CN114807957A - Vanadium solution valence state rapid regulation and control method based on high-current pulse technology - Google Patents
Vanadium solution valence state rapid regulation and control method based on high-current pulse technology Download PDFInfo
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- 229910052720 vanadium Inorganic materials 0.000 title claims abstract description 77
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 title claims abstract description 77
- 238000000034 method Methods 0.000 title claims abstract description 30
- 238000005516 engineering process Methods 0.000 title claims abstract description 17
- 238000005868 electrolysis reaction Methods 0.000 claims abstract description 47
- 239000003792 electrolyte Substances 0.000 claims abstract description 45
- 229910001456 vanadium ion Inorganic materials 0.000 claims abstract description 29
- 230000001105 regulatory effect Effects 0.000 claims abstract description 14
- 230000001276 controlling effect Effects 0.000 claims abstract description 13
- 239000002994 raw material Substances 0.000 claims abstract description 3
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 44
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 34
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 14
- 229910052799 carbon Inorganic materials 0.000 claims description 13
- 229910002804 graphite Inorganic materials 0.000 claims description 13
- 239000010439 graphite Substances 0.000 claims description 13
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 11
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 10
- 229910052719 titanium Inorganic materials 0.000 claims description 10
- 239000010936 titanium Substances 0.000 claims description 10
- 229910052697 platinum Inorganic materials 0.000 claims description 7
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 5
- 229910052737 gold Inorganic materials 0.000 claims description 5
- 239000010931 gold Substances 0.000 claims description 5
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- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 4
- 239000003575 carbonaceous material Substances 0.000 claims description 4
- YADSGOSSYOOKMP-UHFFFAOYSA-N dioxolead Chemical compound O=[Pb]=O YADSGOSSYOOKMP-UHFFFAOYSA-N 0.000 claims description 4
- 239000007769 metal material Substances 0.000 claims description 4
- 238000003756 stirring Methods 0.000 claims description 4
- 229910021397 glassy carbon Inorganic materials 0.000 claims description 3
- 229920000049 Carbon (fiber) Polymers 0.000 claims description 2
- 229910052684 Cerium Inorganic materials 0.000 claims description 2
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 2
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 2
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims description 2
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 2
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 2
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 2
- 229910052782 aluminium Inorganic materials 0.000 claims description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 2
- 229910052788 barium Inorganic materials 0.000 claims description 2
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 claims description 2
- 229910052797 bismuth Inorganic materials 0.000 claims description 2
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 claims description 2
- 239000004917 carbon fiber Substances 0.000 claims description 2
- 229910021393 carbon nanotube Inorganic materials 0.000 claims description 2
- 239000002041 carbon nanotube Substances 0.000 claims description 2
- 229910010293 ceramic material Inorganic materials 0.000 claims description 2
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 claims description 2
- 229910052804 chromium Inorganic materials 0.000 claims description 2
- 239000011651 chromium Substances 0.000 claims description 2
- 239000011248 coating agent Substances 0.000 claims description 2
- 238000000576 coating method Methods 0.000 claims description 2
- 229910017052 cobalt Inorganic materials 0.000 claims description 2
- 239000010941 cobalt Substances 0.000 claims description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 2
- 229910052802 copper Inorganic materials 0.000 claims description 2
- 239000010949 copper Substances 0.000 claims description 2
- 229910003460 diamond Inorganic materials 0.000 claims description 2
- 239000010432 diamond Substances 0.000 claims description 2
- 239000007772 electrode material Substances 0.000 claims description 2
- 239000008187 granular material Substances 0.000 claims description 2
- 229910021389 graphene Inorganic materials 0.000 claims description 2
- 229910052741 iridium Inorganic materials 0.000 claims description 2
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 claims description 2
- 229910052742 iron Inorganic materials 0.000 claims description 2
- 239000011133 lead Substances 0.000 claims description 2
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 claims description 2
- 238000010907 mechanical stirring Methods 0.000 claims description 2
- 150000004706 metal oxides Chemical class 0.000 claims description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 2
- 229910052750 molybdenum Inorganic materials 0.000 claims description 2
- 239000011733 molybdenum Substances 0.000 claims description 2
