methylpyrrolidone (NMP) is selected as a solvent.
In the invention, the solvent is used in an amount of 8ml to 9ml per 1g based on the total mass of the carbon nanotube slurry, the binder and the conductive agent; in a preferred embodiment of the present invention, the total mass of the carbon nanotube paste, binder and conductive agent is 3g and the solvent amount is 25mL.
In the present invention, the mixing process is preferably specifically:
Taking carbon nano tube slurry in a beaker, adding a solvent, and magnetically stirring for 20-40 min at 15-25 ℃ and 1000-3000 r/min; simultaneously, taking the binder and the conductive agent to be ground in a mortar for 20-40 min to obtain a mixture; then placing the mixture into the beaker, adding a solvent, sealing with a sealing film, and continuing magnetic stirring at 15-25 ℃ and 1000-3000 r/min for 10-15 h to obtain bonding slurry;
More preferably:
Taking carbon nano tube slurry in a beaker, adding a solvent, and magnetically stirring for 30min at 20 ℃ and 2000 r/min; simultaneously, taking a binder and a conductive agent, and grinding for 30min in a mortar to obtain a mixture; then the mixture is put into the beaker, then the solvent is added, after the mixture is sealed by a sealing film, the magnetic stirring is continued for 12 hours at 20 ℃ and 2000r/min, and the bonding slurry is obtained.
After the bonding slurry is obtained, the invention coats a first layer of the bonding slurry on one side of the bipolar plate, then coats carbon fiber paper, coats a second layer of the bonding slurry, then coats carbon felt, and sequentially carries out pressing and drying to obtain the semi-finished electrode.
The source of the bipolar plate, the carbon fiber paper and the carbon felt is not particularly limited, and commercially available products known to those skilled in the art can be used.
In the present invention, the process of applying the first layer of the above-mentioned bonding slurry on one side of the bipolar plate is preferably specifically:
cutting the bipolar plate into a size of (22-30) cm x (15-25) cm, horizontally placing the bipolar plate on a glass plate, and cleaning the surface of the bipolar plate with alcohol; drawing a rectangular area with the length of (17-21) cm multiplied by (9-14) cm on the center of the pen; then placing the first layer of the bonding slurry in a rectangular area, adjusting the thickness of a scraper to be 0.1-1 mm, and carrying out scraping coating from left to right;
More preferably:
Cutting the bipolar plate into a size of 24cm multiplied by 20cm, horizontally placing the bipolar plate on a glass plate, and cleaning the surface of the bipolar plate with alcohol; drawing a rectangular area of 20.5cm multiplied by 12cm on the center of the pen; and then placing the first layer of the bonding slurry in a rectangular area, adjusting the thickness of a scraper to be 0.2-0.5 mm, and carrying out scraping coating from left to right.
In the present invention, the process of coating the second layer with the adhesive slurry is substantially identical to the process of coating the first layer with the adhesive slurry, and the present invention is not repeated herein.
In the present invention, the pressing pressure is preferably 0.5N to 5N, more preferably 0.5N to 1N.
In the present invention, the drying temperature is preferably 100 to 150 ℃, more preferably 120 ℃; the drying time is preferably 10 to 15 hours, more preferably 12 hours.
And (c) repeating the step (b) on the other side of the bipolar plate of the semi-finished electrode after the semi-finished electrode is obtained, so as to obtain the vanadium redox flow battery integrated electrode.
In the present invention, the above semi-finished electrode is preferably placed on a resistance test die having a thickness of 6mm.
According to the preparation method provided by the invention, the bipolar plate and the carbon felt are combined and integrated by adopting the specific adhesive slurry, so that the vanadium redox flow battery integrated electrode is obtained, the contact resistance of the bipolar plate and the carbon felt is reduced, the compression thickness of the carbon felt in a galvanic pile is reduced, the flow resistance of the carbon felt is reduced, and the performance efficiency of the galvanic pile is further improved; meanwhile, the preparation method provided by the invention has the advantages of simple process, low raw material cost, easiness in operation, good product stability and wide application prospect.
The invention also provides an integrated electrode of the vanadium redox flow battery, which is prepared by adopting the preparation method of the technical scheme. According to the description of the preparation method, the structural schematic diagram of the vanadium redox flow battery integrated electrode provided by the invention is shown in the figure 1, and the structural schematic diagram is a carbon felt, a coating formed by bonding slurry, carbon fiber paper, a coating formed by bonding slurry, a bipolar plate, a coating formed by bonding slurry, carbon fiber paper, a coating formed by bonding slurry and a carbon felt from top to bottom in sequence.
