CN116505002B - Graphite felt electrode for all-vanadium redox flow battery, and activation method and application thereof - Google Patents
Graphite felt electrode for all-vanadium redox flow battery, and activation method and application thereof Download PDFInfo
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- CN116505002B CN116505002B CN202310781324.2A CN202310781324A CN116505002B CN 116505002 B CN116505002 B CN 116505002B CN 202310781324 A CN202310781324 A CN 202310781324A CN 116505002 B CN116505002 B CN 116505002B
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 153
- 229910002804 graphite Inorganic materials 0.000 title claims abstract description 145
- 239000010439 graphite Substances 0.000 title claims abstract description 145
- 229910052720 vanadium Inorganic materials 0.000 title claims abstract description 42
- 238000000034 method Methods 0.000 title claims abstract description 35
- 230000004913 activation Effects 0.000 title claims abstract description 26
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 claims abstract description 41
- 239000000243 solution Substances 0.000 claims abstract description 41
- 238000010438 heat treatment Methods 0.000 claims abstract description 37
- 239000007789 gas Substances 0.000 claims abstract description 32
- 239000002243 precursor Substances 0.000 claims abstract description 29
- 239000011259 mixed solution Substances 0.000 claims abstract description 28
- 150000001875 compounds Chemical class 0.000 claims abstract description 26
- 238000001035 drying Methods 0.000 claims abstract description 25
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims abstract description 14
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000011261 inert gas Substances 0.000 claims abstract description 13
- 238000002156 mixing Methods 0.000 claims abstract description 13
- 229910052750 molybdenum Inorganic materials 0.000 claims abstract description 13
- 239000011733 molybdenum Substances 0.000 claims abstract description 13
- 229910052721 tungsten Inorganic materials 0.000 claims abstract description 13
- 239000010937 tungsten Substances 0.000 claims abstract description 13
- 239000002608 ionic liquid Substances 0.000 claims abstract description 12
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 30
- 238000009792 diffusion process Methods 0.000 claims description 16
- -1 imidazole ions Chemical class 0.000 claims description 13
- 238000004140 cleaning Methods 0.000 claims description 12
- 239000003792 electrolyte Substances 0.000 claims description 12
- KPGXUAIFQMJJFB-UHFFFAOYSA-H tungsten hexachloride Chemical compound Cl[W](Cl)(Cl)(Cl)(Cl)Cl KPGXUAIFQMJJFB-UHFFFAOYSA-H 0.000 claims description 8
- 230000003213 activating effect Effects 0.000 claims description 7
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical group CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- 238000005868 electrolysis reaction Methods 0.000 claims description 5
- 230000002209 hydrophobic effect Effects 0.000 claims description 5
- BQBYSLAFGRVJME-UHFFFAOYSA-L molybdenum(2+);dichloride Chemical compound Cl[Mo]Cl BQBYSLAFGRVJME-UHFFFAOYSA-L 0.000 claims description 4
- YOUIDGQAIILFBW-UHFFFAOYSA-J Tungsten(IV) chloride Inorganic materials Cl[W](Cl)(Cl)Cl YOUIDGQAIILFBW-UHFFFAOYSA-J 0.000 claims description 3
- UDJQAOMQLIIJIE-UHFFFAOYSA-L dichlorotungsten Chemical compound Cl[W]Cl UDJQAOMQLIIJIE-UHFFFAOYSA-L 0.000 claims description 3
- 239000007788 liquid Substances 0.000 claims description 3
- GICWIDZXWJGTCI-UHFFFAOYSA-I molybdenum pentachloride Chemical compound Cl[Mo](Cl)(Cl)(Cl)Cl GICWIDZXWJGTCI-UHFFFAOYSA-I 0.000 claims description 3
- ZSSVQAGPXAAOPV-UHFFFAOYSA-K molybdenum trichloride Chemical compound Cl[Mo](Cl)Cl ZSSVQAGPXAAOPV-UHFFFAOYSA-K 0.000 claims description 3
- BGRYSGVIVVUJHH-UHFFFAOYSA-N prop-2-ynyl propanoate Chemical compound CCC(=O)OCC#C BGRYSGVIVVUJHH-UHFFFAOYSA-N 0.000 claims description 3
- 239000002904 solvent Substances 0.000 claims description 3
- WIDQNNDDTXUPAN-UHFFFAOYSA-I tungsten(v) chloride Chemical compound Cl[W](Cl)(Cl)(Cl)Cl WIDQNNDDTXUPAN-UHFFFAOYSA-I 0.000 claims description 3
- 238000004321 preservation Methods 0.000 claims description 2
- 230000000630 rising effect Effects 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 10
- 238000001994 activation Methods 0.000 description 21
- UONOETXJSWQNOL-UHFFFAOYSA-N tungsten carbide Chemical compound [W+]#[C-] UONOETXJSWQNOL-UHFFFAOYSA-N 0.000 description 17
- 229920000049 Carbon (fiber) Polymers 0.000 description 16
- 239000004917 carbon fiber Substances 0.000 description 15
- 230000000052 comparative effect Effects 0.000 description 12
- 239000002245 particle Substances 0.000 description 11
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 10
- 239000001301 oxygen Substances 0.000 description 10
- 229910052760 oxygen Inorganic materials 0.000 description 10
- 238000012360 testing method Methods 0.000 description 10
- 150000003681 vanadium Chemical class 0.000 description 10
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 8
- CNEOGBIICRAWOH-UHFFFAOYSA-N methane;molybdenum Chemical compound C.[Mo] CNEOGBIICRAWOH-UHFFFAOYSA-N 0.000 description 8
- 230000003647 oxidation Effects 0.000 description 8
- 238000007254 oxidation reaction Methods 0.000 description 8
- 125000000524 functional group Chemical group 0.000 description 7
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 7
- 238000006243 chemical reaction Methods 0.000 description 6
- 238000012986 modification Methods 0.000 description 6
- 230000004048 modification Effects 0.000 description 5
- 238000002360 preparation method Methods 0.000 description 5
- 229910052799 carbon Inorganic materials 0.000 description 4
- 230000003197 catalytic effect Effects 0.000 description 4
- 238000005530 etching Methods 0.000 description 4
- 239000000835 fiber Substances 0.000 description 4
- 229920002554 vinyl polymer Polymers 0.000 description 4
- IQQRAVYLUAZUGX-UHFFFAOYSA-N 1-butyl-3-methylimidazolium Chemical compound CCCCN1C=C[N+](C)=C1 IQQRAVYLUAZUGX-UHFFFAOYSA-N 0.000 description 3
- 230000002776 aggregation Effects 0.000 description 3
- 239000000460 chlorine Substances 0.000 description 3
