CN111092231B - Vanadium battery integrated electrode prepared from high-molecular resin emulsion - Google Patents
Vanadium battery integrated electrode prepared from high-molecular resin emulsion Download PDFInfo
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- CN111092231B CN111092231B CN202010213874.0A CN202010213874A CN111092231B CN 111092231 B CN111092231 B CN 111092231B CN 202010213874 A CN202010213874 A CN 202010213874A CN 111092231 B CN111092231 B CN 111092231B
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- 239000000839 emulsion Substances 0.000 title claims abstract description 60
- 229910052720 vanadium Inorganic materials 0.000 title claims abstract description 23
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 title claims abstract description 23
- 229920005989 resin Polymers 0.000 title claims abstract description 15
- 239000011347 resin Substances 0.000 title claims abstract description 15
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 114
- 229910002804 graphite Inorganic materials 0.000 claims abstract description 101
- 239000010439 graphite Substances 0.000 claims abstract description 101
- 239000011159 matrix material Substances 0.000 claims abstract description 74
- 239000002952 polymeric resin Substances 0.000 claims abstract description 33
- 229920003002 synthetic resin Polymers 0.000 claims abstract description 33
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- 239000006258 conductive agent Substances 0.000 claims abstract description 12
- 238000000465 moulding Methods 0.000 claims abstract description 7
- 238000002360 preparation method Methods 0.000 claims abstract description 7
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 16
- 238000005507 spraying Methods 0.000 claims description 13
- -1 polytetrafluoroethylene Polymers 0.000 claims description 12
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 11
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 11
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 11
- 239000002033 PVDF binder Substances 0.000 claims description 10
- 239000003795 chemical substances by application Substances 0.000 claims description 10
- 238000001816 cooling Methods 0.000 claims description 10
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- 229910021389 graphene Inorganic materials 0.000 claims description 9
- 238000000034 method Methods 0.000 claims description 9
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 8
- 239000008367 deionised water Substances 0.000 claims description 8
- 229910021641 deionized water Inorganic materials 0.000 claims description 8
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- 239000006185 dispersion Substances 0.000 claims description 7
- 229920002313 fluoropolymer Polymers 0.000 claims description 7
- 239000004094 surface-active agent Substances 0.000 claims description 7
- 238000002156 mixing Methods 0.000 claims description 6
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 6
- 229920000642 polymer Polymers 0.000 claims description 6
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 claims description 5
- DDXLVDQZPFLQMZ-UHFFFAOYSA-M dodecyl(trimethyl)azanium;chloride Chemical compound [Cl-].CCCCCCCCCCCC[N+](C)(C)C DDXLVDQZPFLQMZ-UHFFFAOYSA-M 0.000 claims description 5
- 235000019387 fatty acid methyl ester Nutrition 0.000 claims description 5
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 claims description 5
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 claims description 4
- 239000004925 Acrylic resin Substances 0.000 claims description 4
- 229920000178 Acrylic resin Polymers 0.000 claims description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 4
- 239000002041 carbon nanotube Substances 0.000 claims description 4
- 229910021393 carbon nanotube Inorganic materials 0.000 claims description 4
- 239000007822 coupling agent Substances 0.000 claims description 4
- 229920001568 phenolic resin Polymers 0.000 claims description 4
- 239000012745 toughening agent Substances 0.000 claims description 4
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- 238000010438 heat treatment Methods 0.000 abstract description 6
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- 230000004913 activation Effects 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
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- 125000000524 functional group Chemical group 0.000 description 3
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- RKISUIUJZGSLEV-UHFFFAOYSA-N n-[2-(octadecanoylamino)ethyl]octadecanamide Chemical compound CCCCCCCCCCCCCCCCCC(=O)NCCNC(=O)CCCCCCCCCCCCCCCCC RKISUIUJZGSLEV-UHFFFAOYSA-N 0.000 description 2
- 229920009441 perflouroethylene propylene Polymers 0.000 description 2
- 230000002035 prolonged effect Effects 0.000 description 2
- 229920002943 EPDM rubber Polymers 0.000 description 1
