CN118480829A - Catalytic assembly, vanadium electrolyte electrolysis device and vanadium electrolyte preparation method - Google Patents
Catalytic assembly, vanadium electrolyte electrolysis device and vanadium electrolyte preparation method Download PDFInfo
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- 238000005868 electrolysis reaction Methods 0.000 title claims abstract description 123
- 229910052720 vanadium Inorganic materials 0.000 title claims abstract description 111
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 title claims abstract description 109
- 239000003792 electrolyte Substances 0.000 title claims abstract description 108
- 230000003197 catalytic effect Effects 0.000 title claims abstract description 49
- 238000002360 preparation method Methods 0.000 title abstract description 18
- 239000003054 catalyst Substances 0.000 claims abstract description 114
- 239000007788 liquid Substances 0.000 claims abstract description 96
- 238000003860 storage Methods 0.000 claims abstract description 65
- 239000012528 membrane Substances 0.000 claims abstract description 61
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 46
- 239000010936 titanium Substances 0.000 claims abstract description 32
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 32
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 26
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 23
- 239000000835 fiber Substances 0.000 claims abstract description 19
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical group [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 claims description 38
- 229910052741 iridium Inorganic materials 0.000 claims description 32
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 32
- 238000000034 method Methods 0.000 claims description 27
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 22
- 229910000457 iridium oxide Inorganic materials 0.000 claims description 22
- HTXDPTMKBJXEOW-UHFFFAOYSA-N dioxoiridium Chemical compound O=[Ir]=O HTXDPTMKBJXEOW-UHFFFAOYSA-N 0.000 claims description 21
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 18
- 238000011068 loading method Methods 0.000 claims description 15
- 239000000203 mixture Substances 0.000 claims description 14
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims description 8
- 229910052697 platinum Inorganic materials 0.000 claims description 8
- 229910052707 ruthenium Inorganic materials 0.000 claims description 8
- 239000000758 substrate Substances 0.000 claims 1
- 238000007789 sealing Methods 0.000 abstract description 16
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 17
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 15
- 239000000463 material Substances 0.000 description 12
- 230000008569 process Effects 0.000 description 12
- 150000002500 ions Chemical class 0.000 description 7
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 6
- 239000011248 coating agent Substances 0.000 description 6
- 238000000576 coating method Methods 0.000 description 6
- 238000000354 decomposition reaction Methods 0.000 description 6
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- 238000004070 electrodeposition Methods 0.000 description 4
- 238000005507 spraying Methods 0.000 description 4
- 239000013589 supplement Substances 0.000 description 4
- 238000010023 transfer printing Methods 0.000 description 4
- 229910001456 vanadium ion Inorganic materials 0.000 description 4
- 238000001354 calcination Methods 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 238000005260 corrosion Methods 0.000 description 3
- 230000007797 corrosion Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000006056 electrooxidation reaction Methods 0.000 description 3
- 230000002349 favourable effect Effects 0.000 description 3
- 229910002804 graphite Inorganic materials 0.000 description 3
- 239000010439 graphite Substances 0.000 description 3
- 238000006722 reduction reaction Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- UUUGYDOQQLOJQA-UHFFFAOYSA-L vanadyl sulfate Chemical compound [V+2]=O.[O-]S([O-])(=O)=O UUUGYDOQQLOJQA-UHFFFAOYSA-L 0.000 description 3
- 229940041260 vanadyl sulfate Drugs 0.000 description 3
- 229910000352 vanadyl sulfate Inorganic materials 0.000 description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- 239000004743 Polypropylene Substances 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
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- 239000006229 carbon black Substances 0.000 description 2
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- 229910052802 copper Inorganic materials 0.000 description 2
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- 238000001514 detection method Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 229920001973 fluoroelastomer Polymers 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
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- 238000004519 manufacturing process Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- 229920001155 polypropylene Polymers 0.000 description 2
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 2
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- 229920000915 polyvinyl chloride Polymers 0.000 description 2
- 239000004800 polyvinyl chloride Substances 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 229910001925 ruthenium oxide Inorganic materials 0.000 description 2
- WOCIAKWEIIZHES-UHFFFAOYSA-N ruthenium(iv) oxide Chemical compound O=[Ru]=O WOCIAKWEIIZHES-UHFFFAOYSA-N 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 238000007086 side reaction Methods 0.000 description 2
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- 229910002027 silica gel Inorganic materials 0.000 description 2
- 239000000725 suspension Substances 0.000 description 2
- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical group CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 description 2
- 101100491335 Caenorhabditis elegans mat-2 gene Proteins 0.000 description 1
- 229910021638 Iridium(III) chloride Inorganic materials 0.000 description 1
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- 238000004146 energy storage Methods 0.000 description 1
- UQSQSQZYBQSBJZ-UHFFFAOYSA-N fluorosulfonic acid Chemical group OS(F)(=O)=O UQSQSQZYBQSBJZ-UHFFFAOYSA-N 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 239000012212 insulator Substances 0.000 description 1
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- 239000004408 titanium dioxide Substances 0.000 description 1
- DANYXEHCMQHDNX-UHFFFAOYSA-K trichloroiridium Chemical compound Cl[Ir](Cl)Cl DANYXEHCMQHDNX-UHFFFAOYSA-K 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25C—PROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
- C25C7/00—Constructional parts, or assemblies thereof, of cells; Servicing or operating of cells
- C25C7/02—Electrodes; Connections thereof
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25C—PROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
- C25C1/00—Electrolytic production, recovery or refining of metals by electrolysis of solutions
- C25C1/22—Electrolytic production, recovery or refining of metals by electrolysis of solutions of metals not provided for in groups C25C1/02 - C25C1/20
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25C—PROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
- C25C7/00—Constructional parts, or assemblies thereof, of cells; Servicing or operating of cells
- C25C7/04—Diaphragms; Spacing elements
-
- 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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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Electrolytic Production Of Non-Metals, Compounds, Apparatuses Therefor (AREA)
Abstract
The invention discloses a catalytic assembly, a vanadium electrolyte electrolysis device and a vanadium electrolyte preparation method, wherein the catalytic assembly comprises a titanium mesh, a titanium fiber felt, a conductive ionic membrane and a carbon felt which are sequentially arranged; the conductive ionic membrane is loaded with a first catalyst on one side connected with the titanium fiber felt. According to the invention, the vanadium electrolyte is prepared by adopting the catalytic component, so that the electrolysis current density can be improved, the electrolysis voltage can be reduced, an anode liquid storage tank and an anode liquid circulating device are omitted, required sealing elements are reduced, and the liquid leakage of the electrolysis device is reduced.