- 238000006056 electrooxidation reaction Methods 0.000 description 3
- 150000003254 radicals Chemical class 0.000 description 3
- QIJNJJZPYXGIQM-UHFFFAOYSA-N 1lambda4,2lambda4-dimolybdacyclopropa-1,2,3-triene Chemical compound [Mo]=C=[Mo] QIJNJJZPYXGIQM-UHFFFAOYSA-N 0.000 description 2
- 229910039444 MoC Inorganic materials 0.000 description 2
- 239000011149 active material Substances 0.000 description 2
- 238000005054 agglomeration Methods 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 238000003763 carbonization Methods 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 230000002349 favourable effect Effects 0.000 description 2
- 238000011065 in-situ storage Methods 0.000 description 2
- 238000002203 pretreatment Methods 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 241000519995 Stachys sylvatica Species 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 238000004873 anchoring Methods 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 238000005255 carburizing Methods 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 239000008151 electrolyte solution Substances 0.000 description 1
- 229940021013 electrolyte solution Drugs 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000011534 incubation Methods 0.000 description 1
- 239000011810 insulating material Substances 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000003642 reactive oxygen metabolite Substances 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D11/00—Electrolytic coating by surface reaction, i.e. forming conversion layers
- C25D11/02—Anodisation
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D11/00—Electrolytic coating by surface reaction, i.e. forming conversion layers
- C25D11/005—Apparatus specially adapted for electrolytic conversion coating
-
- 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
- H01M4/90—Selection of catalytic material
-
- 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
- H01M4/90—Selection of catalytic material
- H01M4/9075—Catalytic material supported on carriers, e.g. powder carriers
- H01M4/9083—Catalytic material supported on carriers, e.g. powder carriers on carbon or graphite
-
- 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
- H01M8/18—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 application discloses a graphite felt electrode for an all-vanadium redox flow battery, an activation method and application thereof, and at least comprises the following steps: mixing a solution containing a tungsten source or a molybdenum source with an imidazole ionic liquid to obtain a mixed solution; immersing the pretreated graphite felt electrode in the mixed solution, taking out and drying to obtain a compound precursor; introducing the compound precursor into CO 2 And heating and preserving the temperature of the gas, and then introducing inert gas to cool the gas to obtain the graphite felt electrode for the activated all-vanadium redox flow battery. The graphite felt electrode prepared by the application has high electrochemical activity.
Description
Technical Field
The application relates to the technical field of all-vanadium redox flow batteries, in particular to a graphite felt electrode for an all-vanadium redox flow battery, an activation method and application thereof.
Background
All-vanadium redox flow batteries (vanadium batteries for short) are one of the most widely used flow batteries, which achieve the interconversion of electric energy and chemical energy through reversible electrochemical redox reactions of active materials in electrolyte solutions of positive and negative electrodes. The all-vanadium redox flow battery pile mainly comprises end plates, guide plates, current collecting plates, bipolar plates, electrode frames, electrodes, diaphragms and the like. Among them, the electrode is one of the most important components in the vanadium battery, and provides reactive sites for the active materials, directly affecting the battery performance. The electrode materials commonly used at present are carbon-based materials such as Graphite Felt (GF). The graphite felt not only has excellent conductivity, but also has very large specific surface, so that the effective reaction area of the electrode is greatly increased. Graphite felt sold on the market is mainly used as a heat-insulating material, and if the graphite felt is directly used as a battery electrode, the hydrophilicity and the electrochemical activity of the graphite felt are poor. Although the electrocatalytic performance of the graphite felt electrode can be improved to a certain extent through post-modification such as high-temperature oxidation, electrochemical oxidation, strong acid oxidation, surface modification, doping modification and the like, the overall electrochemical activity still needs to be improved.
Therefore, we propose a graphite felt electrode for an all-vanadium redox flow battery, and an activation method and application thereof.
Disclosure of Invention
The application aims to provide a graphite felt electrode for an all-vanadium redox flow battery, an activation method and application thereof, and solves the problem of insufficient electrochemical activity of the graphite felt electrode in the prior art.
The technical scheme adopted by the application is as follows:
the activation method of the graphite felt electrode for the all-vanadium redox flow battery at least comprises the following steps:
mixing a solution containing a tungsten source or a molybdenum source with an imidazole ionic liquid to obtain a mixed solution;
immersing the pretreated graphite felt electrode in the mixed solution, taking out and drying to obtain a compound precursor;
introducing the compound precursor into CO 2 And heating and preserving the temperature of the gas, and then introducing inert gas to cool the gas to obtain the graphite felt electrode for the activated all-vanadium redox flow battery.
Preferably, the tungsten source is at least one selected from tungsten dichloride, tungsten tetrachloride, tungsten pentachloride and tungsten hexachloride;
the molybdenum source is at least one selected from molybdenum dichloride, molybdenum trichloride and molybdenum pentachloride.