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- HQQADJVZYDDRJT-UHFFFAOYSA-N ethene;prop-1-ene Chemical group C=C.CC=C HQQADJVZYDDRJT-UHFFFAOYSA-N 0.000 description 1
- 125000001153 fluoro group Chemical group F* 0.000 description 1
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Images
Classifications
-
- 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
- H01M4/8825—Methods for deposition of the catalytic active composition
- H01M4/8864—Extrusion
-
- 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
-
- 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
- H01M8/0204—Non-porous and characterised by the material
- H01M8/0221—Organic resins; Organic polymers
-
- 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
-
- 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 provides a vanadium battery integrated electrode prepared from polymer resin emulsion, which is characterized in that polymer resin emulsion is filled with a conductive agent to prepare a conductive matrix, the conductive matrix is prepared from 40-60 wt% of polymer resin emulsion, 40-60 wt% of the conductive agent and 0-10 wt% of an auxiliary agent, wherein the content of polymer resin in the polymer resin emulsion is 30-60%, the surface of a graphite felt is subjected to acid treatment or heat treatment and is sprayed with the polymer resin emulsion, then one surface of the graphite felt sprayed is tightly attached to the conductive matrix, the conductive matrix is solidified by heating and pressurizing in a mold and is tightly adhered to the graphite felt, and the integrated electrode is prepared. The emulsion-state high-molecular resin is used as a raw material to prepare the conductive matrix, and the conductive matrix is easy to operate, mix and carry out hot press molding when being filled with a conductive agent and an auxiliary agent; the high molecular resin emulsion can be a semi-finished product in the preparation of high molecular resin, can be directly purchased in the market, and is used for preparing the conductive substrate, so that the production cost is favorably reduced.
Description
Technical Field
The invention relates to the field of vanadium battery manufacturing, in particular to a vanadium battery integrated electrode prepared from high-molecular resin emulsion.
Technical Field
The vanadium battery is a novel environment-friendly energy storage battery, the material of the conductive matrix and the electrode material are important components, the conductive matrix mainly plays a role in isolating positive and negative electrolytes and conducting and collecting current in the battery, and simultaneously provides mechanical support for the electrode. The electrode material is mainly graphite felt, and the conductive substrate and the electrode are more prone to be compounded technically to prepare the integrated electrode due to the fact that the conductive substrate and the electrode have larger contact resistance. At present, an integrated electrode is mostly prepared by thermally adhering a conductive plastic conductive matrix and a graphite felt, the conductive matrix takes polyethylene, polypropylene, epoxy resin, phenolic resin and other materials as the matrix, and is added with conductive agents such as graphite, carbon black and the like, and the conductive matrix is processed by processing equipment such as an extruder, an open mill, an internal mixer and the like, so that the processing method is complex, and the resistance of the conductive matrix and the contact resistance between the conductive matrix and the electrode are large.
Disclosure of Invention
In order to solve the technical problems, the vanadium battery integrated electrode prepared from the high polymer resin emulsion is provided, so that the processing difficulty is reduced, and the quality of a conductive matrix and the finished product of the integrated electrode is improved.
A vanadium battery integrated electrode prepared from high polymer resin emulsion comprises a graphite felt and a conductive substrate, wherein the conductive substrate is prepared from 40-60 wt% of high polymer resin emulsion, 40-60 wt% of conductive agent and 0-10 wt% of auxiliary agent, the content of high polymer resin in the high polymer resin emulsion is 30-60 wt%, and the preparation method of the vanadium battery integrated electrode comprises the following steps:
uniformly mixing all components of the conductive matrix, and prepressing the conductive matrix into a sheet shape on a tabletting machine;
after the graphite felt is treated by concentrated sulfuric acid, deionized water is cleaned or heat treated;
uniformly spraying high-molecular resin emulsion on the surface of one side of the graphite felt;
and placing the graphite felt in a mold, tightly attaching the conductive substrate to the spraying side of the graphite felt, carrying out hot press molding on the graphite felt and the conductive substrate, and cooling to room temperature.