Description
Technical Field
The invention relates to the field of vanadium electrolyte preparation, in particular to a catalytic assembly, a vanadium electrolyte electrolysis device and a vanadium electrolyte preparation method.
Background
The all-vanadium redox flow battery is also called a vanadium battery, mainly utilizes the change of valence state of vanadium ions to realize the storage and release of electric energy, and has the advantages of high safety, large energy storage capacity, long service life and the like. The electric energy of the vanadium battery is stored in sulfuric acid electrolyte of vanadium ions in different valence states in a chemical energy mode, and the electrolyte is subjected to electrochemical reaction, so that the chemical energy stored in the solution is converted into electric energy.
Vanadium electrolyte is a key material of a flow battery, and is usually prepared in an electrolytic tank by adopting an electrolytic method, and the electrolytic tank adopted by the current vanadium electrolyte electrolytic device has various forms, but the electrolytic tank is mainly a galvanic pile type electrolytic tank. The anode is an oxidation reaction of decomposing water into oxygen, and the cathode is a reduction reaction of vanadium. Wherein, the water decomposition reaction speed of the anode is slow, the overpotential is high, the electrolysis current density is low, and the electrolysis voltage is high. The anode adopts a flaky coating titanium electrode, a titanium foam or graphite electrode, the reaction active sites are few, the electrolysis voltage is high, and the flaky electrode is difficult to seal.
Disclosure of Invention
The present invention has been made based on the findings and knowledge of the inventors regarding the following facts and problems: in the process of preparing the vanadium electrolyte of the all-vanadium redox flow battery by an electrolysis method, the vanadium electrolysis current density is low, the electrolysis voltage is high, the electrolytic stack is complex to construct, and the sealing is difficult.
The present invention aims to solve at least one of the technical problems in the related art to some extent. Therefore, the embodiment of the invention provides a catalytic assembly, a vanadium electrolyte electrolysis device and a vanadium electrolyte preparation method, wherein the catalytic assembly is used for preparing vanadium electrolyte, so that the electrolysis current density can be improved, the electrolysis voltage can be reduced, an anode liquid storage tank and an anode liquid circulation device are omitted, required sealing elements are reduced, and the possibility of liquid leakage of the electrolysis device is reduced.
An embodiment of the present invention provides a catalytic assembly comprising: the titanium mesh, the titanium fiber felt, the conductive ion membrane and the carbon felt are sequentially arranged; the conductive ionic membrane is loaded with a first catalyst on one side connected with the titanium fiber felt.
The catalytic assembly provided by the embodiment of the invention has the advantages and technical effects that: the method of coating the high-performance catalyst on the surface of the conductive ionic membrane is adopted, and the high-efficiency performance of the anode side reaction is realized through the titanium mesh, the titanium fiber felt, the conductive ionic membrane and the carbon felt which are sequentially arranged, so that the catalytic component for preparing the vanadium electrolyte is obtained. The electrolysis is performed by the catalytic component, so that the electrolysis current density can be increased, and the electrolysis voltage can be reduced. Meanwhile, when the catalyst fails, only the conductive ionic membrane needs to be replaced, so that the maintenance difficulty is reduced. The anode side of the catalytic component is a gas-liquid transmission channel formed by a titanium net/titanium fiber felt, and plays a role in reducing resistance; the cathode side adopts carbon felt to play a role in catalyzing the reduction reaction of vanadium.
In the embodiment of the invention, the catalytic component is manufactured by directly coating the oxygen evolution catalyst on the anode side of the conductive ionic membrane, and the water decomposition reaction directly occurs on the membrane, so that the water decomposition reaction can be kept only by keeping the membrane in a wet state. No additional replenishment of anolyte is required, as the membrane can conduct water molecules and hold itself in a wet state. Anolyte may be additionally supplemented for maintaining the membrane in a wet state and stable operation. In addition, the catalytic component adopts titanium material to fill the pores between the membrane and the electrode plate, so that electrons can be directly transferred between the reaction part and the electrode plate, and high-concentration sulfuric acid is not needed to be used as electrolyte, thereby being beneficial to reducing the corrosion of the electrode plate.
In some embodiments, the first catalyst is an iridium-based catalyst; preferably, the iridium-based catalyst comprises at least one of iridium black, iridium oxide supported iridium, and titanium oxide supported iridium oxide;
And/or the loading of the first catalyst on the conductive ionic membrane is 0.5-5 mg/cm 2;
and/or the thickness of the conductive ionic membrane is 250-500 μm;
And/or, the titanium mesh supports a second catalyst on one side or both sides in the thickness direction thereof; the second catalyst comprises at least one of a ruthenium-based catalyst, an iridium-based catalyst and a platinum-based catalyst;
And/or, the surface of the titanium fiber felt is loaded with a third catalyst; the third catalyst comprises at least one of ruthenium-based catalyst, iridium-based catalyst and platinum-based catalyst;
And/or the conductive ionic membrane is loaded with a fourth catalyst on one side connected with the carbon felt; the fourth catalyst comprises a carbon-based catalyst.
The embodiment of the invention provides a vanadium electrolyte electrolysis device, which comprises an electrolysis cell, wherein the electrolysis cell comprises a first bipolar plate, an anode liquid flow frame, a catalytic assembly, a cathode liquid flow frame and a second bipolar plate which are sequentially arranged, and the catalytic assembly is the catalytic assembly provided by the embodiment of the invention.
In the embodiment of the present invention, all advantages of the catalytic assembly are provided, and will not be described herein. Compared with a conventional electrolytic pile, the electrolytic device matched with the catalytic assembly has the advantages that electrolyte does not need to be added to the anode side, an electrolyte inlet is not needed to be arranged, the preparation and the supplement of the anolyte can be omitted, the anolyte flow frame is only provided with a gas-water mixture outlet, and an anode liquid storage tank and an anolyte circulation device are omitted. The vanadium electrolyte electrolysis device has high current density, low electrolysis voltage and relatively simple configuration, reduces required sealing elements, reduces the possibility of liquid leakage, is beneficial to reducing cost and occupied area and improves efficiency.
In some embodiments, the number of the electrolytic cells in the vanadium electrolyte electrolytic device is 2-80, the plurality of electrolytic cells are connected in sequence, and the first bipolar plate of one of two adjacent electrolytic cells and the second bipolar plate of the other electrolytic cell are the same bipolar plate.
In some embodiments, the vanadium electrolyte electrolysis device is further provided with an anode end plate, an anode insulating plate, an anode current collecting plate, a cathode end plate, a cathode insulating plate and a cathode current collecting plate, wherein the anode end plate, the anode insulating plate, the anode current collecting plate, the electrolytic cell, the cathode current collecting plate, the cathode insulating plate and the cathode end plate are sequentially arranged.