Preferably, the solvent in the solution containing the tungsten source or the molybdenum source is ethanol;
the mass percentage of the tungsten source or the molybdenum source in the solution is 1-10%.
Preferably, the imidazole ionic liquid accounts for 1-10% of the mixed liquid by mass.
Preferably, the imidazole ion in the imidazole ion liquid is selected from hydrophobic imidazole ion salt;
the hydrophobic imidazole ion salt is at least one selected from 1, 3-dimethyl imidazole hexafluorophosphate, 1-ethyl-3-methyl hexafluorophosphate, 1-dodecyl-3-methyl hexafluorophosphate, 1-butyl-3-methyl hexafluorophosphate, 1-benzyl-3-methyl hexafluorophosphate, 1-allyl-3-methyl hexafluorophosphate, 1-vinyl-3-methyl hexafluorophosphate, 1-ethyl-3-vinyl hexafluorophosphate, 1-benzyl-3-vinyl hexafluorophosphate and 1-butyl-2, 3-dimethyl hexafluorophosphate.
Preferably, the pretreatment mode of the pretreated graphite felt electrode is as follows:
in an electrolytic tank without a diaphragm, an air diffusion electrode is adopted as a cathode, a graphite felt electrode is adopted as an anode, a dilute sulfuric acid solution is adopted as an electrolyte, direct current constant current electrolytic treatment is conducted, the electrolyzed graphite felt electrode is obtained, and the pretreated graphite felt electrode is finally obtained after cleaning and drying.
Preferably, the concentration of the dilute sulfuric acid is 0.5-4mol/L;
preferably, the concentration of the diluted sulfuric acid is any one or a range of values between 0.5mol/L, 1mol/L, 1.5mol/L, 2mol/L, 2.5mol/L, 3mol/L, 3.5mol/L, 4 mol/L.
The current density of the direct current constant current is 10-120mA/cm 2 The electrolysis time is 10-150min.
Preferably, the DC constant current has a current density of 10mA/cm 2 、20mA/cm 2 、40mA/cm 2 、60mA/cm 2 、80mA/cm 2 、100mA/cm 2 、120mA/cm 2 Or a range of values between two values.
Preferably, the time of electrolysis is any one of 10min, 30min, 60min, 90min, 120min, 140min, 150min or a range between the two values.
Preferably, CO is introduced 2 The flow rate of the gas is 10-150ml/min;
preferably, CO is introduced 2 The flow rate of the gas is any value or a range of values between any two values of 10ml/min, 30ml/min, 60ml/min, 90ml/min, 120ml/min, 140ml/min and 150 ml/min.
The heating rate is 5-15 ℃/min, and the heating temperature is 700-1000 ℃;
preferably, the rate of temperature rise is any value or a range of values between 5 ℃/min, 10 ℃/min, 15 ℃/min.
Preferably, the temperature of the temperature rise is any value or a range of values between two values of 700 ℃, 800 ℃, 900 ℃, 1000 ℃.
The heat preservation time is 1-6h.
Preferably, the time of incubation is any one of 1h, 2h, 3h, 4h, 5h, and 6h or a range between the two values.
The application also provides a graphite felt electrode for the all-vanadium redox flow battery, which is obtained by activating the activation method according to any one of the above.
The application also provides an application of the graphite felt electrode for the all-vanadium redox flow battery, which is obtained by activating the graphite felt electrode for the all-vanadium redox flow battery by the activation method or the application of the graphite felt electrode for the all-vanadium redox flow battery to the all-vanadium redox flow battery.
The beneficial effects of the application at least comprise:
1. precursor WCl of tungsten carbide (WC) or molybdenum carbide (MoC) x Or MoCl y Because the electronegativity of the tungsten (W) end or the molybdenum (Mo) end is smaller than that of the chlorine (Cl), when the imidazole ionic liquid is added, 1-butyl-3-methylimidazole hexafluorophosphate ([ BMIM)][PF6]) For example, positively charged [ BMIM ]] + Is attracted to Cl end, and after the graphite felt electrode is pretreated, said graphite felt electrode contains lots of negatively charged oxygen-containing functional groups, and these functional groups can be used as anchoring points, under the action of electrostatic force, and can be positively charged [ BMIM ]] + Coated WCl x Or MoCl y Molecules are attracted, and tungsten carbide (WC) or molybdenum carbide (MoC) nanocrystalline is formed on the anchor point through carbonization reaction, so that the addition of ionic liquid can well disperse WCl x Or MoCl y Creates favorable conditions for the dispersion of WC or MoC on the carbon fibers of the graphite felt.
2. The application adopts CO 2 Safer and more efficient as a carbon source gas, first, CO 2 The carbon fiber of the graphite felt electrode is reacted with a proper amount of CO at high temperature, the chemical reaction has an etching effect on the graphite felt electrode, etching pits are formed on the carbon fiber of the graphite felt electrode, the surface area of the graphite felt electrode is increased, and on the other hand, the proper amount of CO generated in situ can be used as reducing gas to react with a tungsten source or a molybdenum source adsorbed on the carbon fiber, so that the tungsten source or the molybdenum source is reduced into nano tungsten carbide (WC) or molybdenum carbide (MoC) in situ, and tungsten carbide (WC) or molybdenum carbide (MoC) particles loaded on the graphite felt electrode are formed. Second, CO 2 The oxygen-containing functional groups generated in the pretreatment step on the graphite felt electrode fiber are not reduced by the non-reducing gas, so that the good hydrophilicity of the graphite felt electrode is maintained. The etched pits and the loaded tungsten carbide (WC) or molybdenum carbide (MoC) on the graphite felt electrode fibers not only cause the rugged morphology of the fibers, so that the surface area of the graphite felt electrode is greatly increased, the active sites are greatly increased, but also the tungsten carbide (WC) or molybdenum carbide (MoC) has been proved to have platinum-like catalytic performance, so that the electrochemical activity of the graphite felt electrode is greatly enhanced.