- 229910052759 nickel Inorganic materials 0.000 claims description 2
- 229910052758 niobium Inorganic materials 0.000 claims description 2
- 239000010955 niobium Substances 0.000 claims description 2
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 claims description 2
- 229910000510 noble metal Inorganic materials 0.000 claims description 2
- 229910052762 osmium Inorganic materials 0.000 claims description 2
- SYQBFIAQOQZEGI-UHFFFAOYSA-N osmium atom Chemical compound [Os] SYQBFIAQOQZEGI-UHFFFAOYSA-N 0.000 claims description 2
- 229910052763 palladium Inorganic materials 0.000 claims description 2
- 229910052702 rhenium Inorganic materials 0.000 claims description 2
- WUAPFZMCVAUBPE-UHFFFAOYSA-N rhenium atom Chemical compound [Re] WUAPFZMCVAUBPE-UHFFFAOYSA-N 0.000 claims description 2
- 229910052703 rhodium Inorganic materials 0.000 claims description 2
- 239000010948 rhodium Substances 0.000 claims description 2
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 claims description 2
- 229910052707 ruthenium Inorganic materials 0.000 claims description 2
- 229910052709 silver Inorganic materials 0.000 claims description 2
- 239000004332 silver Substances 0.000 claims description 2
- 229910052715 tantalum Inorganic materials 0.000 claims description 2
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 claims description 2
- 229910052718 tin Inorganic materials 0.000 claims description 2
- 239000011135 tin Substances 0.000 claims description 2
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 2
- 229910052721 tungsten Inorganic materials 0.000 claims description 2
- 239000010937 tungsten Substances 0.000 claims description 2
- 229910052725 zinc Inorganic materials 0.000 claims description 2
- 239000011701 zinc Substances 0.000 claims description 2
- 229910052726 zirconium Inorganic materials 0.000 claims description 2
- 238000004146 energy storage Methods 0.000 abstract description 6
- 239000000243 solution Substances 0.000 description 50
- 239000007864 aqueous solution Substances 0.000 description 8
- 239000007773 negative electrode material Substances 0.000 description 5
- 239000007774 positive electrode material Substances 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 238000006722 reduction reaction Methods 0.000 description 3
- 239000003638 chemical reducing agent Substances 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 238000006479 redox reaction Methods 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 230000003750 conditioning effect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000003487 electrochemical reaction Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
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- 230000009467 reduction Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B1/00—Electrolytic production of inorganic compounds or non-metals
- C25B1/01—Products
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- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B15/00—Operating or servicing cells
- C25B15/02—Process control or regulation
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B9/00—Cells or assemblies of cells; Constructional parts of cells; Assemblies of constructional parts, e.g. electrode-diaphragm assemblies; Process-related cell features
- C25B9/60—Constructional parts of cells
- C25B9/65—Means for supplying current; Electrode connections; Electric inter-cell connections
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/18—Regenerative fuel cells, e.g. redox flow batteries or secondary fuel cells
- H01M8/184—Regeneration by electrochemical means
- H01M8/188—Regeneration by electrochemical means by recharging of redox couples containing fluids; Redox flow type batteries
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Abstract
The invention discloses a method for quickly regulating and controlling the valence state of a vanadium solution based on a large-current pulse technology, and relates to the field of energy storage batteries. The method takes high-valence vanadium electrolyte, low-valence vanadium electrolyte and vanadium electrolyte with unbalanced valence as main raw materials, and adopts a pulse mode to carry out electrolysis in an electrolytic cell to prepare the electrolyte with the valence of vanadium ions conforming to that of a vanadium battery; the electrolytic cell consists of a positive half cell and a negative half cell, the two half cells are separated by a diaphragm, an electrode inserted into the positive half cell is connected with the positive pole of a direct current pulse power supply, an electrode inserted into the negative half cell is connected with the negative pole of the direct current pulse power supply, and pulse electrolysis parameters are controlled to carry out electrolysis. The method is simple and easy to operate, can quickly adjust the vanadium valence state of the electrolyte, can obtain the electrolyte with the specified vanadium valence state, can meet the use requirements under different conditions, and has very wide application prospect.
Description
Technical Field
The invention relates to the technical field of energy storage batteries, in particular to a method for quickly regulating and controlling the valence state of a vanadium solution based on a large-current pulse technology.
