CN114142074B - Method for improving stability of vanadium battery electrolyte - Google Patents
Method for improving stability of vanadium battery electrolyte Download PDFInfo
- Publication number
- CN114142074B CN114142074B CN202111439787.8A CN202111439787A CN114142074B CN 114142074 B CN114142074 B CN 114142074B CN 202111439787 A CN202111439787 A CN 202111439787A CN 114142074 B CN114142074 B CN 114142074B
- Authority
- CN
- China
- Prior art keywords
- electrolyte
- solution
- dihydrogen phosphate
- vanadium
- stability
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 239000003792 electrolyte Substances 0.000 title claims abstract description 78
- 229910052720 vanadium Inorganic materials 0.000 title claims abstract description 38
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 title claims abstract description 36
- 238000000034 method Methods 0.000 title claims abstract description 16
- 239000000243 solution Substances 0.000 claims abstract description 34
- 238000010438 heat treatment Methods 0.000 claims abstract description 25
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 claims abstract description 13
- NBIIXXVUZAFLBC-UHFFFAOYSA-M dihydrogenphosphate Chemical compound OP(O)([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-M 0.000 claims abstract description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 20
- 238000003756 stirring Methods 0.000 claims description 13
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 12
- 239000008367 deionised water Substances 0.000 claims description 12
- 229910021641 deionized water Inorganic materials 0.000 claims description 12
- 239000011550 stock solution Substances 0.000 claims description 12
- UUUGYDOQQLOJQA-UHFFFAOYSA-L vanadyl sulfate Chemical compound [V+2]=O.[O-]S([O-])(=O)=O UUUGYDOQQLOJQA-UHFFFAOYSA-L 0.000 claims description 12
- 229940041260 vanadyl sulfate Drugs 0.000 claims description 12
- 229910000352 vanadyl sulfate Inorganic materials 0.000 claims description 12
- 229910000403 monosodium phosphate Inorganic materials 0.000 claims description 11
- 235000019799 monosodium phosphate Nutrition 0.000 claims description 11
- AJPJDKMHJJGVTQ-UHFFFAOYSA-M sodium dihydrogen phosphate Chemical compound [Na+].OP(O)([O-])=O AJPJDKMHJJGVTQ-UHFFFAOYSA-M 0.000 claims description 11
- 238000001914 filtration Methods 0.000 claims description 9
- 239000007787 solid Substances 0.000 claims description 9
- 238000005303 weighing Methods 0.000 claims description 6
- LFVGISIMTYGQHF-UHFFFAOYSA-N ammonium dihydrogen phosphate Chemical compound [NH4+].OP(O)([O-])=O LFVGISIMTYGQHF-UHFFFAOYSA-N 0.000 claims description 5
- 229910000387 ammonium dihydrogen phosphate Inorganic materials 0.000 claims description 5
- 235000019837 monoammonium phosphate Nutrition 0.000 claims description 5
- 229910000402 monopotassium phosphate Inorganic materials 0.000 claims description 5
- 235000019796 monopotassium phosphate Nutrition 0.000 claims description 5
- PJNZPQUBCPKICU-UHFFFAOYSA-N phosphoric acid;potassium Chemical compound [K].OP(O)(O)=O PJNZPQUBCPKICU-UHFFFAOYSA-N 0.000 claims description 5
- 239000007864 aqueous solution Substances 0.000 claims description 4
- 238000005868 electrolysis reaction Methods 0.000 claims description 4
- 229910019142 PO4 Inorganic materials 0.000 claims description 3
- 238000000354 decomposition reaction Methods 0.000 claims description 3
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 3
- 239000010452 phosphate Substances 0.000 claims description 3
- 238000011534 incubation Methods 0.000 claims description 2
- 238000001556 precipitation Methods 0.000 abstract description 13
- 229910001456 vanadium ion Inorganic materials 0.000 abstract description 13
- 239000000654 additive Substances 0.000 abstract description 7
- 230000000996 additive effect Effects 0.000 abstract description 6
- 239000008151 electrolyte solution Substances 0.000 abstract description 5
- 239000013078 crystal Substances 0.000 abstract description 4
- 230000000694 effects Effects 0.000 abstract description 4
- 239000013522 chelant Substances 0.000 abstract description 2
- 238000004090 dissolution Methods 0.000 abstract description 2
- 230000007062 hydrolysis Effects 0.000 abstract description 2
- 238000006460 hydrolysis reaction Methods 0.000 abstract description 2