In some embodiments, the cathode end plate is provided with a cathode end plate liquid inlet and a cathode end plate liquid outlet;
the anode end plate is provided with an anode end plate outlet;
The catholyte flow frame is provided with a catholyte inlet and a catholyte outlet;
the anode liquid flow frame is provided with a gas-water mixture outlet;
The vanadium electrolyte electrolysis device also comprises a catholyte storage tank; the catholyte storage tank is provided with a catholyte storage tank inlet and a catholyte storage tank outlet;
The liquid inlet of the cathode end plate, the catholyte inlet of the catholyte flow frame of the electrolytic cell and the outlet of the catholyte storage tank are communicated; the liquid outlet of the cathode end plate, the catholyte outlet of the catholyte flow frame of the electrolytic cell and the inlet of the catholyte storage tank are communicated;
The outlet of the anode end plate, the outlet of the gas-water mixture of the anode liquid flow frame of the electrolytic cell and the outside of the vanadium electrolyte electrolytic device are communicated.
In some embodiments, the cathode end plate is provided with a cathode end plate liquid inlet and a cathode end plate liquid outlet;
The anode end plate is provided with an anode end plate liquid inlet and an anode end plate liquid outlet;
The catholyte flow frame is provided with a catholyte inlet and a catholyte outlet;
The anolyte flow frame is provided with an anolyte inlet and an anolyte outlet;
The vanadium electrolyte electrolysis device also comprises a catholyte storage tank and an anolyte storage tank; the catholyte storage tank is provided with a catholyte storage tank inlet and a catholyte storage tank outlet; the anolyte storage tank is provided with an anolyte storage tank inlet and an anolyte storage tank outlet;
The liquid inlet of the cathode end plate, the catholyte inlet of the catholyte flow frame of the electrolytic cell and the outlet of the catholyte storage tank are communicated; the liquid outlet of the cathode end plate, the catholyte outlet of the catholyte flow frame of the electrolytic cell and the inlet of the catholyte storage tank are communicated;
the liquid inlet of the anode end plate, the anode liquid inlet of the anode liquid flow frame of the electrolytic cell and the outlet of the anode liquid storage tank are communicated; the liquid outlet of the anode end plate, the anolyte outlet of the anolyte flow frame of the electrolytic cell and the inlet of the anolyte storage tank are communicated.
The embodiment of the invention provides a preparation method of vanadium electrolyte, which comprises the steps of carrying out electrolysis by adopting the vanadium electrolyte electrolysis device provided by the embodiment of the invention, and stopping electrolysis after the required vanadium electrolyte is obtained.
In the embodiment of the invention, the anode side does not need to be added with electrolyte, and an anode liquid storage tank and an anode liquid circulating device are omitted. The vanadium electrolyte has high current density, low electrolysis voltage and relatively simple configuration in the preparation process, and reduces required sealing elements and liquid leakage possibility.
In some embodiments, the vanadium electrolyte electrolysis apparatus has a cathode side and an anode side, the cathode side incorporating catholyte; adding an anode solution to the anode side; or, the anode side is not added with an anolyte.
In some embodiments, the catholyte comprises a tetravalent vanadium solution and/or a pentavalent vanadium solution;
And/or the concentration of the catholyte is 1-4mol/L;
And/or, the anolyte comprises water or sulfuric acid solution;
And/or the current density of the electrolysis is 0.1-3A/cm 2;
and/or the temperature of the electrolysis is 20-50 ℃.
Drawings
FIG. 1 is a schematic view of a catalytic assembly of the present invention.
FIG. 2 is a schematic view of a vanadium electrolyte electrolysis apparatus in accordance with one embodiment of the invention.
FIG. 3 is a schematic view of a vanadium electrolyte electrolysis apparatus according to another embodiment of the invention.
Reference numerals:
Titanium mesh 1, titanium fiber felt 2, conductive ionic membrane 3, carbon felt 4, anode end plate 5, anode insulating plate 6, anode current collecting plate 7, first bipolar plate 8, anode flow frame 9, cathode flow frame 10, second bipolar plate 11, vanadium electrolyte electrolyzer 12, electrolysis power supply 13, cathode end plate liquid outlet 14, cathode end plate liquid inlet 15, cathode liquid storage tank 16, anode end plate outlet 17.
Detailed Description
Reference will now be made in detail to embodiments of the present invention, examples of which are illustrated in the accompanying drawings. The embodiments described below by referring to the drawings are illustrative and intended to explain the present invention and should not be construed as limiting the invention.
As shown in fig. 1, a catalytic assembly according to an embodiment of the present invention includes: the titanium mesh 1, the titanium fiber felt 2, the conductive ion membrane 3 and the carbon felt 4 are sequentially arranged; the conductive ionic membrane 3 supports a first catalyst on the side connected to the titanium fiber felt 2.
According to the catalytic component provided by the embodiment of the invention, a method of coating a high-performance catalyst on the surface of the conductive ionic membrane is adopted, and the high-efficiency performance of the anode side reaction is realized through the titanium mesh, the titanium fiber felt, the conductive ionic membrane and the carbon felt which are sequentially arranged, so that the catalytic component for preparing the vanadium electrolyte is obtained. The electrolysis is performed by the catalytic component, so that the electrolysis current density can be increased, and the electrolysis voltage can be reduced. Meanwhile, when the catalyst fails, only the conductive ionic membrane needs to be replaced, so that the maintenance difficulty is reduced. The anode side of the catalytic component is a gas-liquid transmission channel formed by a titanium net/titanium fiber felt, and plays a role in reducing resistance; the cathode side adopts carbon felt to play a role in catalyzing the reduction reaction of vanadium.
In the embodiment of the invention, the catalytic component is manufactured by directly coating the oxygen evolution catalyst on the anode side of the conductive ionic membrane, and the water decomposition reaction directly occurs on the membrane, so that the water decomposition reaction can be kept only by keeping the membrane in a wet state. No additional replenishment of anolyte is required, as the membrane can conduct water molecules and hold itself in a wet state. Anolyte may be additionally supplemented for maintaining the membrane in a wet state and stable operation. In addition, the catalytic component adopts titanium material to fill the pores between the membrane and the electrode plate, so that electrons can be directly transferred between the reaction part and the electrode plate, and high-concentration sulfuric acid is not needed to be used as an anode side electrolyte, thereby being beneficial to reducing the corrosion of the electrode plate.
In some embodiments, the catalytic assembly is used for the electrolytic preparation of vanadium electrolyte.