Background
An all-vanadium redox flow battery (vanadium battery) is a secondary energy system that utilizes redox reactions between vanadium ions of different valence states for energy storage and conversion. The method is characterized in that: no discharge pollution, adjustable capacity, long cycle life, deep heavy current density discharge, quick charge and high energy conversion rate. The vanadium battery is mainly applied to energy storage power supplies of power station peak shaving, large-scale photoelectric conversion and wind power generation as well as energy storage systems of remote areas, uninterrupted power supplies or emergency power supply systems.
Along with the charge and discharge of the vanadium battery, vanadium ion migration, divalent vanadium ion oxidation in the cathode electrolyte, hydrogen evolution of the cathode and the like can be generated between the anode electrolyte and the cathode electrolyte, so that the concentration and the valence state of the vanadium ion in the anode electrolyte and the cathode electrolyte are not matched. When the utilization rate of the electrolyte does not meet the design requirement, the vanadium electrolyte needs to be replaced by a new vanadium electrolyte, so that the energy storage cost of the vanadium battery is increased.
Currently, more valence state adjustment methods are used, including chemical reduction and oxidation, gas reduction and oxidation, and low current density direct current electrolysis (<200mA/cm 2 ) The method of (1). Impurity ions are easy to introduce by a chemical method, and the redox reaction degree of vanadium ions is not controlled; direct current electrolytic methods require a lower current density to control the end point of the electrochemical reaction, resulting in an excessively long conditioning time, a slow speed and an increase in cost to varying degrees.
Disclosure of Invention
In view of the above, the invention provides a method for rapidly regulating and controlling the valence state of a vanadium solution based on a large-current pulse technology, which overcomes the technical limitations of chemical reduction, low-current direct current electrolysis and other methods.
The invention discloses a method for quickly regulating and controlling the valence state of a vanadium solution based on a large-current pulse technology, which takes high-valence vanadium electrolyte, low-valence vanadium electrolyte and vanadium electrolyte with unbalanced valence state as main raw materials, and carries out electrolysis in an electrolytic cell by adopting a pulse mode to prepare the electrolyte with the valence state of vanadium ions conforming to that required by a vanadium battery; the electrolytic cell consists of a positive half cell and a negative half cell, the two half cells are separated by a diaphragm, an electrode inserted into the positive half cell is connected with the positive pole of a direct current pulse power supply, an electrode inserted into the negative half cell is connected with the negative pole of the direct current pulse power supply, and pulse electrolysis parameters are controlled to carry out electrolysis.
Further, during electrolysis, when the valence state of the vanadium solution needs to be raised, the positive half pool is the vanadium solution, and the negative half pool is the sulfuric acid solution; when the valence state of the vanadium solution needs to be reduced, the negative half pool is the vanadium solution, and the positive half pool is the sulfuric acid solution.
Further, the high valence vanadium electrolyte comprises VO 2 + And VO 2+ (ii) a The low-valence vanadium electrolyte comprises V 3+ And V 2 + (ii) a V in the vanadium electrolyte with the valence state unbalance 3+ And VO 2+ The ratio of (A) deviates from 1: 1.
Further, the positive electrode and the negative electrode both adopt graphite electrodes or size-stable electrodes; the concentration of the sulfuric acid solution in the positive half pool and the negative half pool is 2-8 mol/L.
Further, the electrolysis mode adopts constant current pulse electrolysis, and the average current density is 200-2000 mA/cm 2 The frequency is 200-2000 Hz, and the duty ratio is 20-80%.
Further, the positive electrode is any one of a platinum electrode, a gold electrode, a titanium-based lead dioxide electrode, a titanium-based noble metal oxide coating electrode, a titanium-based platinum electrode, and a titanium suboxide electrode.
Further, the electrode material of the negative electrode comprises at least one of a metal material, a carbon material and a conductive ceramic material; wherein the metal material comprises at least one of titanium, vanadium, chromium, manganese, iron, cobalt, nickel, copper, zinc, niobium, tantalum, zirconium, tungsten, cerium, aluminum, bismuth, rhenium, barium, osmium, tin, lead, gold, silver, platinum, palladium, iridium, rhodium, molybdenum and ruthenium; the carbon material comprises any one of graphite, glassy carbon, boron-doped diamond, activated carbon, graphene, carbon fiber, carbon nanotube, carbon sponge, carbon felt and graphite felt.