3. Special electrolytic cell in the applicationDuring electrolysis, oxygen in the air reaches the cathode through the air diffusion electrode to generate hydrogen peroxide through electroreduction reaction, and the anode (graphite felt electrode) generates oxygen evolution reaction, because the electrolytic cell adopts a diaphragm-free design, the hydrogen peroxide (H) generated by the cathode is intentionally caused 2 O 2 ) Migration and diffusion to the anode and decomposition reactions occur in the anode portion to generate reactive oxygen species and highly oxidizing radicals (.ho), (. HO) 2 ) The graphite felt electrode can undergo electrochemical oxidation, hydrogen peroxide oxidation, active oxygen and strong-oxidability free radical oxidation in the process, and the hydrophilicity and activity of the graphite felt electrode are greatly improved.
Drawings
FIG. 1 is a schematic cross-sectional view of carbon fiber of graphite felt electrode for an activated vanadium redox flow battery of example 4 of the present application;
FIG. 2 is a graph of a carbon fiber transmission electron microscope of the graphite felt of example 4 of the present application;
FIG. 3 is an X-ray diffraction pattern of the graphite felt of example 4 of the present application;
fig. 4 is a contact angle test chart of comparative example 1 of the present application.
Detailed Description
The following description of at least one exemplary embodiment is merely exemplary in nature and is in no way intended to limit the application, its application, or uses. All other embodiments, which can be made by those skilled in the art based on the embodiments of the application without making any inventive effort, are intended to be within the scope of the application.
Unless otherwise indicated, all starting materials in the examples of the present application were purchased commercially.
The air diffusion electrode used in the present application refers to an electrode disclosed in patent publication No. CN103326039 a.
Example 1
The activation method of the graphite felt electrode for the all-vanadium redox flow battery comprises the following steps:
mixing a tungsten dichloride solution with the mass percentage of 1% with a 1, 3-dimethyl imidazole hexafluorophosphate solution with the mass percentage of 1% to obtain a mixed solution;
in an electrolytic tank without a diaphragm, an air diffusion electrode is adopted as a cathode, a graphite felt electrode is adopted as an anode, a dilute sulfuric acid solution with the concentration of 0.5mol/L is adopted as electrolyte, direct current constant current electrolytic treatment is conducted, and the current density is 10mA/cm 2 And (3) electrolyzing for 150min to obtain an electrolyzed graphite felt electrode, cleaning and drying to finally obtain the pretreated graphite felt electrode.
Immersing the pretreated graphite felt electrode in the mixed solution, taking out and drying to obtain a compound precursor;
introducing the compound precursor into CO with the flow rate of 10ml/min 2 And heating and preserving heat of the gas, wherein the heating rate is 5 ℃/min, the heating temperature is 700 ℃, the preserving heat time is 1h, and then, inert gas is introduced to cool the gas, so that the graphite felt electrode for the activated vanadium redox flow battery is obtained.
Example 2
The activation method of the graphite felt electrode for the all-vanadium redox flow battery comprises the following steps:
mixing a tungsten tetrachloride solution with the mass percentage of 2% with a 1-ethyl-3-methyl hexafluorophosphate solution with the mass percentage of 2% to obtain a mixed solution;
in an electrolytic tank without a diaphragm, an air diffusion electrode is adopted as a cathode, a graphite felt electrode is adopted as an anode, a dilute sulfuric acid solution with the concentration of 1mol/L is adopted as electrolyte, direct current is connected for constant current electrolytic treatment, and the current density is 20mA/cm 2 And (3) electrolyzing for 120min to obtain an electrolyzed graphite felt electrode, cleaning and drying to finally obtain the pretreated graphite felt electrode.
Immersing the pretreated graphite felt electrode in the mixed solution, taking out and drying to obtain a compound precursor;
introducing the compound precursor into CO with the flow rate of 20ml/min 2 And heating and preserving heat of the gas, wherein the heating rate is 6 ℃/min, the heating temperature is 750 ℃, the preserving heat time is 1.5h, and then inert gas is introduced to cool the gas, so that the graphite felt electrode for the activated vanadium redox flow battery is obtained.
Example 3
The activation method of the graphite felt electrode for the all-vanadium redox flow battery comprises the following steps:
mixing a tungsten pentachloride solution with the mass percentage of 3% with a 1-dodecyl-3-methyl hexafluorophosphate solution with the mass percentage of 3% to obtain a mixed solution;
in an electrolytic tank without a diaphragm, an air diffusion electrode is adopted as a cathode, a graphite felt electrode is adopted as an anode, a dilute sulfuric acid solution with the concentration of 1.5mol/L is adopted as electrolyte, direct current constant current electrolytic treatment is conducted, and the current density is 30mA/cm 2 And (3) electrolyzing for 100min to obtain an electrolyzed graphite felt electrode, cleaning and drying to finally obtain the pretreated graphite felt electrode.
Immersing the pretreated graphite felt electrode in the mixed solution, taking out and drying to obtain a compound precursor;
introducing the compound precursor into CO with the flow rate of 30ml/min 2 And heating and preserving heat of the gas, wherein the heating rate is 7 ℃/min, the heating temperature is 800 ℃, the preserving heat time is 2h, and then, inert gas is introduced to cool the gas, so that the graphite felt electrode for the activated vanadium redox flow battery is obtained.