Preferably, the polymer resin emulsion comprises a dispersion emulsion of a water-based epoxy resin, a water-based acrylic resin, a water-based phenolic resin or a fluoroplastic.
Preferably, the fluoroplastic comprises polytetrafluoroethylene, polyvinylidene fluoride, polyfluoroethylpropylene, or meltable polytetrafluoroethylene.
Preferably, the conductive agent includes one or a mixture of graphite, conductive carbon black, graphene, carbon nanotubes, silver powder and copper powder.
Preferably, the auxiliary agent comprises a surfactant, and the surfactant comprises sodium dodecyl benzene sulfonate, dodecyl trimethyl ammonium chloride or α -sulfo fatty acid methyl ester.
Preferably, the auxiliary agent further comprises one or a mixture of a curing agent, a toughening agent, a compatilizer and a coupling agent.
Preferably, the method for treating the surface of the graphite felt by concentrated sulfuric acid comprises the following steps: and (3) treating the graphite felt in 98% concentrated sulfuric acid for 3-10 hours.
Preferably, the method for heat treatment of the graphite felt comprises the following steps: and (3) preserving the heat of the graphite felt for 10-40 hours in a nitrogen atmosphere at the temperature of 300-600 ℃.
Preferably, the polymer emulsion sprayed on the graphite felt is the same as the polymer resin contained in the polymer emulsion of the conductive substrate.
Preferably, two sides of the conductive substrate are respectively adhered with a graphite felt.
Compared with the prior art, the invention has the beneficial effects that: 1. the emulsion-state high-molecular resin is used as a raw material to prepare the conductive matrix, and the conductive matrix is easy to operate, mix and carry out hot press molding when being filled with a conductive agent and an auxiliary agent; 2. the high molecular resin emulsion can be a semi-finished product in the preparation of high molecular resin, can be directly purchased in the market, and is used for preparing the conductive substrate, so that the production cost is favorably reduced; 3. the graphite felt is treated by concentrated sulfuric acid to increase the number of oxygen-containing functional groups on the surface of the graphite felt so as to catalyze electrochemical reaction, so that the performance of the electrode is improved, and the heat treatment of the graphite felt is beneficial to improving the surface activation position and increasing the effective specific surface area; 4. the surface of one side of the graphite felt is uniformly sprayed with the high polymer resin emulsion to improve the compatibility of the graphite felt and the conductive matrix; 5. the conductive matrix prepared from the polymer resin dispersion emulsion is cured and formed in one step to prepare the integrated electrode, so that the process flow is simplified, the corrosion resistance of the conductive matrix is improved, and the service life of the conductive matrix is prolonged.
Drawings
FIG. 1 is a process flow diagram of the present invention.
DETAILED DESCRIPTION OF EMBODIMENT (S) OF INVENTION
The following detailed description of embodiments of the present invention is provided in connection with the accompanying drawings and examples. The following examples are intended to illustrate the invention but are not intended to limit the scope of the invention.
A vanadium battery integrated electrode prepared from a high polymer resin emulsion comprises a graphite felt and a conductive matrix, wherein the conductive matrix is prepared from 40-60% of the high polymer resin emulsion, 40-60% of a conductive agent and 0-10% of an auxiliary agent in percentage by mass, the content of high polymer resin in the high polymer resin emulsion is 30-60 wt%, as shown in figure 1, and the preparation method of the vanadium battery integrated electrode comprises the following steps:
step 101: after all the components of the conductive matrix are uniformly mixed, a certain amount of mixture is taken and pre-pressed into a sheet shape on a tablet press.