Further, the electrode shape of the positive electrode and the negative electrode includes any one of a sheet, a rod, a filament, a granule, a sponge, a mesh, and a porous structure.
Further, the stirring manner is mechanical stirring or air stirring.
Due to the adoption of the technical scheme, the invention has the following advantages: (1) the method is simple and easy to operate, can quickly adjust the vanadium valence state of the electrolyte, obtain the electrolyte with various vanadium valence states, and can meet the use requirements under different conditions; (2) the invention adopts a pulse electrolysis mode to carry out high valence state (VO) 2 + 、VO 2+ ) Lower valence state (V) 3+ 、V 2+ ) Vanadium electrolyte, valence state unbalance (V) 3+ ：VO 2+ The valence state adjustment of the vanadium electrolyte deviating from 1:1), compared with the traditional technology, the method has the advantages of high adjustment speed, high current efficiency, simple process method, low operation cost and wide application prospect.
Drawings
In order to more clearly illustrate the technical solutions in the embodiments of the present invention, the drawings needed to be used in the description of the embodiments are briefly introduced below, and it is obvious that the drawings in the following description are only some embodiments described in the embodiments of the present invention, and it is obvious for those skilled in the art that other drawings can be obtained according to the drawings.
Fig. 1 is a schematic diagram of a rapid adjustment and control of a valence state of a vanadium solution based on a high current pulse technique according to an embodiment of the present invention.
Detailed Description
The present invention will be further described with reference to the accompanying drawings and examples, it being understood that the examples described are only some of the examples and are not intended to limit the invention to the embodiments described herein. All other embodiments available to those of ordinary skill in the art are intended to be within the scope of the embodiments of the present invention.
Example 1:
regulation of tetravalent Vanadium (VO) 2+ ) Solution to V 3+ ：VO 2+ The solution 1:1 is specifically: adding 2.0mol/L sulfuric acid solution into a positive half pool of an electrolytic cell, wherein a negative half pool is sulfuric acid aqueous solution with tetravalent vanadium of 2.0mol/L +2.0mol/L, the volumes of the two half pools are both 50mL, the positive half pool adopts a DSA electrode, the negative half pool adopts a graphite electrode, the effective electrode area is 10cm 2 At 600mA/cm 2 The average current density of (2) was electrolyzed at a frequency of 500Hz, a duty ratio of 20% and an electrolysis adjustment time of 0.3 hour. And (3) measuring the concentration of the electrolyte passing through the negative half cell to show that the trivalent vanadium ions in the solution: the concentration ratio of tetravalent vanadium ions is 1: 1. if direct current electrolysis is used, 1.44h is required.
Graphite felt is used as a positive electrode material and a negative electrode material, the positive electrode solution and the negative electrode solution are electrolyte which is prepared by electrolysis and contains vanadium ions with the concentration of 2.0mol/L, and the charge-discharge current density is 100mA/cm 2 The energy efficiency is 82 percent and is 150mA/cm 2 The energy efficiency was 76%.
Example 2:
regulation of trivalent vanadium (V) 3+ ) Solution to V 3+ ：VO 2+ The solution 1:1 is specifically: adding 3.0mol/L sulfuric acid solution into a negative half pool of an electrolytic cell, wherein the positive half pool is sulfuric acid aqueous solution with trivalent vanadium of 2.2mol/L +3.0mol/L, the volumes of the two half pools are both 50mL, the positive half pool adopts a platinum electrode, the negative half pool adopts a graphite felt electrode, and the effective electrode area is 10cm 2 At 1000mA/cm 2 The electrolysis was carried out at a frequency of 800Hz, a duty ratio of 30% and an electrolysis time of 0.23 hours. And (3) measuring the concentration of the negative half-cell electrolyte to show that the concentration of the trivalent vanadium ions: the concentration ratio of tetravalent vanadium ions is 1: 1. if direct current electrolysis is used, 159h is required.