Example 4
The activation method of the graphite felt electrode for the all-vanadium redox flow battery comprises the following steps:
mixing a tungsten hexachloride solution with the mass percentage of 5% with a 1-butyl-3-methyl hexafluorophosphate solution with the mass percentage of 10% to obtain a mixed solution;
in an electrolytic tank without a diaphragm, an air diffusion electrode is adopted as a cathode, a graphite felt electrode is adopted as an anode, a dilute sulfuric acid solution with the concentration of 2mol/L is adopted as electrolyte, direct current is connected for constant current electrolytic treatment, and the current density is 50mA/cm 2 And (3) electrolyzing for 80min to obtain an electrolyzed graphite felt electrode, and cleaning and drying to finally obtain the pretreated graphite felt electrode.
Immersing the pretreated graphite felt electrode in the mixed solution, taking out and drying to obtain a compound precursor;
introducing the compound precursor into CO with the flow rate of 100ml/min 2 Gas, heating and preserving heat, and heating rateAnd (3) heating at 10 ℃/min, maintaining the temperature at 900 ℃ for 3 hours, and then introducing inert gas for cooling to obtain the graphite felt electrode for the activated all-vanadium redox flow battery, wherein white spots in the cross section of the graphite felt carbon fiber are etching pits, black spots are tungsten carbide particles, and the carbon fiber is provided with a concave-convex alternate morphology, so that the surface area of the graphite felt electrode is greatly increased. The transmission electron microscope image of fig. 2 can clearly see etching pits on the edges of the carbon fibers of the graphite felt and deep black tungsten carbide particles on the carbon fibers, and the particle sizes of the particles are mostly less than 20 nanometers and are uniformly dispersed, which indicates that the addition of the ionic liquid is helpful for preparing uniformly dispersed nanoscale tungsten carbide particles. Fig. 3 shows XRD comparison of the graphite felt of example 4 with that of the unactivated graphite felt, and it is known from two strongest peaks of WC (001) and WC (100) that tungsten carbide particles have been successfully supported on the carbon fibers of the graphite felt, and at the same time, the peaks of WC (001) and WC (100) are wider, indicating that the particle size of the tungsten carbide particles is smaller, which is consistent with the result of fig. 2.
Example 5
The activation method of the graphite felt electrode for the all-vanadium redox flow battery comprises the following steps:
mixing molybdenum dichloride solution with the mass percentage of 2% with 1-benzyl-3-methyl hexafluorophosphate solution with the mass percentage of 4% to obtain mixed solution;
in an electrolytic tank without a diaphragm, an air diffusion electrode is adopted as a cathode, a graphite felt electrode is adopted as an anode, a dilute sulfuric acid solution with the concentration of 2.4mol/L is adopted as electrolyte, direct current constant current electrolytic treatment is conducted, and the current density is 60mA/cm 2 And (3) electrolyzing for 60min to obtain an electrolyzed graphite felt electrode, cleaning and drying to finally obtain the pretreated graphite felt electrode.
Immersing the pretreated graphite felt electrode in the mixed solution, taking out and drying to obtain a compound precursor;
introducing the compound precursor into CO with the flow rate of 50ml/min 2 Heating and preserving heat of the gas, wherein the heating rate is 8 ℃/min, the heating temperature is 930 ℃, the preserving heat time is 2.5h, and then inert gas is introduced for cooling to obtain the graphite felt electrode for the activated vanadium redox flow battery。
Example 6
The activation method of the graphite felt electrode for the all-vanadium redox flow battery comprises the following steps:
mixing a tungsten hexachloride solution with the mass percentage of 8% with a 1-allyl-3-methyl hexafluorophosphate solution with the mass percentage of 5% to obtain a mixed solution;
in an electrolytic tank without a diaphragm, an air diffusion electrode is adopted as a cathode, a graphite felt electrode is adopted as an anode, a dilute sulfuric acid solution with the concentration of 2.8mol/L is adopted as electrolyte, direct current constant current electrolytic treatment is conducted, and the current density is 70mA/cm 2 And (3) electrolyzing for 50min to obtain an electrolyzed graphite felt electrode, cleaning and drying to finally obtain the pretreated graphite felt electrode.
Immersing the pretreated graphite felt electrode in the mixed solution, taking out and drying to obtain a compound precursor;
introducing the compound precursor into CO with the flow rate of 60ml/min 2 And heating and preserving heat of the gas, wherein the heating rate is 9 ℃/min, the heating temperature is 1000 ℃, the preserving heat time is 4 hours, and then, inert gas is introduced to cool the gas, so that the graphite felt electrode for the activated vanadium redox flow battery is obtained.
Example 7
The activation method of the graphite felt electrode for the all-vanadium redox flow battery comprises the following steps:
mixing a molybdenum trichloride solution with the mass percentage of 5% with a 1-vinyl-3-methyl hexafluorophosphate solution with the mass percentage of 6% to obtain a mixed solution;
in an electrolytic tank without a diaphragm, an air diffusion electrode is adopted as a cathode, a graphite felt electrode is adopted as an anode, a dilute sulfuric acid solution with the concentration of 3mol/L is adopted as electrolyte, direct current is connected for constant current electrolytic treatment, and the current density is 80mA/cm 2 And (3) electrolyzing for 40min to obtain an electrolyzed graphite felt electrode, cleaning and drying to finally obtain the pretreated graphite felt electrode.
Immersing the pretreated graphite felt electrode in the mixed solution, taking out and drying to obtain a compound precursor;
the saidCO with the flow rate of 80ml/min for introducing the compound precursor 2 And heating and preserving heat of the gas, wherein the heating rate is 11 ℃/min, the heating temperature is 900 ℃, the preserving heat time is 4.5h, and then inert gas is introduced to cool the gas, so that the graphite felt electrode for the activated vanadium redox flow battery is obtained.