In some embodiments, the first catalyst is an iridium-based catalyst; preferably, the iridium-based catalyst includes at least one of iridium black, iridium oxide supported iridium catalyst (iridium/iridium oxide), titanium oxide supported iridium oxide catalyst (iridium oxide/titanium oxide), preferably titanium oxide supported iridium oxide catalyst; optionally, in the iridium oxide supported iridium catalyst, the mass percentage of iridium element in the catalyst is 80% -95%, specifically, for example, 80%,82%,85%,88%,90%,92%,95%; optionally, in the titanium oxide supported iridium oxide catalyst, the mass percentage of iridium is 20% -70%, specifically, for example, 20%,30%,35%,40%,50%,60%,70%.
Optionally, the titanium oxide-supported iridium oxide catalyst is prepared by a colloid method; specifically, for example, a precursor of titanium oxide is synthesized into titanium oxide by a plasma method to obtain a titanium oxide suspension; adding the iridium-containing precursor solution into the titanium oxide suspension, drying, and calcining to obtain a titanium oxide-supported iridium oxide catalyst; the iridium precursor is selected from at least one of iridium-containing compounds, for example, at least one of chloroiridic acid (H 2IrCl6) or iridium trichloride (IrCl 3); preparing an iridium precursor into a solution to obtain a solution containing the iridium precursor; the precursor of the titanium oxide is selected from titanium tetraisopropoxide; the drying temperature is 60-80 ℃; the calcining temperature is 200-300 ℃; the calcination time is 2-4 hours.
In the embodiment of the invention, the first catalyst is optimized, so that the overpotential of the anode is reduced, and the electrolytic voltage is further reduced. The carrier of iridium oxide/titanium oxide is titanium dioxide, so that the dispersion of the catalyst can be promoted, the activity of the catalyst is improved, the noble metal loading in the catalyst is reduced, meanwhile, the titanium oxide serving as the carrier has good chemical stability and mechanical strength, and good stability can be provided under severe electrolysis conditions, so that the service life of the catalyst is prolonged. The iridium-based catalyst support does not employ a carbon support because carbon is easily oxidized to CO 2 at high voltage.
In some embodiments, the loading of the first catalyst on the conductive ionic membrane 3 is 0.5-5 mg/cm 2, specifically, for example ,0.5mg/cm2,1mg/cm2,1.5mg/cm2,2mg/cm2,3mg/cm2,4mg/cm2,5mg/cm2. in the embodiments of the present invention, the anode overpotential is reduced, and the electrolytic voltage is further reduced by adjusting the loading of the first catalyst. The catalytic effect is not obvious when the loading is too low, and the cost is increased when the loading is too high.
In some embodiments, the first catalyst is supported on the electrically conductive ionic membrane 3, optionally in a manner that includes at least one of transfer printing, electrochemical deposition, or ultrasonic spraying.
In some embodiments, the thickness of the conductive ionic membrane 3 is 250-500 μm, in particular, for example, 250 μm,300 μm,350 μm,400 μm,450 μm,500 μm; and/or, the conductive ion membrane 3 is a perfluorosulfonic acid proton exchange membrane. In the embodiment of the invention, the current conductive ionic membrane, for example, the conductive ionic membrane for a flow battery is generally 50-150 mu m in thickness, and the catalytic assembly for preparing the vanadium electrolyte is prepared by adopting the conductive ionic membrane with the thickness of more than 200 mu m, has thicker membrane thickness, has the effects of reinforcing support and vanadium resistance, and is further beneficial to preparing the vanadium electrolyte.
In some embodiments, the titanium mesh 1 is one or more layers.
In some embodiments, the titanium mesh 1 supports the second catalyst on one or both sides in the thickness direction thereof; optionally, the second catalyst comprises at least one of a ruthenium-based catalyst, an iridium-based catalyst, and a platinum-based catalyst; optionally, the iridium-based catalyst comprises at least one of iridium black, iridium oxide supported iridium catalyst and titanium oxide supported iridium oxide catalyst; the ruthenium-based catalyst comprises ruthenium oxide; the platinum-based catalyst comprises platinum black; the loading capacity of the second catalyst is 0.5-5.0mg/cm 2, specifically, for example, ,0.5mg/cm2,1mg/cm2,1.5mg/cm2,2mg/cm2,3mg/cm2,4mg/cm2,5mg/cm2. in the embodiment of the invention, the second catalyst is supported by the titanium mesh, which is favorable for further reducing the electrolysis voltage and prolonging the service life.
In some embodiments, the second catalyst is supported by at least one of transfer printing, electrochemical deposition, or ultrasonic spraying.
In some embodiments, the surface of the titanium fiber mat 2 carries a third catalyst; optionally, the third catalyst comprises at least one of a ruthenium-based catalyst, an iridium-based catalyst, and a platinum-based catalyst; optionally, the iridium-based catalyst comprises at least one of iridium black, iridium oxide supported iridium catalyst and titanium oxide supported iridium oxide catalyst; the ruthenium-based catalyst comprises ruthenium oxide; the platinum-based catalyst comprises platinum black; the third catalyst has a loading of 0.5-5.0mg/cm 2, and specifically, for example, ,0.5mg/cm2,1mg/cm2,1.5mg/cm2,2mg/cm2,3mg/cm2,4mg/cm2,5mg/cm2. in the embodiment of the invention, the third catalyst is supported by the titanium fiber felt, which is favorable for further reducing the electrolysis voltage and prolonging the service life.
In some embodiments, the third catalyst is supported by at least one of transfer printing, electrochemical deposition, or ultrasonic spraying.
In some embodiments, the electrically conductive ionic membrane 3 is supported with a fourth catalyst on the side connected to the carbon felt 4; the fourth catalyst includes a carbon-based catalyst, specifically, for example, conductive carbon black, a conductive carbon black supported MOF type catalyst; the loading capacity of the fourth catalyst is 0.5-5.0mg/cm 2, specifically, for example, ,0.5mg/cm2,1mg/cm2,1.5mg/cm2,2mg/cm2,3mg/cm2,4mg/cm2,5mg/cm2. in the embodiment of the invention, the fourth catalyst is loaded by the conductive ion membrane, which is favorable for further reducing the electrolysis voltage, improving the electrolysis efficiency and prolonging the service life.
In some embodiments, the fourth catalyst is supported by at least one of transfer printing, electrochemical deposition, or ultrasonic spraying.
In some embodiments, the catalytic assembly is integral.