- 230000002035 prolonged effect Effects 0.000 abstract description 2
- 229910021645 metal ion Inorganic materials 0.000 description 5
- 238000009835 boiling Methods 0.000 description 4
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 230000001376 precipitating effect Effects 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 241000282414 Homo sapiens Species 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 description 2
- DTQVDTLACAAQTR-UHFFFAOYSA-N Trifluoroacetic acid Chemical compound OC(=O)C(F)(F)F DTQVDTLACAAQTR-UHFFFAOYSA-N 0.000 description 2
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 2
- 238000004146 energy storage Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000006259 organic additive Substances 0.000 description 2
- FBPFZTCFMRRESA-KVTDHHQDSA-N D-Mannitol Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)[C@H](O)CO FBPFZTCFMRRESA-KVTDHHQDSA-N 0.000 description 1
- 229930091371 Fructose Natural products 0.000 description 1
- RFSUNEUAIZKAJO-ARQDHWQXSA-N Fructose Chemical compound OC[C@H]1O[C@](O)(CO)[C@@H](O)[C@@H]1O RFSUNEUAIZKAJO-ARQDHWQXSA-N 0.000 description 1
- 239000005715 Fructose Substances 0.000 description 1
- 229930195725 Mannitol Natural products 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 229920002125 Sokalan® Polymers 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- -1 alkali metal sulfate Chemical class 0.000 description 1
- 229910052936 alkali metal sulfate Inorganic materials 0.000 description 1
- OBESRABRARNZJB-UHFFFAOYSA-N aminomethanesulfonic acid Chemical compound NCS(O)(=O)=O OBESRABRARNZJB-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 1
- 239000004327 boric acid Substances 0.000 description 1
- 230000003139 buffering effect Effects 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 239000002738 chelating agent Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 235000010355 mannitol Nutrition 0.000 description 1
- 239000000594 mannitol Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229940098779 methanesulfonic acid Drugs 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000004584 polyacrylic acid Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 239000003115 supporting electrolyte Substances 0.000 description 1
Classifications
-
- 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
-
- 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
-
- 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
- C25B1/50—Processes
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Electrochemistry (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Metallurgy (AREA)
- Materials Engineering (AREA)
- Inorganic Chemistry (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Manufacturing & Machinery (AREA)
- Sustainable Development (AREA)
- Sustainable Energy (AREA)
- General Chemical & Material Sciences (AREA)
- Secondary Cells (AREA)
- Fuel Cell (AREA)
Abstract
The invention discloses a method for improving the stability of vanadium battery electrolyte, which is characterized in that ethylenediamine tetraacetic acid is added to chelate vanadium ions, so that the stability of vanadium ions in different valence states is enhanced, and precipitation can be generated in the electrolyte; the invention reduces the growth rate of crystals by adding the dihydrogen phosphate to adsorb on the surface of vanadium ions, can buffer electrolyte solution, further enhances the stability of the electrolyte, and the dihydrogen phosphate in the dihydrogen phosphate can be combined with the electrolyte to generate V-O-P bond, thereby avoiding the generation of V-O-V bond, and particularly effectively avoiding VO (OH) in pentavalent electrolyte 3 Hydrolysis to form V 2 O 5 The stability of the vanadium ion electrolyte with different valence states is effectively improved by precipitation, so that the service life of the vanadium battery is obviously prolonged; according to the invention, the additive is further combined with the electrolyte solution by heating, so that the use effect of the additive is enhanced, and the dissolution of fine crystal nucleus in the solution can be promoted.
Description
Technical Field
The invention relates to the technical field of vanadium battery production, in particular to a method for improving the stability of vanadium battery electrolyte.