Graphite felt is used as a positive electrode material and a negative electrode material, the positive electrode solution and the negative electrode solution are electrolyte which is prepared by electrolysis and contains vanadium ions with the concentration of 2.2mol/L, and the charge-discharge current density is 100mA/cm 2 The energy efficiency is 80 percent and is 150mA/cm 2 The energy efficiency was 75%.
Example 3:
adjusting pentavalent Vanadium (VO) 2 + ) Solution to V 3+ ：VO 2+ The solution 1:1 is specifically: in thatAdding 4.0mol/L sulfuric acid solution into a positive half pool of an electrolytic cell, wherein a negative half pool is sulfuric acid aqueous solution with pentavalent vanadium of 1.8mol/L +3.0mol/L, the volume of the two half pools is 50mL, the positive half pool adopts a gold electrode, the negative half pool adopts a glassy carbon electrode, and the effective electrode area is 10cm 2 At 1500mA/cm 2 The electrolysis was carried out at a frequency of 1200Hz, a duty ratio of 30% and an electrolysis time of 0.185 hours. And (3) measuring the concentration of the negative half-cell electrolyte to show that the concentration of the trivalent vanadium ions: the concentration ratio of tetravalent vanadium ions is 1: 1. if direct current electrolysis is used, 1.95h is required.
Graphite felt is used as a positive electrode material and a negative electrode material, the positive electrode solution and the negative electrode solution are electrolyte which is prepared by electrolysis and contains vanadium ions with the concentration of 1.8mol/L, and the charge-discharge current density is 100mA/cm 2 The energy efficiency is 85 percent and is 150mA/cm 2 The energy efficiency was 79%.
Example 4:
regulating V 3+ ：VO 2+ 2:1 solution to V 3+ ：VO 2+ The solution 1:1 is specifically: adding 3.0mol/L sulfuric acid solution into a negative half pool of an electrolytic cell, wherein the positive half pool is sulfuric acid aqueous solution with trivalent vanadium of 1.2mol/L, tetravalent vanadium of 0.6mol/L and 3.0mol/L, the volumes of the two half pools are both 50mL, the half pool adopts a platinum-plated electrode, the negative half pool adopts a carbon felt electrode, and the concentration of the carbon felt electrode is 2000mA/cm 2 The electrolysis was carried out at a frequency of 1500Hz, a duty ratio of 20% and an electrolysis time of 0.07 hours. And (3) measuring the concentration of the positive half cell electrolyte to show that the trivalent vanadium ions: the concentration ratio of tetravalent vanadium ions is 1: 1. if direct current electrolysis is used, 0.87h is required.
Graphite felt is used as a positive electrode material and a negative electrode material, the positive electrode solution and the negative electrode solution are electrolyte which is prepared by electrolysis and contains vanadium ions with the concentration of 1.8mol/L, and the charge-discharge current density is 100mA/cm 2 The energy efficiency is 86 percent and is 150mA/cm 2 The energy efficiency was 79%.
Example 5:
regulation of pentavalent (VO) 2 + ) Vanadium ion: quadrivalence (VO) 2+ ) The vanadium ion ratio is 3: 1 vanadium solution to tetravalent (VO) 2+ ) The vanadium ion solution specifically comprises: adding 3.0mol/L sulfuric acid solution into the negative half pool of the electrolytic cellThe positive half pool is sulfuric acid aqueous solution with trivalent vanadium of 1.5mol/L, tetravalent vanadium of 0.5mol/L and 3.0mol/L, the volumes of the two half pools are both 50mL, the half pool adopts a platinum-plated electrode, the negative half pool adopts a carbon felt electrode at 2000mA/cm 2 The electrolysis was carried out at a frequency of 1500Hz, a duty ratio of 20% and an electrolysis time of 0.15 hours. And (3) measuring the concentration of the positive half cell electrolyte to show that the trivalent vanadium ions: the concentration ratio of tetravalent vanadium ions is 1: 1. if direct current electrolysis is used, it takes 2.16 h.
Graphite felt is used as a positive electrode material and a negative electrode material, the positive electrode solution and the negative electrode solution are electrolyte which is prepared by electrolysis and contains vanadium ions with the concentration of 1.8mol/L, and the charge-discharge current density is 100mA/cm 2 The energy efficiency is 86 percent and is 150mA/cm 2 The energy efficiency was 79%.