Step 201: and (3) after the graphite felt is treated by concentrated sulfuric acid, washing the graphite felt by deionized water or performing heat treatment. The graphite felt is treated by concentrated sulfuric acid to increase the number of oxygen-containing functional groups on the surface of the graphite felt so as to catalyze electrochemical reaction, thereby improving the performance of the electrode; the heat treatment of the graphite felt is beneficial to improving the surface activation position of the graphite felt and increasing the effective specific surface area.
Step 202: and uniformly spraying high-molecular resin emulsion on the surface of one side of the graphite felt. The surface of one side of the graphite felt is uniformly sprayed with the polymer resin emulsion to improve the compatibility of the graphite felt and the conductive matrix.
Step 203: and placing the graphite felt in a mold, tightly attaching the conductive matrix to the spraying side of the graphite felt, carrying out hot-press forming on the graphite felt and the conductive matrix in a tablet press, and cooling to room temperature.
The emulsion-state high-molecular resin is used as a raw material to prepare the conductive matrix, and the conductive matrix is easy to operate, mix and carry out hot press molding when being filled with a conductive agent and an auxiliary agent; the high molecular resin emulsion can be a semi-finished product in the preparation of high molecular resin, can be directly purchased in the market, and is used for preparing the conductive substrate, so that the production cost is favorably reduced; the polymer resin dispersion emulsion is used as a matrix to prepare the integrated electrode through one-step curing molding, so that the process flow is simplified, the corrosion resistance of the conductive matrix is improved, and the service life of the conductive matrix is prolonged.
The polymer resin emulsion comprises a dispersion emulsion of waterborne epoxy resin, waterborne acrylic resin, waterborne phenolic resin or fluoroplastic and the like, can be a semi-finished product in polymer resin preparation, can be directly purchased in the market, and is used for preparing a conductive substrate, so that the production cost is favorably reduced.
Wherein the fluoroplastic may include Polytetrafluoroethylene (PTFE), polyvinylidene fluoride (PVDF), Fluorinated Ethylene Propylene (FEP), or meltable Polytetrafluoroethylene (PFA). The fluoroplastic has a molecular structure containing fluorine atoms, has a plurality of excellent properties such as excellent electrical insulation property, heat resistance, oil resistance, solvent resistance and wear resistance, and is widely applied to national defense, electromechanics, metallurgy, petrochemical industry and the like.
The conductive agent can comprise one of graphite, conductive carbon black, graphene, carbon nanotubes, silver powder, copper powder and the like or a mixture of the graphite, the conductive carbon black, the graphene, the carbon nanotubes, the silver powder and the copper powder, and the like, and is used for improving the conductivity of the conductive matrix.
The auxiliary agent can comprise a surfactant, wherein the surfactant comprises sodium dodecyl benzene sulfonate, dodecyl trimethyl ammonium chloride or α -sulfo fatty acid methyl ester and the like, and the surfactant is used for improving the surface tension among various constituent phases in the emulsion to form a uniform and stable dispersion system or emulsion so as to play a role in emulsification or dispersion.
The auxiliary agent can also comprise one or a mixture of a curing agent, a toughening agent, a compatilizer, a coupling agent, an antioxidant and the like. Wherein, the curing agent can adopt modified polyamide, phenolic aldehyde amine (T-31) epoxy resin curing agent, 593 curing agent or 810 curing agent, and the toughening agent can adopt EVA, POE or EPDM; the compatilizer can adopt PP-g-MAH, PE-g-MAH or POE-g-MAH; the coupling agent can be KH-550 or KH-570; the antioxidant can adopt 168, 1010, 1098 or 1076; the dispersant may be Ethylene Bis Stearamide (EBS) or silicone powder.
The polymer emulsion sprayed on the graphite felt is the same as the polymer resin contained in the polymer emulsion of the conductive substrate. The same kind of high-molecular emulsion improves the interface binding force, compatibility and adhesion of the graphite felt and the conductive substrate.
In specific implementation, two graphite felts are respectively adhered to two sides of the conductive substrate.