As shown in fig. 2, a vanadium electrolyte electrolysis device 12 according to an embodiment of the present invention includes an electrolysis cell, where the electrolysis cell includes a first bipolar plate 8, an anode flow frame 9, a catalytic assembly, a cathode flow frame 10, and a second bipolar plate 11, which are sequentially arranged, and the catalytic assembly is a catalytic assembly according to the embodiment of the present invention.
In the embodiment of the present invention, all advantages of the catalytic assembly are provided, and will not be described herein. Compared with a conventional electrolytic pile, the electrolytic device matched with the catalytic assembly has the advantages that electrolyte does not need to be added to the anode side, an electrolyte inlet is not needed to be arranged, the preparation and the supplement of the anolyte can be omitted, the anolyte flow frame is only provided with a gas-water mixture outlet, and an anode liquid storage tank and an anolyte circulation device are omitted. The vanadium electrolyte electrolysis device has high current density, low electrolysis voltage and relatively simple configuration, reduces required sealing elements, reduces the possibility of liquid leakage, is beneficial to reducing cost and occupied area and improves efficiency.
In some embodiments, the vanadium electrolyte electrolysis apparatus 12 is used to prepare a vanadium electrolyte.
In some embodiments, the titanium mesh 1 of the catalytic assembly is adjacent to the anolyte flow frame 9; the carbon felt 4 of the catalytic assembly is adjacent to the cathode flow frame 10.
In some embodiments, the anode current collector plate 7 is selected from a graphite plate or a metal plate, alternatively a titanium plate or a copper plate; and/or the cathode current collector plate is selected from a graphite plate or a metal plate, optionally a titanium plate or a copper plate.
In some embodiments, seals are provided between the first bipolar plate 8 and the anode flow frame 9, between the anode flow frame 9 and the catalytic component, between the catalytic component and the cathode flow frame 10, and between the cathode flow frame 10 and the second bipolar plate 11 for sealing, optionally, the seals are sealing gaskets or sealing washers, and the materials of the seals are at least one of silica gel, fluororubber, polyethylene, polypropylene, polyvinyl chloride or polytetrafluoroethylene.
In some embodiments, the number of cells in the vanadium electrolyte electrolysis device 12 is 2-80, specifically, for example, 2,3,4,5,6,7,8,9, 10, 20, 30, 40, 50, 60, 70, 80; the multiple electrolytic cells are connected in turn, the first bipolar plate 8 of one of the two adjacent electrolytic cells and the second bipolar plate 11 of the other are the same bipolar plate, namely the two adjacent electrolytic cells share one bipolar plate, one side of the bipolar plate is the anode flow frame 9 of one of the two adjacent electrolytic cells, and the other side of the bipolar plate is the cathode flow frame 10 of the other of the two adjacent electrolytic cells.
In some embodiments, the vanadium electrolyte electrolysis device is further provided with an anode end plate 5, an anode insulating plate 6, an anode current collecting plate 7, a cathode end plate, a cathode insulating plate and a cathode current collecting plate, wherein the anode end plate 5, the anode insulating plate 6, the anode current collecting plate 7, the electrolytic cell, the cathode current collecting plate, the cathode insulating plate and the cathode end plate are sequentially arranged.
In some embodiments, sealing elements are arranged between the anode end plate 5 and the anode insulating plate 6, between the anode insulating plate 6 and the anode current collecting plate 7, between the anode current collecting plate 7 and the electrolytic cell, between the electrolytic cell and the cathode current collecting plate, between the cathode current collecting plate and the cathode insulating plate, and between the cathode insulating plate and the cathode end plate for sealing, optionally, the sealing elements are sealing gaskets or sealing washers, and the sealing elements are made of at least one of silica gel, fluororubber, polyethylene, polypropylene, polyvinyl chloride or polytetrafluoroethylene.
In some embodiments, the anode current collector 7 is on one side the anode insulating plate 6 and on the other side the first bipolar plate 8 of the cell; the first bipolar plate 8 connected to the anode current collecting plate 7 functions as a single electrode plate only, or the first bipolar plate 8 connected to the anode current collecting plate 7 adopts a single electrode plate.
In some embodiments, the cathode collector plate is on one side a cathode insulator plate and on the other side a second bipolar plate 11 of the cell; the second bipolar plate connected to the cathode current collector serves as a single electrode plate only, or the second bipolar plate connected to the cathode current collector employs a single electrode plate.
In some embodiments, as shown in fig. 3, a cathode end plate is provided with a cathode end plate liquid inlet 15 and a cathode end plate liquid outlet 14; the anode end plate 5 is provided with an anode end plate outlet 17; the catholyte frame 10 is provided with a catholyte inlet and a catholyte outlet; the anode liquid flow frame 9 is provided with a gas-water mixture outlet; the vanadium electrolyte electrolysis device 12 further comprises a catholyte storage tank 16; the catholyte tank 16 is provided with a catholyte tank inlet and a catholyte tank outlet; the cathode end plate liquid inlet 15, the catholyte inlet of the catholyte flow frame 10 of the electrolytic cell and the outlet of the catholyte storage tank are communicated; the cathode end plate liquid outlet 14, the catholyte outlet of the catholyte flow frame 10 of the electrolytic cell and the catholyte storage tank inlet are communicated; the anode end plate outlet 17, the gas-water mixture outlet of the anode liquid flow frame 9 of the electrolytic cell and the outside of the vanadium electrolyte electrolysis device 12 are communicated; i.e., the vanadium electrolyte electrolyzer 12 does not include an anolyte reservoir and does not contain anolyte.
In the embodiment of the invention, unlike other vanadium electrolyte preparation devices, the anode liquid flow frame of the vanadium electrolyte electrolysis device is only provided with the gas-water mixture outlet, and the anode does not need to be added with electrolyte, so that an electrolyte inlet is not provided, the preparation and the supplement of the anode electrolyte can be omitted, an anode liquid storage tank and an anode liquid circulation device are omitted, the anode electrochemical corrosion caused by direct contact of a bipolar plate with acidic liquid is avoided, and therefore, a material with more common material can be adopted as a bipolar plate, and the production cost is reduced; or extend the life of the bipolar plate with the same material.
In some embodiments, the gas-water mixture outlets of the anolyte flow frame 9 of the plurality of electrolytic cells are in communication via a first flow channel; the anode end plate outlet 17, the first flow passage, and the outside of the vanadium electrolyte electrolysis device 12 communicate.
In some embodiments, catholyte inlets of the catholyte flow frame 10 of the plurality of cells are in communication through a second flow passage, and the cathode end plate inlet 15, the second flow passage, and the catholyte reservoir outlet are in communication; the catholyte outlet of the catholyte flow frame 10 is connected by a third flow passage, and the catholyte end plate liquid outlet 14, the third flow passage and the catholyte storage tank inlet are connected.