Example 8
The activation method of the graphite felt electrode for the all-vanadium redox flow battery comprises the following steps:
mixing a tungsten hexachloride solution with the mass percentage of 10% with a 1-ethyl-3-vinyl hexafluorophosphate solution with the mass percentage of 7% to obtain a mixed solution;
in an electrolytic tank without a diaphragm, an air diffusion electrode is adopted as a cathode, a graphite felt electrode is adopted as an anode, a dilute sulfuric acid solution with the concentration of 3.2mol/L is adopted as electrolyte, direct current constant current electrolytic treatment is conducted, and the current density is 90mA/cm 2 And (3) electrolyzing for 30min to obtain an electrolyzed graphite felt electrode, and cleaning and drying to finally obtain the pretreated graphite felt electrode.
Immersing the pretreated graphite felt electrode in the mixed solution, taking out and drying to obtain a compound precursor;
introducing the compound precursor into CO with the flow rate of 100ml/min 2 And heating and preserving heat of the gas, wherein the heating rate is 13 ℃/min, the heating temperature is 850 ℃, the preserving heat time is 5h, and then, inert gas is introduced to cool the gas, so that the graphite felt electrode for the activated vanadium redox flow battery is obtained.
Example 9
The activation method of the graphite felt electrode for the all-vanadium redox flow battery comprises the following steps:
mixing a molybdenum pentachloride solution with the mass percentage of 6% with a 1-benzyl-3-vinyl hexafluorophosphate solution with the mass percentage of 8% to obtain a mixed solution;
in an electrolytic tank without a diaphragm, an air diffusion electrode is adopted as a cathode, a graphite felt electrode is adopted as an anode, a dilute sulfuric acid solution with the concentration of 3.5mol/L is adopted as electrolyte, direct current constant current electrolytic treatment is conducted, and the current density is 100mA/cm 2 The electrolysis time is 20min, and the obtained product is after electrolysisAnd cleaning and drying the graphite felt electrode to finally obtain the pretreated graphite felt electrode.
Immersing the pretreated graphite felt electrode in the mixed solution, taking out and drying to obtain a compound precursor;
introducing the compound precursor into CO with the flow rate of 120ml/min 2 And heating and preserving heat of the gas, wherein the heating rate is 14 ℃/min, the heating temperature is 960 ℃, the preserving heat time is 5.5h, and then inert gas is introduced to cool the gas, so that the graphite felt electrode for the activated vanadium redox flow battery is obtained.
Example 10
The activation method of the graphite felt electrode for the all-vanadium redox flow battery comprises the following steps:
mixing a molybdenum dichloride solution with the mass percentage of 10% with a 1-butyl-2, 3-dimethyl hexafluorophosphate solution with the mass percentage of 9% to obtain a mixed solution;
in an electrolytic tank without a diaphragm, an air diffusion electrode is adopted as a cathode, a graphite felt electrode is adopted as an anode, a dilute sulfuric acid solution with the concentration of 4mol/L is adopted as electrolyte, direct current is connected for constant current electrolytic treatment, and the current density is 120mA/cm 2 And (3) electrolyzing for 10min to obtain an electrolyzed graphite felt electrode, cleaning and drying to finally obtain the pretreated graphite felt electrode.
Immersing the pretreated graphite felt electrode in the mixed solution, taking out and drying to obtain a compound precursor;
introducing the compound precursor into CO with the flow rate of 150ml/min 2 And heating and preserving heat of the gas, wherein the heating rate is 15 ℃/min, the heating temperature is 1000 ℃, the preserving heat time is 6h, and then, inert gas is introduced to cool the gas, so that the graphite felt electrode for the activated vanadium redox flow battery is obtained.
Comparative example 1: the preparation process was identical to example 4, except that conventional heat treatment was used as a pretreatment method for graphite felt.
Comparative example 2: the preparation process was identical to example 4, except that no tungsten hexachloride solution was added to the mixture.
Comparative example 3: the preparation process was identical to example 4, except that no imidazole ionic liquid was added to prepare the complex precursor.
Comparative example 4: the preparation process was identical to example 4, except that the final activation was carried out with CO as carbon source gas.
The graphite felt electrodes in examples 1 to 10 and comparative examples 1 to 4 were subjected to contact angle and specific surface area tests under the same conditions, and the test results are shown in table 1:
table 1 contact angle and specific surface area test
The graphite felt electrodes fabricated in examples 1-10 and comparative examples 1-4 were assembled on a cell stack for testing, and coulombic efficiency, voltage efficiency and energy efficiency were tested and recorded under the same test conditions. The test results are shown in table 2:
table 2 cell performance test table for assembled stacks using hydrophilic-hydrophobic double sided graphite felt electrodes
From the above test results, the conventional heat treatment is adopted as a pretreatment method of the graphite felt in comparative example 1, so that the oxidation degree of the graphite felt is insufficient, and as can be seen from the contact angle test results in table 1, the electrocatalytic activity is affected, and the voltage efficiency is 87.4% and lower than that of examples 1-10; comparative example 2 is that no tungsten hexachloride solution is added into the mixed solution, namely the activated graphite felt does not contain active catalytic particles of tungsten carbide, so that the specific surface area and the voltage efficiency are low; in the preparation process of comparative example 3, imidazole ionic liquid is not added into the mixed solution, which can lead to aggregation of precursor tungsten hexachloride on carbon fibers, then agglomeration of tungsten carbide particles is caused after carbonization, the catalytic activity of graphite felt is affected, and the voltage efficiency is low and is only 86.9%; comparative example 4 CO was used as the carbon source gas during the final activation process, and excess CO not only reduced the active oxygen-containing functional groups on the carbon fibers of the graphite felt, resulting inThe hydrophilicity was deteriorated (the contact angle of the graphite felt of comparative example 4 in table 1 was as high as 130 degrees, the test photograph was shown in fig. 4), and the decrease of the oxygen-containing functional group caused the diffusion and the agglomeration adsorption of the tungsten group adsorbed to the interlayer on a small amount of the oxygen-containing functional group, resulting in the enlargement of WC crystal nucleus, the difficulty of the carburizing process, and the tungsten carbide (W) 2 C) Is generated. In addition, CO cannot etch the carbon fibers, and is not beneficial to increasing the specific surface area of the graphite felt body.