Background
With the development of economy and society and the improvement of human living standard, the conventional energy supply structure mainly using fossil energy cannot meet the sustainable development requirement of human beings. The all-vanadium redox flow battery has wide capacity adjustment range, high charge and discharge efficiency, long cycle life, rapid response and environment-friendly energy storage technology, and has wide application prospect and great market potential. The all-vanadium redox flow battery pile integration technology has made a major breakthrough nowadays, but the performance of the electrolyte serving as an energy storage medium is limited by the concentration of active substances, so that the whole vanadium redox battery industry is slow in development; in particular, the electrolyte with the vanadium ion concentration exceeding 2.0mol/L has the problem of poor stability under various vanadium valence states.
At present, most of the literature discusses enhancing the stability of the positive pentavalent electrolyte, and an inorganic or organic additive is usually added, and inorganic additives such as inorganic acids including alkali metal sulfate, hydrochloric acid, boric acid and the like are commonly used, and organic additives such as organic acids including urea, fructose, mannitol, methanesulfonic acid, aminomethylsulfonic acid, trifluoroacetic acid, polyacrylic acid, oxalic acid, methacrylic acid, citric acid and the like are commonly used. However, for vanadium electrolyte, particularly high-concentration electrolyte, the stability of various vanadium ion valence state solutions should be improved to enable the electrolyte to normally operate.
Disclosure of Invention
The technical problems to be solved by the invention are as follows: the method for improving the stability of the vanadium battery electrolyte can improve the stability of the vanadium battery electrolyte in different valence states.
The technical scheme adopted by the invention for solving the technical problems is as follows: the method for improving the stability of the electrolyte of the vanadium battery comprises the following steps:
firstly, weighing a corresponding amount of vanadyl sulfate solid according to the concentration of electrolyte prepared as required, dissolving the vanadyl sulfate solid by deionized water, heating until the vanadyl sulfate solid is completely dissolved, and filtering to obtain tetravalent vanadium stock solution;
weighing at least one of sodium dihydrogen phosphate, ammonium dihydrogen phosphate or potassium dihydrogen phosphate, adding into deionized water, heating and stirring to obtain clarified dihydrogen phosphate aqueous solution, and preserving heat;
adding the tetravalent vanadium stock solution obtained in the step one into the diluted sulfuric acid solution, then adding ethylenediamine tetraacetic acid and simultaneously adding the monobasic phosphate water solution obtained in the step two, heating the solution on a resistance furnace until the solution boils after stirring, filtering and collecting the solution after the solution is cooled, and adding deionized water into the tetravalent electrolyte diluted to the required concentration for later use;
and fourthly, putting the tetravalent electrolyte obtained in the third step into an electrolytic tank for spot decomposition, and changing the parameters of the electrolysis conditions to obtain the divalent, trivalent or pentavalent electrolyte in the same state.
Further is: in the second step, at least one of sodium dihydrogen phosphate, ammonium dihydrogen phosphate or potassium dihydrogen phosphate is weighed according to the mass ratio of 2-5% of the electrolyte.
Further is: in the second step, the heating temperature is 75-85 ℃, the stirring rotating speed is 150-300 r/min, and the stirring time is 5-10 min; the incubation temperature was 60 ℃.
Further is: in the third step, the relative V concentration of the ethylenediamine tetraacetic acid is 30-50%.
Further is: in the third step, the temperature is kept for 60 to 120 minutes after heating in a resistance furnace.
The beneficial effects of the invention are as follows:
1. according to the invention, the ethylenediamine tetraacetic acid is added to chelate vanadium ions, so that the stability of vanadium ions in different valence states is enhanced, and precipitation can be generated in the electrolyte;
2. the invention reduces the growth rate of crystals by adding the dihydrogen phosphate to adsorb on the surface of vanadium ions, can buffer electrolyte solution, further enhances the stability of the electrolyte, and the dihydrogen phosphate in the dihydrogen phosphate can be combined with the electrolyte to generate V-O-P bond, thereby avoiding the generation of V-O-V bond, and particularly effectively avoiding VO (OH) in pentavalent electrolyte 3 Hydrolysis to form V 2 O 5 The stability of the vanadium ion electrolyte with different valence states is effectively improved by precipitation, so that the service life of the vanadium battery is obviously prolonged;
3. according to the invention, the additive is further combined with the electrolyte solution by heating, so that the use effect of the additive is enhanced, and the dissolution of fine crystal nucleus in the solution can be promoted;
4. the alkaline metal ions in the additive adopted by the invention can improve the electrochemical activity of the electrolyte to a certain extent, can not generate larger hardness on the whole vanadium battery component, and has lower requirements on galvanic piles;
5. the source of the additive adopted by the invention is wide, the price is low, the use amount is small, the viscosity and the conductivity of the electrolyte are not greatly influenced, and the invention is suitable for different supporting electrolytes;
6. the method has the advantages of simple process flow, easy operation, suitability for industrial production and no pollution to the environment.