Example 6:
regulation of pentavalent (VO) 2 + ) Vanadium solution to trivalent (V) 3+ ) The vanadium solution specifically comprises: adding 3.0mol/L sulfuric acid solution into a positive half pool of an electrolytic cell, wherein a negative half pool is sulfuric acid aqueous solution with pentavalent vanadium of 1.6mol/L and 3.0mol/L, the volume of the two half pools is 50mL, the half pool adopts a platinum-plated electrode, the negative half pool adopts a carbon felt electrode, and the concentration of the carbon felt electrode is 2000mA/cm 2 The electrolysis was carried out at a frequency of 1200Hz, a duty ratio of 20% and an electrolysis time of 0.144 hours. And the concentration of the positive half cell electrolyte is measured, which shows that the trivalent vanadium ion is 1.6 mol/L. If direct current electrolysis is used, it takes 2.3 h.
Example 7:
regulation of quadrivalence (VO) 2+ ) Vanadium solution to divalent (V) 2+ ) The vanadium solution specifically comprises: adding 3.0mol/L sulfuric acid solution into a positive half pool of an electrolytic cell, wherein a negative half pool is sulfuric acid aqueous solution with tetravalent vanadium of 2.0mol/L and 3.0mol/L, the volume of the two half pools is 50mL, a platinum-plated electrode is adopted in the half pool, a carbon felt electrode is adopted in the negative half pool, and the concentration of the carbon felt electrode is 1600mA/cm 2 The electrolysis was carried out at a frequency of 1500Hz, a duty ratio of 20% and an electrolysis time of 0.225 hours. And the concentration of the positive half cell electrolyte is measured, and the divalent vanadium ions are 2.0 mol/L. If direct current electrolysis is used, 2.88h is required.
Example 8:
see FIG. 1, modulation of bivalent (V) 2+ ) Vanadium solution to pentavalent (VO) 2 + ) The vanadium solution specifically comprises: adding 3.0mol/L sulfuric acid solution into a negative half pool of an electrolytic cell, wherein the positive half pool is aqueous solution of divalent vanadium of 1.5mol/L and 3.0mol/L sulfuric acid, the volume of the two half pools is 50mL, the half pool adopts a platinum-plated electrode, the negative half pool adopts a carbon felt electrode, and the concentration of the carbon felt electrode is 1200mA/cm 2 The electrolysis was carried out at a frequency of 1500Hz, a duty ratio of 30% and an electrolysis time of 0.77 hours. And the concentration of the positive half cell electrolyte is measured, and the pentavalent vanadium ions are 1.5 mol/L. If direct current electrolysis is used, it takes 6.48 h.
The embodiment result shows that the method for rapidly regulating and controlling the valence state of the vanadium solution based on the large-current pulse technology can perform rapid electrolysis under a larger current density, has simple process and short time consumption, and is easy to form industrialization.
Finally, it should be noted that: the above embodiments are only for illustrating the technical solutions of the present invention and not for limiting the same, and although the present invention is described in detail with reference to the above embodiments, those of ordinary skill in the art should understand that: modifications and equivalents may be made to the embodiments of the invention without departing from the spirit and scope of the invention, which is to be covered by the claims.
Claims (9)
1. A vanadium solution valence state rapid regulation and control method based on a large current pulse technology is characterized in that high valence state vanadium electrolyte, low valence state vanadium electrolyte and vanadium electrolyte with unbalanced valence state are used as main raw materials, electrolysis is carried out in an electrolytic cell by adopting a pulse mode, and electrolyte with vanadium ion valence state meeting the requirement of a vanadium battery is prepared; the electrolytic cell consists of a positive half cell and a negative half cell, the two half cells are separated by a diaphragm, an electrode inserted into the positive half cell is connected with the positive pole of a direct current pulse power supply, an electrode inserted into the negative half cell is connected with the negative pole of the direct current pulse power supply, and pulse electrolysis parameters are controlled to carry out electrolysis.
2. The method for rapidly regulating and controlling the valence state of the vanadium solution based on the high-current pulse technology as claimed in claim 1, wherein during electrolysis, when the valence state of the vanadium solution needs to be raised, the positive half tank is the vanadium solution, and the negative half tank is the sulfuric acid solution; when the valence state of the vanadium solution needs to be reduced, the negative half pool is the vanadium solution, and the positive half pool is the sulfuric acid solution.