The invention provides a vanadium redox flow battery integrated electrode and a preparation method thereof; the preparation method comprises the following steps: a) Mixing carbon nano tube slurry, a binder and a conductive agent in a solvent to obtain a binding slurry; b) Coating a first layer of the bonding slurry on one side of the bipolar plate, then covering carbon fiber paper, coating a second layer of the bonding slurry, then covering a carbon felt, and sequentially pressing and drying to obtain a semi-finished electrode; c) And b) repeating the step b) on the other side of the bipolar plate of the semi-finished electrode to obtain the integrated electrode of the vanadium redox flow battery. Compared with the prior art, the preparation method provided by the invention has the advantages that the bipolar plate and the carbon felt are combined and integrated by adopting the specific bonding slurry, so that the vanadium redox flow battery integrated electrode is obtained, the contact resistance of the bipolar plate and the carbon felt is reduced, the compression thickness of the carbon felt in a galvanic pile is reduced, the flow resistance of the carbon felt is reduced, and the performance efficiency of the galvanic pile is further improved; meanwhile, the preparation method provided by the invention has the advantages of simple process, low raw material cost, easiness in operation, good product stability and wide application prospect.
In order to further illustrate the present invention, the following examples are provided. The raw materials used in the following examples of the present invention are all commercially available sources; wherein the carbon nanotube slurry is WXCL-07 provided by Harbin gold technology Co., ltd, and the SP is Super P conductive carbon black provided by MTI Co., ltd, 0012101.
Example 1
(1) 1.2G of carbon nanotube slurry (with 5 percent of CNT content, 0.06 g) is taken in a beaker, and 5mlNMP g is added and magnetically stirred for 30min at 20 ℃ and 2000 r/min; meanwhile, 2.1g of PVDF and 0.84g of SP were taken in a mortar, and ground with a mortar hammer for 30min (powder has no obvious white particles), to obtain a mixture; then, the mixture was placed in the beaker, 20ml of NMP was added thereto, and after sealing with a sealing film, magnetic stirring was continued at 20℃and 2000r/min for 12 hours to obtain a slurry for bonding.
(2) Cutting the bipolar plate into a size of 24cm multiplied by 20cm, horizontally placing the bipolar plate on a glass plate, and cleaning the surface of the bipolar plate with alcohol; drawing a rectangular area of 20.5cm multiplied by 12cm on the center of the pen; then placing the bonding slurry obtained in the step (1) in a rectangular area, adjusting the thickness of a scraper to be 0.2mm, carrying out scraping coating from left to right, and cleaning up the redundant bonding slurry outside the rectangular area; then coating carbon fiber paper on the carbon fiber paper, repeating the operation, and continuously scraping the carbon fiber paper, namely placing the bonding slurry obtained in the step (1) in a rectangular area corresponding to the carbon fiber paper, adjusting the thickness of a scraper to be 0.2mm, scraping the carbon fiber paper from left to right, and cleaning the redundant bonding slurry outside the rectangular area; and finally covering the carbon felt, applying external pressure of 0.5N, and drying in a vacuum drying oven at 120 ℃ for 12 hours to obtain the semi-finished electrode.
(3) Repeating the step (2), and coating and bonding the back surface of the semi-finished electrode to obtain the finished integrated electrode.
Example 2
(1) 1.2G of carbon nanotube slurry (CNT content 5%, 0.06 g) is taken in a beaker, 5ml of NMP is added and magnetically stirred at 20 ℃ and 2000r/min for 30min; simultaneously, 1.8g of PVDF and 1.14g of SP were taken in a mortar, and ground with a mortar hammer for 30 minutes (powder has no obvious white particles), to obtain a mixture; then the mixture is put into the beaker, then 20mlNMP is added, after the mixture is sealed by a sealing film, the magnetic stirring is continued for 12 hours at 20 ℃ and 2000r/min, and the bonding slurry is obtained.
(2) Cutting the bipolar plate into a size of 24cm multiplied by 20cm, horizontally placing the bipolar plate on a glass plate, and cleaning the surface of the bipolar plate with alcohol; drawing a rectangular area of 20.5cm multiplied by 12cm on the center of the pen; then placing the bonding slurry obtained in the step (1) in a rectangular area, adjusting the thickness of a scraper to be 0.5mm, carrying out scraping coating from left to right, and cleaning up the redundant bonding slurry outside the rectangular area; then coating carbon fiber paper on the carbon fiber paper, repeating the operation, and continuously scraping the carbon fiber paper, namely placing the bonding slurry obtained in the step (1) in a rectangular area corresponding to the carbon fiber paper, adjusting the thickness of a scraper to be 0.5mm, scraping the carbon fiber paper from left to right, and cleaning the redundant bonding slurry outside the rectangular area; and finally covering the carbon felt, applying external pressure of 1N, and drying in a vacuum drying oven at 120 ℃ for 12 hours to obtain the semi-finished electrode.
(3) Repeating the step (2), and coating and bonding the back surface of the semi-finished electrode to obtain the finished integrated electrode.
The structural schematic diagram of the finished integrated electrode obtained by the preparation method provided by the embodiment of the invention is shown in fig. 1.
Resistance test:
(1) Loading the carbon felt and the polar plate before compounding into a test fixture, externally applying 2000N pressure, opening a loop resistance meter, and setting the current to be 100A for testing;
(2) And loading the compounded integrated electrode into a test fixture, externally applying 2000N pressure, opening a loop resistance meter, and setting the current to be 100A for testing.