Detailed Description
In order that the invention may be readily understood, a further description of the invention will be provided with reference to the following examples.
The invention discloses a method for improving the stability of vanadium battery electrolyte, which comprises the following steps:
firstly, weighing a corresponding amount of vanadyl sulfate solid according to the concentration of electrolyte prepared as required, dissolving the vanadyl sulfate solid by deionized water, heating until the vanadyl sulfate solid is completely dissolved, and filtering to obtain tetravalent vanadium stock solution;
weighing at least one of sodium dihydrogen phosphate, ammonium dihydrogen phosphate or potassium dihydrogen phosphate according to the mass ratio of 2-5% of the electrolyte, adding into deionized water, heating at 75-85 ℃, stirring at the rotating speed of 150-300 r/min for 5-10 min to obtain clarified monobasic phosphate aqueous solution, and preserving heat at the temperature of 60 ℃;
adding the tetravalent vanadium stock solution obtained in the step one into diluted sulfuric acid solution, then adding ethylenediamine tetraacetic acid with the relative V concentration of 30-50%, simultaneously adding the dihydrogen phosphate aqueous solution obtained in the step two, heating the solution to boiling on a resistance furnace after stirring, preserving heat for 60-120 min, filtering and collecting the solution after the solution is cooled, and adding deionized water into the tetravalent electrolyte diluted to the required concentration for later use;
and fourthly, putting the tetravalent electrolyte obtained in the third step into an electrolytic tank for spot decomposition, and changing the parameters of the electrolysis conditions to obtain the divalent, trivalent or pentavalent electrolyte in the same state.
The ethylenediamine tetraacetic acid adopted in the invention is a chelating agent capable of combining with different metal ions, so that the stability of the metal ions in the solution can be greatly enhanced, the adopted dihydrogen phosphate can not only reduce the crystallization rate by adsorbing on the surface of the metal ions so as to ensure that the metal ions are not easy to crystallize, but also play a certain role in buffering the electrolyte, so that the whole solution system is more stable, and the phosphorus element is a substance capable of generating a stronger combining effect with vanadium, and through the combined action of the two substances, the stability of the vanadium electrolyte in long-time operation can be better improved.
According to the invention, the ethylenediamine tetraacetic acid and the dihydrogen phosphate are simultaneously introduced into the tetravalent vanadium battery electrolyte, and the ethylenediamine tetraacetic acid and the dihydrogen phosphate can be combined with substances in the solution more effectively in a heating manner, so that the stability of the electrolyte is improved, and the electrolyte solution in the rest valence states obtained by carrying out electrolysis on the tetravalent electrolyte obtained by adopting the method disclosed by the invention can inherit the excellent stability, so that the long-term service life of the whole vanadium battery system is ensured.
Example 1
Taking vanadyl sulfate stock solution with vanadium content of 2.5mol for standby, preparing sodium dihydrogen phosphate with the mass ratio of 3% relative to vanadium ion, adding into a proper amount of deionized water, stirring at a temperature of 75 ℃ for 5min at a rotating speed of 200r/min to obtain a clear solution, and preserving heat at 60 ℃; adding tetravalent vanadium stock solution into diluted sulfuric acid solution according to the requirement, adding ethylenediamine tetraacetic acid with the relative V concentration of 30% and simultaneously adding clarified solution containing sodium dihydrogen phosphate, heating to boiling on a resistance furnace for 60min, cooling, filtering and collecting after heating, and placing the solution in a 1000ml volumetric flask to obtain tetravalent electrolyte with the volume of 2.5 mol/L; taking tetravalent electrolyte to electrolyze in an electrolytic tank to obtain corresponding divalent, trivalent and pentavalent electrolyte, taking the electrolyte out, placing the divalent, trivalent and tetravalent electrolyte in a container, placing the electrolyte in the container at the temperature of minus 20 ℃ for 180 days without precipitation, placing the electrolyte in a water bath for 365 days without precipitation at the normal temperature, heating the electrolyte in the water bath for 50 days without precipitation at the temperature of 50 ℃, and not precipitating for 365 days at the normal temperature, wherein the kinematic viscosity and the conductivity of all the electrolytes in the valence state have no obvious change before and after the addition, and the assembled battery is subjected to charge and discharge test for 300 cycles, wherein the average utilization rate is 64.7%, the coulombic efficiency is 95.6%, and the energy efficiency is 82.1%.