In summary, according to the graphite felt electrode for the all-vanadium redox flow battery and the activation method and application thereof, firstly, a special electrolytic tank is utilized to perform a series of oxidation modifications of electrochemical oxidation, hydrogen peroxide oxidation, active oxygen and strong-oxidability free radical oxidation on the graphite felt, so that the number of active oxygen-containing functional groups on carbon fibers of the graphite felt is greatly increased, and the hydrophilicity and activity of the graphite felt are greatly improved (see table 1); secondly, the effective dispersion of the tungsten source or the molybdenum source in the ethanol solvent by utilizing the hydrophobic ionic liquid, and the successful loading of the graphite felt with the nano-scale tungsten carbide or molybdenum carbide provides favorable conditions; third, in the final activation step, the present application employs CO 2 As a carbon source gas, the etched pits and the loaded tungsten carbide (WC) or molybdenum carbide (MoC) on the activated carbon fibers of the graphite felt electrode not only cause uneven morphology of the fibers, so that the surface area of the graphite felt electrode is greatly increased (see table 1), the active sites are greatly increased, but also the tungsten carbide (WC) or molybdenum carbide (MoC) has been proved to have platinum-like catalytic performance, so that the electrochemical activity of the graphite felt electrode is greatly enhanced, and the voltage efficiency and the energy efficiency are improved in the battery performance by the reaction, as shown in table 2.
The above description is only of the preferred embodiments of the present application and is not intended to limit the present application, but various modifications and variations can be made to the present application by those skilled in the art. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present application should be included in the protection scope of the present application.
Claims (8)
1. The activation method of the graphite felt electrode for the all-vanadium redox flow battery is characterized by at least comprising the following steps:
mixing a solution containing a tungsten source or a molybdenum source with an imidazole ionic liquid to obtain a mixed solution;
immersing the pretreated graphite felt electrode in the mixed solution, taking out and drying to obtain a compound precursor;
introducing the compound precursor into CO 2 Heating and preserving heat of the gas, and then introducing inert gas to cool to obtain the graphite felt electrode for the activated all-vanadium redox flow battery;
the tungsten source is at least one selected from tungsten dichloride, tungsten tetrachloride, tungsten pentachloride and tungsten hexachloride;
the molybdenum source is at least one of molybdenum dichloride, molybdenum trichloride and molybdenum pentachloride;
the pretreatment mode of the pretreated graphite felt electrode is as follows:
in an electrolytic tank without a diaphragm, an air diffusion electrode is adopted as a cathode, a graphite felt electrode is adopted as an anode, a dilute sulfuric acid solution is adopted as an electrolyte, direct current constant current electrolytic treatment is conducted, the electrolyzed graphite felt electrode is obtained, and the pretreated graphite felt electrode is finally obtained after cleaning and drying;
the temperature is 700-1000 ℃; the heat preservation time is 1-6h.
2. The method for activating graphite felt electrode for vanadium redox flow battery according to claim 1, wherein the method comprises the steps of,
the solvent in the solution containing tungsten source or molybdenum source is ethanol;
the mass percentage of the tungsten source or the molybdenum source in the solution is 1-10%.
3. The method for activating graphite felt electrode for vanadium redox flow battery according to claim 1, wherein the method comprises the steps of,
the imidazole ionic liquid accounts for 1-10% of the mixed liquid by mass.
4. The method for activating graphite felt electrode for vanadium redox flow battery according to claim 1, wherein the method comprises the steps of,
the imidazole ions in the imidazole ionic liquid are selected from hydrophobic imidazole ion salts;
the hydrophobic imidazole ion salt is selected from 1, 3-dimethyl imidazole hexafluorophosphate.
5. The method for activating graphite felt electrode for vanadium redox flow battery according to claim 1, wherein the method comprises the steps of,
the concentration of the dilute sulfuric acid is 0.5-4mol/L;
the current density of the direct current constant current is 10-120mA/cm 2 The electrolysis time is 10-150min.
6. The method for activating graphite felt electrode for vanadium redox flow battery according to claim 1, wherein the method comprises the steps of,
CO is introduced into 2 The flow rate of the gas is 10-150ml/min; the temperature rising rate is 5-15 ℃/min.
7. A graphite felt electrode for an all-vanadium redox flow battery, characterized in that the graphite felt electrode is activated by the activation method according to any one of claims 1 to 6.
8. The application of the graphite felt electrode for the all-vanadium redox flow battery is characterized in that the graphite felt electrode for the all-vanadium redox flow battery, which is obtained by activation through the activation method according to any one of claims 1-6, is applied to the all-vanadium redox flow battery.