Referring to fig. 2, the test results are shown in fig. 2, which is a graph showing the change of contact resistance before and after the combination of the integrated electrode prepared in example 1, wherein the numbers 1 to 5 are five identical samples in example 1, the carbon felt+bipolar plate which is not bonded is before the combination, and the carbon felt+bipolar plate (integrated electrode) which is bonded is after the combination; from the graph, it can be seen that the contact resistance after recombination was reduced by about 30%.
FIG. 3 is a plot of integrated electrode resistance versus bond line carbon content; as can be seen, as the carbon content (the total amount of SP and CNT in the coating layer formed by the binder slurry is 30% of the total amount of SP, CNT and PVDF, for example, 30% in example 1 and 40% in example 2), the other data in fig. 3 is the data obtained by maintaining 0.06g of CNT and adjusting SP and PVDF on the basis of example 1) is decreasing, the resistance is reduced to the lowest point when the carbon content reaches 30%, so that 30% is the optimum carbon content of the present formulation.
Flow test:
Before compounding: assembling a carbon felt and a bipolar plate into 2 small galvanic piles, connecting the small galvanic piles into a test bench, respectively setting the pump pressure to 20-50 kpa, operating the pump for 3min, and storing and measuring the electrolyte flowing through the galvanic piles;
after compounding: and (3) assembling the integrated electrode into 2 small stacks, connecting the stacks into a test bench, setting the pump pressure to 20-50 kpa respectively, operating the pump for 3min, and storing and measuring the electrolyte flowing through the stacks.
FIG. 4 is a graph showing the flow rate as a function of pressure before and after compounding in example 1; from the graph, the flow rate is obviously increased after the composition, and the integral electrode is proved to obviously reduce the flow resistance in the pile.
Fig. 5 shows the pile performance of example 1.
In summary, the invention has the following beneficial effects:
(1) The materials used in the invention are the raw materials used by the bipolar plate and the carbon felt, and the introduction of new materials is not involved, so that side reactions are not caused;
(2) The carbon felt bipolar plate has excellent bonding effect, and does not generate falling off after long-time circulation;
(3) Through verification, the invention can reduce the contact resistance of the bipolar plate and the carbon felt by 20% -30%;
(4) The preparation method of the comparative foundation such as mixing coating is wide in application range, simple in process flow, low in industrialization difficulty and capable of producing in a large scale;
(5) The manufacturing process of the invention has high safety coefficient, and does not involve dangerous operations such as hot pressing, electroplating and the like.
The previous description of the disclosed embodiments is provided to enable any person skilled in the art to make or use the present invention. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the invention. Thus, the present invention is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.
Claims (8)
1. The preparation method of the vanadium redox flow battery integrated electrode comprises the following steps:
a) Mixing carbon nano tube slurry, a binder and a conductive agent in a solvent to obtain a binding slurry; the mass ratio of the carbon nano tube slurry to the binder to the conductive agent is 1: (1.2-2): (0.5-1); the mixing process comprises the following steps:
Taking carbon nano tube slurry in a beaker, adding a solvent, and magnetically stirring for 20-40 min at 15-25 ℃ and 1000-3000 r/min; simultaneously, taking the binder and the conductive agent to be ground in a mortar for 20-40 min to obtain a mixture; then placing the mixture into the beaker, adding a solvent, and continuing to magnetically stir at the temperature of 15-25 ℃ and the speed of 1000-3000 r/min for 10-15 h to obtain bonding slurry;
b) Coating a first layer of the bonding slurry on one side of the bipolar plate, then covering carbon fiber paper, coating a second layer of the bonding slurry, then covering a carbon felt, and sequentially pressing and drying to obtain a semi-finished electrode;
c) And b) repeating the step b) on the other side of the bipolar plate of the semi-finished electrode to obtain the integrated electrode of the vanadium redox flow battery.
2. The method according to claim 1, wherein the carbon nanotube content of the carbon nanotube slurry in step a) is 1wt% to 10wt%.
3. The method according to claim 1, wherein the binder in step a) is selected from the group consisting of polyvinyl alcohol, polytetrafluoroethylene, carboxymethyl cellulose and polyvinylidene fluoride.
4. The method according to claim 1, wherein the conductive agent in step a) is selected from one or more of conductive carbon black, ketjen black, acetylene black, conductive graphite, carbon fiber and graphene.
5. The method according to claim 1, wherein the step b) of applying the first layer of the bonding paste to the bipolar plate comprises:
Cutting the bipolar plate into a size of (22-30) cm x (15-25) cm, horizontally placing the bipolar plate on a glass plate, and cleaning the surface of the bipolar plate with alcohol; drawing a rectangular area with the length of (17-21) cm multiplied by (9-14) cm on the center of the pen; and then placing the first layer of the bonding slurry in a rectangular area, adjusting the thickness of a scraper to be 0.1-1 mm, and carrying out scraping coating from left to right.
6. The method of claim 1, wherein the pressing pressure in step b) is 0.5N to 5N.
7. The process according to claim 1, wherein the drying in step b) is carried out at a temperature of 100 ℃ to 150 ℃ for a time of 10h to 15h.
8. The vanadium redox flow battery integrated electrode is characterized by being prepared by adopting the preparation method of any one of claims 1-7.
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