In some embodiments, the system further comprises a gas-liquid separation device for separating the gas-water mixture into gas and liquid, optionally, evacuating the gas, and sending the liquid to an external water treatment device or recycling; optionally, the anode end plate outlet 17, the gas-water mixture outlet of the anode liquid flow frame 9 and the gas-liquid separation device are communicated.
In some embodiments, a first circulation pump is also included for circulating catholyte between catholyte frame 10 and catholyte reservoir 16. In the embodiment of the invention, catholyte enters the catholyte frame through a first circulating pump in a catholyte storage tank, a liquid flowing channel is arranged on the catholyte frame, and the catholyte flows out through a liquid flow channel on the catholyte frame after entering the catholyte frame and being dispersed to a catalytic assembly, so that circulating flow is formed.
In some embodiments, a cathode end plate liquid inlet 15 and a cathode end plate liquid outlet 14 are arranged on the cathode end plate; the anode end plate 5 is provided with an anode end plate liquid inlet and an anode end plate liquid outlet; the catholyte frame 10 is provided with a catholyte inlet and a catholyte outlet; the anolyte flow frame 9 is provided with an anolyte inlet and an anolyte outlet; the vanadium electrolyte electrolysis device 12 further comprises a catholyte storage tank 16 and an anolyte storage tank; the catholyte tank 16 is provided with a catholyte tank inlet and a catholyte tank outlet; the anolyte storage tank is provided with an anolyte storage tank inlet and an anolyte storage tank outlet; the cathode end plate liquid inlet 15, the catholyte inlet of the catholyte flow frame 10 of the electrolytic cell and the outlet of the catholyte storage tank are communicated; the cathode end plate liquid outlet 14, the catholyte outlet of the catholyte flow frame 10 of the electrolytic cell and the catholyte storage tank inlet are communicated; the liquid inlet of the anode end plate, the anode liquid inlet of the anode liquid flow frame 9 of the electrolytic cell and the outlet of the anode liquid storage tank are communicated; the liquid outlet of the anode end plate, the anode liquid outlet of the anode liquid flow frame 9 of the electrolytic cell and the inlet of the anode liquid storage tank are communicated.
In some embodiments, the anolyte inlets of the anolyte flow frames 9 of the plurality of electrolytic cells are communicated through a fourth flow channel, and the anolyte inlet of the anode end plate, the fourth flow channel and the anolyte storage tank outlet are communicated; the anolyte outlet of the anolyte frame 9 is communicated through a fifth runner, and the liquid outlet of the anode end plate, the fifth runner and the anolyte storage tank inlet are communicated.
In some embodiments, a second circulation pump is further included for circulating anolyte between anolyte frame 9 and the anolyte storage tank.
In some embodiments, the vanadium electrolyte electrolysis apparatus 12 further comprises an electrolysis power supply 13.
According to the preparation method of the vanadium electrolyte, the vanadium electrolyte electrolysis device 12 is adopted for electrolysis, and the electrolysis is stopped after the required vanadium electrolyte is obtained. In the embodiment of the invention, the anode side does not need to be added with electrolyte, and an anode liquid storage tank and an anode liquid circulating device are omitted. The vanadium electrolyte has high current density, low electrolysis voltage and relatively simple configuration in the preparation process, and reduces required sealing elements and liquid leakage possibility.
In some embodiments, the vanadium electrolyte electrolyzer 12 has a cathode side and an anode side, the cathode side incorporating catholyte.
In some embodiments, the anode side is added with an anolyte.
In some embodiments, the anode side is free of added anolyte; the anode side produces a gas-water mixture comprising oxygen and water.
In the embodiment of the invention, the anode does not need to be added with electrolyte, so that the preparation and the supplement of the anolyte are omitted, an anode liquid storage tank and an anolyte circulating device are omitted, the electrochemical corrosion of the anode caused by direct contact of the bipolar plate with acidic liquid is avoided, a material with more common material can be adopted as the bipolar plate, and the production cost is reduced; or extend the life of the bipolar plate with the same material. The water molecules on the cathode side reach the anode side of the membrane through permeation, lose electrons directly under the action of a catalyst on the surface of the membrane, and decompose into oxygen; oxygen and water on the anode side are directly discharged through the outlet, and electrons are transferred between an external circuit, bipolar plates, titanium mesh, titanium fiber felt, membranes, etc.
In some embodiments, the catholyte comprises a tetravalent vanadium solution and/or a pentavalent vanadium solution, optionally an vanadyl sulfate solution; and/or the concentration of the catholyte is 1 to 4mol/L, specifically, for example, 1mol/L,2mol/L,3mol/L,4mol/L; optionally, the catholyte further comprises sulfuric acid having a concentration of 1-4mol/L, specifically, for example, 1mol/L,2mol/L,3mol/L,4mol/L.
In some embodiments, the anolyte comprises water or sulfuric acid solution; alternatively, the concentration of the sulfuric acid solution is 0 to 4mol/L, specifically, for example, 0.1mol/L,1mol/L,2mol/L,3mol/L,4mol/L.
In some embodiments, the current density is 0.1-3A/cm 2, particularly, e.g ,0.1A/cm2,0.3A/cm2,0.5A/cm2,0.8A/cm2,1A/cm2,2A/cm2,3A/cm2.
In some embodiments, the temperature of the electrolysis is 20-50 ℃, specifically, for example, 20 ℃,25 ℃,30 ℃,40 ℃,50 ℃.
In some embodiments, the electrolysis time is determined through calculation according to the concentration of the catholyte and the valence state of the required vanadium electrolyte, and when the endpoint is approached, the electrolysis is stopped after the required vanadium electrolyte is obtained through sampling detection or through an online detection device.
The invention will now be described with reference to specific examples, which are intended to be illustrative only and not limiting in any way.
Example 1
The preparation method of the vanadium electrolyte adopts a vanadium electrolyte electrolysis device 12 shown in figures 2 and 3 to carry out electrolysis, the number of electrolytic cells is 1, the thickness of the conductive ion membrane 3 in a catalytic assembly (the effective area is 5 x 5cm 2) is 300 mu m, the conductive ion membrane 3 is loaded with a first catalyst on one side connected with the titanium fiber felt 2, the first catalyst is titanium oxide loaded iridium oxide catalyst, the mass percentage of iridium is 35%, and the loading amount of the first catalyst on the conductive ion membrane 3 is 1mg/cm 2. The first bipolar plate 8 and the second bipolar plate 11 are both titanium plates. The vanadium electrolyte electrolysis device 12 does not comprise an anolyte storage tank and does not add anolyte; and adding a cathode liquid on the cathode side, wherein the cathode liquid is 1L of electrolyte containing 2mol/L vanadyl sulfate and 3.5mol/L sulfuric acid.