Example 2
Taking vanadyl sulfate stock solution with vanadium content of 3.0mol for standby, preparing sodium dihydrogen phosphate with the mass ratio of 4% relative to vanadium ion, adding into a proper amount of deionized water, stirring at 80 ℃ and a rotating speed of 250r/min for 8min to obtain a clear solution, and preserving heat at 65 ℃; adding tetravalent vanadium stock solution into diluted sulfuric acid solution according to the requirement, adding ethylenediamine tetraacetic acid with the relative V concentration of 40% and simultaneously adding clarified solution containing sodium dihydrogen phosphate, heating to boiling on a resistance furnace for 90min, cooling, filtering and collecting after heating, and placing the solution in a 1000ml volumetric flask to obtain tetravalent electrolyte with the volume of 3.0 mol/L; taking tetravalent electrolyte to electrolyze in an electrolytic tank to obtain corresponding divalent, trivalent and pentavalent electrolyte, taking the electrolyte out, placing the divalent, trivalent and tetravalent electrolyte in a container, placing the electrolyte in the container at the temperature of minus 20 ℃ for 180 days without precipitation, placing the electrolyte in a water bath for 365 days without precipitation at the normal temperature, heating the electrolyte in the water bath for 50 days without precipitation at the temperature of 50 ℃, and not precipitating for 365 days at the normal temperature, wherein the kinematic viscosity and the conductivity of all the electrolytes in the valence state have no obvious change before and after the addition, and the assembled battery is subjected to charge and discharge test for 300 cycles, wherein the average utilization rate is 63.8%, the coulombic efficiency is 94.3%, and the energy efficiency is 80.4%.
Example 3
Taking vanadyl sulfate stock solution with vanadium content of 3.5mol for standby, preparing sodium dihydrogen phosphate with the mass ratio of 5% relative to vanadium ion, adding into a proper amount of deionized water, stirring at a temperature of 55 ℃ for 10min at a rotating speed of 300r/min to obtain a clear solution, and preserving heat at 70 ℃; adding tetravalent vanadium stock solution into diluted sulfuric acid solution according to the requirement, adding ethylenediamine tetraacetic acid with the relative V concentration of 50% and simultaneously adding clarified solution containing sodium dihydrogen phosphate, heating to boiling on a resistance furnace for 120min, cooling, filtering and collecting after heating, and placing the solution in a 1000ml volumetric flask to obtain tetravalent electrolyte with the volume of 3.5 mol/L; taking tetravalent electrolyte to electrolyze in an electrolytic tank to obtain corresponding divalent, trivalent and pentavalent electrolyte, taking the electrolyte out, placing the divalent, trivalent and tetravalent electrolyte in a container, placing the electrolyte in the container at the temperature of minus 20 ℃ for 180 days without precipitation, placing the electrolyte in a water bath for 365 days without precipitation at the normal temperature, heating the electrolyte in the water bath for 50 days without precipitation at the temperature of 50 ℃, and not precipitating for 365 days at the normal temperature, wherein the kinematic viscosity and the conductivity of the electrolyte in all the valence states have no obvious change before and after the addition, and the assembled battery is subjected to charge and discharge test for 300 cycles, wherein the average utilization rate is 63.1%, the coulombic efficiency is 93.2%, and the energy efficiency is 77.8%.