3. The method for rapidly regulating and controlling the valence state of a vanadium solution based on a high-current pulse technology as claimed in claim 1, wherein the high-valence vanadium electrolyte comprises VO 2 + And VO 2+ (ii) a The low-valence vanadium electrolyte comprises V 3+ And V 2+ (ii) a V in the vanadium electrolyte with the valence state unbalance 3+ And VO 2+ The ratio of (A) deviates from 1: 1.
4. The method for rapidly regulating and controlling the valence state of the vanadium solution based on the high-current pulse technology as claimed in claim 1, wherein the positive electrode and the negative electrode both adopt graphite electrodes or size-stable electrodes; the concentration of the sulfuric acid solution in the positive half pool and the negative half pool is 2-8 mol/L.
5. The method for rapidly regulating and controlling the valence state of a vanadium solution based on a high-current pulse technology as claimed in claim 1, wherein the electrolysis mode adopts constant-current pulse electrolysis, and the average current density is 200-2000 mA/cm 2 The frequency is 200-2000 Hz, and the duty ratio is 20-80%.
6. The method for rapidly regulating and controlling the valence state of the vanadium solution based on the high-current pulse technology as claimed in claim 1, wherein the positive electrode is any one of a platinum electrode, a gold electrode, a titanium-based lead dioxide electrode, a titanium-based noble metal oxide coating electrode, a titanium-based platinum electrode and a titanium suboxide electrode.
7. The method for rapidly regulating and controlling the valence state of the vanadium solution based on the high-current pulse technology as claimed in claim 1, wherein the electrode material of the negative electrode comprises at least one of a metal material, a carbon material and a conductive ceramic material; wherein the metal material comprises at least one of titanium, vanadium, chromium, manganese, iron, cobalt, nickel, copper, zinc, niobium, tantalum, zirconium, tungsten, cerium, aluminum, bismuth, rhenium, barium, osmium, tin, lead, gold, silver, platinum, palladium, iridium, rhodium, molybdenum and ruthenium; the carbon material comprises any one of graphite, glassy carbon, boron-doped diamond, activated carbon, graphene, carbon fiber, carbon nanotube, carbon sponge, carbon felt and graphite felt.
8. The method for rapidly regulating and controlling the valence state of the vanadium solution based on the high-current pulse technology as claimed in claim 1, wherein the shapes of the positive electrode and the negative electrode include any one of a sheet, a rod, a filament, a granule, a sponge, a net and a porous structure.
9. The method for rapidly regulating and controlling the valence state of the vanadium solution based on the high-current pulse technology as claimed in claim 1, wherein the stirring manner is mechanical stirring or air stirring.
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| CN115655383A (en) * | 2022-12-27 | 2023-01-31 | 杭州德海艾科能源科技有限公司 | Method and system for detecting valence state imbalance state of electrolyte of all-vanadium redox flow battery |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101812698A (en) * | 2009-02-23 | 2010-08-25 | 中国科学院金属研究所 | Pulse electrolytic preparation method of all vanadium ion redox flow battery electrolyte |
| CN103762377A (en) * | 2014-01-27 | 2014-04-30 | 中国东方电气集团有限公司 | Vanadium redox battery and electrolyte rebalancing method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101812698A (en) * | 2009-02-23 | 2010-08-25 | 中国科学院金属研究所 | Pulse electrolytic preparation method of all vanadium ion redox flow battery electrolyte |
| CN103762377A (en) * | 2014-01-27 | 2014-04-30 | 中国东方电气集团有限公司 | Vanadium redox battery and electrolyte rebalancing method thereof |
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| CN115655383A (en) * | 2022-12-27 | 2023-01-31 | 杭州德海艾科能源科技有限公司 | Method and system for detecting valence state imbalance state of electrolyte of all-vanadium redox flow battery |
| CN115655383B (en) * | 2022-12-27 | 2023-04-07 | 杭州德海艾科能源科技有限公司 | Method and system for detecting valence state imbalance state of electrolyte of all-vanadium redox flow battery |
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