During electrolysis, the current of 5A and the current density of 0.2A/cm 2 reduce the vanadium in 1L of 2mol/L electrolyte from +4 to +3.5 (i.e. the molar ratio of 3-valent vanadium to 4-valent vanadium is 1:1). The electrolysis time is about 320 minutes, and the total electrolysis voltage of the vanadium electrolyte electrolysis device 12 is less than 3.0V.
Example 2
The same procedure as in example 1 was followed except that the vanadium electrolyte electrolysis apparatus 12 included an anolyte storage tank to which an anolyte was added, the anolyte being water.
In the electrolysis process, the current is 5A, the current density is 0.2A/cm 2, and 1L of vanadium in the 2mol/L electrolyte is reduced from +4 valence to +3.5 valence. The electrolysis time is about 320 minutes, and the total electrolysis voltage of the vanadium electrolyte electrolysis device 12 is less than 3.2V.
Example 3
The same procedure as in example 1 was followed except that the number of electrolytic cells was 2 and the loading of the first catalyst on the conductive ionic membrane 3 was 0.5mg/cm 2.
In the electrolysis process, the current is 10A, the current density is 0.4A/cm 2, and 1L of vanadium in the 2mol/L electrolyte is reduced from +4 to +3.5. The electrolysis time is about 80 minutes, and the total electrolysis voltage of the vanadium electrolyte electrolysis device 12 is less than 7.0V.
Example 4
The same method as in example 3, except that the conductive ionic membrane 3 was supported with a fourth catalyst on the side connected to the carbon felt 4; the fourth catalyst is a conductive carbon black-supported MOF type catalyst, and the loading capacity of the fourth catalyst on the conductive ionic membrane 3 is 2mg/cm 2.
During the electrolysis, the current is 25A, the current density is 1A/cm 2, and 1L of vanadium in the 2mol/L electrolyte is reduced from +4 to +3.5. The electrolysis time is about 30 minutes, and the total electrolysis voltage of the vanadium electrolyte electrolysis device 12 is less than 7.2V.
Example 5
The same procedure as in example 3 was repeated except that the first catalyst used was an iridium oxide-supported iridium catalyst, and the loading of the first catalyst on the conductive ionic membrane 3 was 2.0mg/cm 2.
In the electrolysis process, the current is 10A, the current density is 0.4A/cm 2, and 1L of vanadium in the 2mol/L electrolyte is reduced from +4 to +3.5. The electrolysis time is about 80 minutes, and the total electrolysis voltage of the vanadium electrolyte electrolysis device 12 is less than 2.8V.
Example 6
The same procedure as in example 3 was followed except that the number of electrolytic cells was 20.
In the electrolysis process, the current is 10A, the current density is 0.4A/cm 2, and 1L of vanadium in the 2mol/L electrolyte is reduced from +4 to +3.5. The electrolysis time is about 8 minutes, and the total voltage of the electrolysis cell is less than 72V.
Comparative example 1
The preparation method of the vanadium electrolyte comprises the steps that an iridium oxide coating titanium electrode is adopted as an anode, a carbon felt and carbon plastic composite electrode is adopted as a cathode, a 200-mu m conductive ionic membrane is adopted as a conductive ionic membrane, and the effective area of the electrode is 25cm 2. The anode liquid adopts 2mol/L sulfuric acid, and the cathode liquid adopts 1L electrolyte of 2mol/L vanadyl sulfate and 3.5mol/L sulfuric acid.
In the electrolysis process, the current is 2.5A, the current density is 0.1A/cm 2, the vanadium in 1L of 2mol/L electrolyte is reduced from +4 to +3.5 (namely 3-4 vanadium is 1:1), the electrolysis time is about 660 minutes, and the electrolysis voltage is 3.3-3.7V.
Comparative example 2
The same procedure as in example 3 was followed except that the first catalyst was not supported on the conductive ionic membrane 3.
In the electrolysis process, the current is 2.5A, the current density is 0.1A/cm 2, the vanadium in 1L of 2mol/L electrolyte is reduced from +4 to +3.5, the voltage is suddenly increased in the electrolysis process, and the electrolysis process cannot be successfully completed. This is because comparative example 2 does not support the first catalyst, and the water decomposition potential is too high, resulting in high electrode potential, severe electrochemical corrosion, and rapid corrosion failure of the electrode plate.
Comparative example 3
The same procedure as in example 3 was followed except that the thickness of the conductive ionic membrane 3 was 50. Mu.m.
In the electrolysis process, the current is 2.5A, the current density is 0.1A/cm 2, and 1L of vanadium in the 2mol/L electrolyte is reduced from +4 valence to +3.5 valence. In the electrolysis process, the permeation speed of water molecules through the membrane is too high, the membrane thickness is small, and the performance of blocking the concentration of vanadium ions is poor, so that a gas-water mixture carrying vanadium ions flows out from an outlet on the anode side, and the loss of vanadium and the concentration change of vanadium electrolyte on the cathode side are caused.
Comparative example 4
The same procedure as in example 3 was followed except that the first catalyst on the conductive ionic membrane 3 was carbon black-supported iridium oxide, the carbon black was XC72, the mass percentage of iridium oxide was 50%, and the loading was 0.5mg/cm 2.
In the electrolysis process, the carbon black is oxidized, the catalyst rapidly drops and is pulverized, so that the voltage of the electrolytic cell is increased, the electrode plate is severely corroded by electrochemistry, and the electrolytic cell is destroyed and fails.
Furthermore, the terms "first," "second," and the like, are used for descriptive purposes only and are not to be construed as indicating or implying a relative importance or implicitly indicating the number of technical features indicated. Thus, a feature defining "a first" or "a second" may explicitly or implicitly include at least one such feature. In the description of the present invention, the meaning of "plurality" means at least two, for example, two, three, etc., unless specifically defined otherwise.
In the present invention, unless explicitly specified and limited otherwise, the terms "mounted," "connected," "secured," and the like are to be construed broadly, and may be, for example, fixedly connected, detachably connected, or integrally formed; may be mechanically connected, may be electrically connected or may be in communication with each other; either directly or indirectly, through intermediaries, or both, may be in communication with each other or in interaction with each other, unless expressly defined otherwise. The specific meaning of the above terms in the present invention can be understood by those of ordinary skill in the art according to the specific circumstances.