Example 1
Preparing a conductive matrix: taking 150g of water-based epoxy resin emulsion with the solid content of 60%, 90g of modified polyamide, 200g of conductive carbon black and 10g of graphene, placing the mixture in an internal mixer at room temperature for mixing for 15min, taking out the mixture, weighing 100g of the mixture, placing the mixture in a mold, and uniformly coating the surface of a conductive substrate by using tools such as a scraper and the like. The modified polyamide is used as a curing agent and also used as a polymer resin to participate in the structure of the conductive matrix, and in specific implementation, the modified polyamide is calculated as the polymer resin.
Treating a graphite felt: treating the graphite felt in 98% concentrated sulfuric acid for 3-10h, taking out, cleaning with deionized water, drying in the air, spraying or soaking the aqueous epoxy resin emulsion on the side to be bonded, and drying in the air.
Bonding: placing the graphite felt in a fixed position in a mould, placing on a tablet press, contacting the treated side of the graphite felt with the conductive matrix, adjusting the temperature to 50-80 ℃, applying pressure to tightly bond the graphite felt and the conductive matrix, and cooling to room temperature after the conductive matrix is solidified.
Example 2
Preparing a conductive matrix: 200g of PTFE emulsion with the solid content of 50%, 200g of graphite, 10g of graphene and 20g of sodium dodecyl benzene sulfonate are taken and placed in an internal mixer to be mixed for 20min at room temperature, 100g of the mixture is taken out and then placed in a mold, and tools such as a scraper are used for uniformly coating the surface of the conductive substrate.
Treating a graphite felt: treating the graphite felt in 98% concentrated sulfuric acid for 3-10h, taking out, cleaning with deionized water, drying in the air, spraying or soaking PTFE emulsion on the side to be bonded, and drying in the air.
Bonding: and placing the graphite felt at a fixed position in a mould, placing the graphite felt on a tablet press, enabling the treated side of the graphite felt to be in contact with the conductive matrix, adjusting the temperature to be 350-380 ℃, applying pressure to enable the graphite felt and the conductive matrix to be tightly bonded, and cooling the conductive matrix to room temperature after the conductive matrix is solidified.
Example 3
Preparing a conductive matrix: 250g of PVDF emulsion with solid content of 48%, 200g of conductive carbon black, 50g of silver powder and 20g of dodecyl trimethyl ammonium chloride are taken and placed in an internal mixer to be mixed for 20min at room temperature, 100g of the PVDF emulsion, the conductive carbon black and the silver powder are taken out and weighed and placed in a mold, and tools such as a scraper are used for uniformly coating the surface of a conductive substrate.
Treating a graphite felt: and (3) insulating the graphite felt for 10-40h in the nitrogen atmosphere at the temperature of 300-600 ℃, spraying or dipping PVDF emulsion on the side to be bonded, and airing.
Bonding: and placing the graphite felt at a fixed position in a mould, placing the graphite felt on a tablet press, enabling the treated side of the graphite felt to be in contact with the conductive matrix, adjusting the temperature to be 150-200 ℃, applying pressure to enable the graphite felt and the conductive matrix to be tightly bonded, and cooling the conductive matrix to room temperature after the conductive matrix is solidified.
Example 4
Preparing a conductive substrate, namely taking 250g of PFA emulsion with the solid content of 52%, 200g of conductive carbon black, 100g of silver powder and 20g of α -sulfo fatty acid methyl ester, placing the PFA emulsion, the conductive carbon black, the silver powder and the α -sulfo fatty acid methyl ester in an internal mixer, mixing for 20min at room temperature, taking out, weighing 100g, placing in a mold, and uniformly coating the surface of the conductive substrate by using tools such as a scraper and the like.
Treating a graphite felt: and (3) insulating the graphite felt for 10-40h in the nitrogen atmosphere at the temperature of 300-600 ℃, spraying or dipping PFA emulsion on the side to be bonded, and airing.