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Citations (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4873121A (en) * | 1986-04-09 | 1989-10-10 | Kernforschungsaniage Julich Gmbh | Cathode/membrane assembly and method of making same |
| CN101182678A (en) * | 2007-11-05 | 2008-05-21 | 攀钢集团攀枝花钢铁研究院 | Graphite felt watch surface modified method and modified mineral carbon felt |
| CN102683706A (en) * | 2012-01-20 | 2012-09-19 | 石家庄学院 | Preparation method of graphite felt modified electrode and preparation method of all-vanadium flow battery |
| CN102683715A (en) * | 2012-01-20 | 2012-09-19 | 石家庄学院 | Electrode material for all-vanadium redox flow battery and preparation method thereof |
| CN103531827A (en) * | 2013-10-31 | 2014-01-22 | 大连交通大学 | Method for improving electrochemical activity of graphite felt of positive electrode of flow battery |
| CN107364934A (en) * | 2017-08-09 | 2017-11-21 | 南京大学 | Electro-catalysis reduction combination electrode, preparation method and applications |
| KR20180017679A (en) * | 2016-08-10 | 2018-02-21 | 주식회사 제이앤티지 | Electrode for vanadium redox flow battery and vanadium redox flow battery including the same |
| CN112316957A (en) * | 2020-10-31 | 2021-02-05 | 清芯未来(北京)科技有限公司 | graphene/MoS2Graphite felt electrode material modified by heterojunction and application thereof |
| WO2021238912A1 (en) * | 2020-05-25 | 2021-12-02 | 北京化工大学 | Transition metal compound-hybridized and nitrogen-doped porous carbon material and preparation method therefor |
| CN114031079A (en) * | 2021-11-03 | 2022-02-11 | 北京化工大学 | Molybdenum carbide carbon nanofiber composite material and preparation method and application thereof |
| KR20220025562A (en) * | 2020-08-24 | 2022-03-03 | 한국전력공사 | felt electrode for redox flow battery and surface modified method |
| CN114335567A (en) * | 2021-12-15 | 2022-04-12 | 天津大学 | Modification method of carbon electrode for anthraquinone/potassium ferrocyanide flow battery |
| CN115346803A (en) * | 2022-08-03 | 2022-11-15 | 昆明理工大学 | W 18 O 49 Carbon paper composite electrode material and preparation method thereof |
| WO2023274441A1 (en) * | 2021-06-30 | 2023-01-05 | Schaeffler Technologies AG & Co. KG | Component for an electrochemical cell, redox flow cell, fuel cell, and electrolyser |
| CN116111109A (en) * | 2021-11-11 | 2023-05-12 | 南方科技大学 | Carbon electrode composite material, preparation method thereof and secondary battery |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| AU2019425621A1 (en) * | 2019-01-29 | 2021-07-22 | Sumitomo Electric Industries, Ltd. | Battery cell, cell stack, and redox flow battery |
-
2023
- 2023-06-29 CN CN202310781324.2A patent/CN116505002B/en active Active
Patent Citations (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4873121A (en) * | 1986-04-09 | 1989-10-10 | Kernforschungsaniage Julich Gmbh | Cathode/membrane assembly and method of making same |
| CN101182678A (en) * | 2007-11-05 | 2008-05-21 | 攀钢集团攀枝花钢铁研究院 | Graphite felt watch surface modified method and modified mineral carbon felt |
| CN102683706A (en) * | 2012-01-20 | 2012-09-19 | 石家庄学院 | Preparation method of graphite felt modified electrode and preparation method of all-vanadium flow battery |
| CN102683715A (en) * | 2012-01-20 | 2012-09-19 | 石家庄学院 | Electrode material for all-vanadium redox flow battery and preparation method thereof |
| CN103531827A (en) * | 2013-10-31 | 2014-01-22 | 大连交通大学 | Method for improving electrochemical activity of graphite felt of positive electrode of flow battery |
| KR20180017679A (en) * | 2016-08-10 | 2018-02-21 | 주식회사 제이앤티지 | Electrode for vanadium redox flow battery and vanadium redox flow battery including the same |
| CN107364934A (en) * | 2017-08-09 | 2017-11-21 | 南京大学 | Electro-catalysis reduction combination electrode, preparation method and applications |
| WO2021238912A1 (en) * | 2020-05-25 | 2021-12-02 | 北京化工大学 | Transition metal compound-hybridized and nitrogen-doped porous carbon material and preparation method therefor |
| KR20220025562A (en) * | 2020-08-24 | 2022-03-03 | 한국전력공사 | felt electrode for redox flow battery and surface modified method |
| CN112316957A (en) * | 2020-10-31 | 2021-02-05 | 清芯未来(北京)科技有限公司 | graphene/MoS2Graphite felt electrode material modified by heterojunction and application thereof |
| WO2023274441A1 (en) * | 2021-06-30 | 2023-01-05 | Schaeffler Technologies AG & Co. KG | Component for an electrochemical cell, redox flow cell, fuel cell, and electrolyser |
| CN114031079A (en) * | 2021-11-03 | 2022-02-11 | 北京化工大学 | Molybdenum carbide carbon nanofiber composite material and preparation method and application thereof |
| CN116111109A (en) * | 2021-11-11 | 2023-05-12 | 南方科技大学 | Carbon electrode composite material, preparation method thereof and secondary battery |
| CN114335567A (en) * | 2021-12-15 | 2022-04-12 | 天津大学 | Modification method of carbon electrode for anthraquinone/potassium ferrocyanide flow battery |
| CN115346803A (en) * | 2022-08-03 | 2022-11-15 | 昆明理工大学 | W 18 O 49 Carbon paper composite electrode material and preparation method thereof |
Non-Patent Citations (5)
| Title |
|---|
| Nitrogen-Doped Tungsten Carbide-Modified Graphite Felt as a Bifunctional Electrocatalyst for an All-Vanadium Redox Flow Battery;Anteneh Wodaje Bayeh等;ACS SUSTAINABLE CHEMISTRY & ENGINEERING;第10卷(第37期);12271-12278 * |
| WC和Ti3C2作为高效微生物燃料电池阳极的研究;刘达;中国优秀硕士学位论文全文数据库 工程科技Ⅰ辑(第02期);B015-333 * |
| 二维碳质材料的制备和应用;汤艳萍;徐庆;唐睿智;张帆;;新型炭材料(第03期);213-231 * |
| 全钒氧化还原液流电池一体化复合电极的研究;崔旭梅;王军;陈孝娥;赵英涛;李云;;电源技术(第11期);1019-1021 * |
| 全钒液流电池性能及电极材料研究;杜涛;廖小东;郝彰翔;李爱魁;滕隽;;电源技术(第02期);231-233 * |
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