In the present invention, unless expressly stated or limited otherwise, a first feature "up" or "down" a second feature may be the first and second features in direct contact, or the first and second features in indirect contact via an intervening medium. Moreover, a first feature being "above," "over" and "on" a second feature may be a first feature being directly above or obliquely above the second feature, or simply indicating that the first feature is level higher than the second feature. The first feature being "under", "below" and "beneath" the second feature may be the first feature being directly under or obliquely below the second feature, or simply indicating that the first feature is less level than the second feature.
For purposes of this disclosure, the terms "one embodiment," "some embodiments," "example," "a particular example," or "some examples," etc., mean that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the invention. In this specification, schematic representations of the above terms are not necessarily directed to the same embodiment or example. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples. Furthermore, the different embodiments or examples described in this specification and the features of the different embodiments or examples may be combined and combined by those skilled in the art without contradiction.
While the above embodiments have been shown and described, it should be understood that the above embodiments are illustrative and not to be construed as limiting the invention, and that variations, modifications, alternatives, and variations of the above embodiments may be made by those of ordinary skill in the art without departing from the scope of the invention.
Claims (10)
1. A catalytic assembly comprising a substrate and a catalytic layer, characterized by comprising the following steps: the titanium mesh, the titanium fiber felt, the conductive ion membrane and the carbon felt are sequentially arranged; the conductive ionic membrane is loaded with a first catalyst on one side connected with the titanium fiber felt.
2. The catalytic assembly of claim 1 wherein the first catalyst is an iridium-based catalyst; the iridium-based catalyst comprises at least one of iridium black, iridium oxide-supported iridium and titanium oxide-supported iridium oxide;
And/or the loading of the first catalyst on the conductive ionic membrane is 0.5-5 mg/cm 2;
and/or the thickness of the conductive ionic membrane is 250-500 μm;
And/or, the titanium mesh supports a second catalyst on one side or both sides in the thickness direction thereof; the second catalyst comprises at least one of a ruthenium-based catalyst, an iridium-based catalyst and a platinum-based catalyst;
And/or, the surface of the titanium fiber felt is loaded with a third catalyst; the third catalyst comprises at least one of ruthenium-based catalyst, iridium-based catalyst and platinum-based catalyst;
And/or the conductive ionic membrane is loaded with a fourth catalyst on one side connected with the carbon felt; the fourth catalyst comprises a carbon-based catalyst.
3. A vanadium electrolyte electrolysis device, which is characterized by comprising an electrolysis cell, wherein the electrolysis cell comprises a first bipolar plate, an anode flow frame, a catalytic component, a cathode flow frame and a second bipolar plate which are sequentially arranged, and the catalytic component is the catalytic component of claim 1 or 2.
4. A vanadium electrolyte electrolysis device according to claim 3, wherein the number of the electrolysis cells in the vanadium electrolyte electrolysis device is 2-80, a plurality of electrolysis cells are connected in sequence, and the first bipolar plate of one of two adjacent electrolysis cells and the second bipolar plate of the other are the same bipolar plate.
5. The vanadium electrolyte electrolysis device according to claim 3, further comprising an anode end plate, an anode insulating plate, an anode current collecting plate, a cathode end plate, a cathode insulating plate and a cathode current collecting plate, wherein the anode end plate, the anode insulating plate, the anode current collecting plate, the electrolytic cell, the cathode current collecting plate, the cathode insulating plate and the cathode end plate are sequentially arranged.
6. The vanadium electrolyte electrolysis device according to claim 5, wherein the cathode end plate is provided with a cathode end plate liquid inlet and a cathode end plate liquid outlet;
the anode end plate is provided with an anode end plate outlet;
The catholyte flow frame is provided with a catholyte inlet and a catholyte outlet;
the anode liquid flow frame is provided with a gas-water mixture outlet;
The vanadium electrolyte electrolysis device also comprises a catholyte storage tank; the catholyte storage tank is provided with a catholyte storage tank inlet and a catholyte storage tank outlet;
The liquid inlet of the cathode end plate, the catholyte inlet of the catholyte flow frame of the electrolytic cell and the outlet of the catholyte storage tank are communicated; the liquid outlet of the cathode end plate, the catholyte outlet of the catholyte flow frame of the electrolytic cell and the inlet of the catholyte storage tank are communicated;
The outlet of the anode end plate, the outlet of the gas-water mixture of the anode liquid flow frame of the electrolytic cell and the outside of the vanadium electrolyte electrolytic device are communicated.
7. The vanadium electrolyte electrolysis device according to claim 5, wherein the cathode end plate is provided with a cathode end plate liquid inlet and a cathode end plate liquid outlet;
The anode end plate is provided with an anode end plate liquid inlet and an anode end plate liquid outlet;
The catholyte flow frame is provided with a catholyte inlet and a catholyte outlet;
The anolyte flow frame is provided with an anolyte inlet and an anolyte outlet;
The vanadium electrolyte electrolysis device also comprises a catholyte storage tank and an anolyte storage tank; the catholyte storage tank is provided with a catholyte storage tank inlet and a catholyte storage tank outlet; the anolyte storage tank is provided with an anolyte storage tank inlet and an anolyte storage tank outlet;
The liquid inlet of the cathode end plate, the catholyte inlet of the catholyte flow frame of the electrolytic cell and the outlet of the catholyte storage tank are communicated; the liquid outlet of the cathode end plate, the catholyte outlet of the catholyte flow frame of the electrolytic cell and the inlet of the catholyte storage tank are communicated;
the liquid inlet of the anode end plate, the anode liquid inlet of the anode liquid flow frame of the electrolytic cell and the outlet of the anode liquid storage tank are communicated; the liquid outlet of the anode end plate, the anolyte outlet of the anolyte flow frame of the electrolytic cell and the inlet of the anolyte storage tank are communicated.
8. A method for preparing vanadium electrolyte, characterized in that the electrolysis is performed by adopting the vanadium electrolyte electrolysis device according to any one of claims 3-7, and the electrolysis is stopped after the required vanadium electrolyte is obtained.
9. The method of preparing a vanadium electrolyte according to claim 8, wherein the vanadium electrolyte electrolysis device has a cathode side and an anode side, the cathode side being added with a catholyte;
adding an anode solution to the anode side; or, the anode side is not added with an anolyte.
10. The method for preparing a vanadium electrolyte according to claim 9, wherein the catholyte comprises a tetravalent vanadium solution and/or a pentavalent vanadium solution;
And/or the concentration of the catholyte is 1-4mol/L;
And/or, the anolyte comprises water or sulfuric acid solution;
And/or the current density of the electrolysis is 0.1-3A/cm 2;
and/or the temperature of the electrolysis is 20-50 ℃.
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