Bonding: and placing the graphite felt at a fixed position in a mould, placing the graphite felt on a tablet press, enabling the treated side of the graphite felt to be in contact with the conductive matrix, adjusting the temperature to 350-400 ℃, applying pressure to enable the graphite felt and the conductive matrix to be tightly bonded, and cooling the conductive matrix to room temperature after the conductive matrix is solidified.
Example 5
Preparing a conductive matrix: taking 120g of water-based acrylic resin emulsion with the solid content of 55%, 50g of T-31 curing agent, 230g of conductive carbon black and 20g of graphene, placing the mixture in an internal mixer at room temperature for mixing for 15min, taking out the mixture, weighing 100g of the mixture, placing the mixture in a mold, and uniformly coating the surface of a conductive substrate by using tools such as a scraper. Wherein T31 is used as a curing agent and is used as a polymer resin to participate in the structure of the conductive matrix.
Treating a graphite felt: treating the graphite felt in 98% concentrated sulfuric acid for 3-10h, taking out, cleaning with deionized water, drying in the air, spraying or soaking the aqueous epoxy resin emulsion on the side to be bonded, and drying in the air.
Bonding: placing the graphite felt in a fixed position in a mould, placing on a tablet press, contacting the treated side of the graphite felt with the conductive matrix, adjusting the temperature to 50-80 ℃, applying pressure to tightly bond the graphite felt and the conductive matrix, and cooling to room temperature after the conductive matrix is solidified.
Example 6
Preparing a conductive matrix: taking 260g of PTFE emulsion with 50% of solid content, 200g of graphite, 10g of graphene and 50g of sodium dodecyl benzene sulfonate, placing the mixture in an internal mixer at room temperature, mixing for 20min, taking out, weighing 100g, placing the mixture in a mold, and uniformly coating the surface of the conductive substrate by using tools such as a scraper and the like.
Treating a graphite felt: treating the graphite felt in 98% concentrated sulfuric acid for 3-10h, taking out, cleaning with deionized water, drying in the air, spraying or soaking PTFE emulsion on the side to be bonded, and drying in the air.
Bonding: and placing the graphite felt at a fixed position in a mould, placing the graphite felt on a tablet press, enabling the treated side of the graphite felt to be in contact with the conductive matrix, adjusting the temperature to be 350-380 ℃, applying pressure to enable the graphite felt and the conductive matrix to be tightly bonded, and cooling the conductive matrix to room temperature after the conductive matrix is solidified.
Example 7
Preparing a conductive matrix: 290g of PVDF emulsion with the solid content of 45%, 190g of conductive carbon black, 10g of graphene and 5g of dodecyl trimethyl ammonium chloride are taken and placed in an internal mixer to be mixed for 20min at room temperature, 100g of the PVDF emulsion is taken out and then is placed in a mold, and tools such as a scraper are used for uniformly coating the surface of a conductive substrate.
Treating a graphite felt: and (3) insulating the graphite felt for 10-40h in the nitrogen atmosphere at the temperature of 300-600 ℃, spraying or dipping PVDF emulsion on the side to be bonded, and airing.
Bonding: and placing the graphite felt at a fixed position in a mould, placing the graphite felt on a tablet press, enabling the treated side of the graphite felt to be in contact with the conductive matrix, adjusting the temperature to be 150-200 ℃, applying pressure to enable the graphite felt and the conductive matrix to be tightly bonded, and cooling the conductive matrix to room temperature after the conductive matrix is solidified.
The vanadium battery integrated electrode prepared in the embodiment 1-7 is assembled into a battery for charge and discharge tests, and the charge and discharge current is 60mA/cm2The test results are shown in the following table.
| Coulomb efficiency% | Voltage efficiency% | Energy efficiency% | |
| Example 1 | 94.0 | 85.6 | 80.5 |
| Example 2 | 94.5 | 86.2 | 81.5 |
| Example 3 | 95.2 | 86.2 | 82.1 |
| Example 4 | 95.7 | 87.3 | 83.5 |
| Example 5 | 96.4 | 87.4 | 84.3 |
| Example 6 | 93.2 | 83.0 | 77.4 |
| Example 7 | 94.0 | 85.7 | 80.6 |
The above description is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, several modifications and variations can be made without departing from the technical principle of the present invention, and these modifications and variations should also be regarded as the protection scope of the present invention.
Claims (10)
1. The vanadium battery integrated electrode prepared from high polymer resin emulsion is characterized by comprising a graphite felt and a conductive matrix, wherein the conductive matrix is prepared from 40-60 wt% of high polymer resin emulsion, 40-60 wt% of conductive agent and 0-10 wt% of auxiliary agent, the content of high polymer resin in the high polymer resin emulsion is 30-60 wt%, and the preparation method of the vanadium battery integrated electrode comprises the following steps:
uniformly mixing all components of the conductive matrix, and prepressing the conductive matrix into a sheet shape on a tabletting machine;
after the graphite felt is treated by concentrated sulfuric acid, deionized water is cleaned or heat treated;
uniformly spraying high-molecular resin emulsion on the surface of one side of the graphite felt;
placing a graphite felt in a mold, tightly attaching a conductive substrate to the spraying side of the graphite felt, carrying out hot press molding on the graphite felt and the conductive substrate, cooling to room temperature, and carrying out one-step curing molding on the integrated electrode as the conductive substrate.
2. The vanadium battery integrated electrode according to claim 1, wherein the polymer resin emulsion comprises a dispersion emulsion of a water-based epoxy resin, a water-based acrylic resin, a water-based phenolic resin or a fluoroplastic.
3. The vanadium battery integrated electrode according to claim 2, wherein the fluoroplastic comprises polytetrafluoroethylene, polyvinylidene fluoride, polyfluoroethylene propylene, or meltable polytetrafluoroethylene.
4. The vanadium battery integrated electrode according to claim 1, wherein the conductive agent comprises one of graphite, conductive carbon black, graphene, carbon nanotubes, silver powder and copper powder or a mixture thereof.
5. The vanadium battery integrated electrode according to claim 1, wherein the auxiliary agent comprises a surfactant, and the surfactant comprises sodium dodecyl benzene sulfonate, dodecyl trimethyl ammonium chloride or α -sulfo fatty acid methyl ester.
6. The vanadium battery integrated electrode according to claim 1 or 5, wherein the auxiliary agent comprises one of a curing agent, a toughening agent, a compatilizer and a coupling agent or a mixture thereof.
7. The vanadium battery integrated electrode according to claim 1, wherein the method for treating the surface of the graphite felt with concentrated sulfuric acid comprises the following steps:
and (3) treating the graphite felt in 98% concentrated sulfuric acid for 3-10 hours.
8. The vanadium battery integrated electrode according to claim 1, wherein the method for heat-treating the graphite felt comprises:
and (3) preserving the heat of the graphite felt for 10-40 hours in a nitrogen atmosphere at the temperature of 300-600 ℃.
9. The vanadium battery integrated electrode according to claim 1, wherein the polymer emulsion sprayed on the graphite felt is the same as the polymer resin contained in the polymer emulsion of the conductive matrix.
10. The vanadium battery integrated electrode according to claim 1, wherein a graphite felt is adhered to each of two sides of the conductive substrate.
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| CN114156493A (en) * | 2021-12-07 | 2022-03-08 | 上海电气(安徽)储能科技有限公司 | Pretreatment method of carbon felt electrode for all-vanadium redox flow battery |
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| CN102623718A (en) * | 2012-04-16 | 2012-08-01 | 四川省达州钢铁集团有限责任公司 | Method for preparing current collectors for all vanadium flow batteries |
| KR20180036389A (en) * | 2016-09-30 | 2018-04-09 | 롯데케미칼 주식회사 | Preparation method of bipolar plate for vanadium redox flow battery |
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