Claims (5)
1. The method for improving the stability of the vanadium battery electrolyte is characterized by comprising the following steps of: the method comprises the following steps:
firstly, weighing a corresponding amount of vanadyl sulfate solid according to the concentration of electrolyte prepared as required, dissolving the vanadyl sulfate solid by deionized water, heating until the vanadyl sulfate solid is completely dissolved, and filtering to obtain tetravalent vanadium stock solution;
weighing at least one of sodium dihydrogen phosphate, ammonium dihydrogen phosphate or potassium dihydrogen phosphate, adding into deionized water, heating and stirring to obtain clarified dihydrogen phosphate aqueous solution, and preserving heat;
adding the tetravalent vanadium stock solution obtained in the step one into the diluted sulfuric acid solution, then adding ethylenediamine tetraacetic acid and simultaneously adding the monobasic phosphate water solution obtained in the step two, heating the solution on a resistance furnace until the solution boils after stirring, filtering and collecting the solution after the solution is cooled, and adding deionized water into the tetravalent electrolyte diluted to the required concentration for later use;
and fourthly, putting the tetravalent electrolyte obtained in the third step into an electrolytic tank for spot decomposition, and changing the parameters of the electrolysis conditions to obtain the divalent, trivalent or pentavalent electrolyte in the same state.
2. The method for improving the stability of the electrolyte of the vanadium battery according to claim 1, wherein: in the second step, at least one of sodium dihydrogen phosphate, ammonium dihydrogen phosphate or potassium dihydrogen phosphate is weighed according to the mass ratio of 2-5% of the electrolyte.
3. The method for improving the stability of the electrolyte of the vanadium battery according to claim 1, wherein: in the second step, the heating temperature is 75-85 ℃, the stirring rotating speed is 150-300 r/min, and the stirring time is 5-10 min; the incubation temperature was 60 ℃.
4. The method for improving the stability of the electrolyte of the vanadium battery according to claim 1, wherein: in the third step, the relative V concentration of the ethylenediamine tetraacetic acid is 30-50%.
5. The method for improving the stability of the electrolyte of the vanadium battery according to claim 1, wherein: in the third step, the temperature is kept for 60 to 120 minutes after heating in a resistance furnace.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111439787.8A CN114142074B (en) | 2021-11-30 | 2021-11-30 | Method for improving stability of vanadium battery electrolyte |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111439787.8A CN114142074B (en) | 2021-11-30 | 2021-11-30 | Method for improving stability of vanadium battery electrolyte |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN114142074A CN114142074A (en) | 2022-03-04 |
| CN114142074B true CN114142074B (en) | 2023-10-27 |
Family
ID=80389422
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202111439787.8A Active CN114142074B (en) | 2021-11-30 | 2021-11-30 | Method for improving stability of vanadium battery electrolyte |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN114142074B (en) |
Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6143443A (en) * | 1993-11-17 | 2000-11-07 | Pinnacle Arb Limited | Stabilized electrolyte solutions, methods of preparation thereof and redox cells and batteries containing stabilized electrolyte solutions |
| CN101110481A (en) * | 2006-07-19 | 2008-01-23 | 中国科学院金属研究所 | Method for preparing all vanadium ion redox flow battery electrolyte |
| CN102110836A (en) * | 2011-01-26 | 2011-06-29 | 上海林洋储能科技有限公司 | High-reliability vanadium ion electrolyte |
| CN102170007A (en) * | 2011-03-29 | 2011-08-31 | 华中科技大学 | Anode electrolyte of highly stable full-vanadium fluid battery and preparation method thereof |
| CN104269572A (en) * | 2014-10-13 | 2015-01-07 | 四川长虹电源有限责任公司 | Preparation method of vanadium redox flow battery electrolyte optimized by compound stabilizer |
| CN107210475A (en) * | 2015-01-21 | 2017-09-26 | 洛克希德马丁尖端能量存储有限公司 | For electrolyte solution solid buffer material and use its flow battery group |
| CN109065931A (en) * | 2018-08-02 | 2018-12-21 | 大连融科储能技术发展有限公司 | Electrolyte of vanadium redox battery additive and its preparation method and application |
| JP2019023955A (en) * | 2017-07-21 | 2019-02-14 | 三菱瓦斯化学株式会社 | Positive electrode electrolyte and redox flow battery |
| JP2019129037A (en) * | 2018-01-23 | 2019-08-01 | 三菱瓦斯化学株式会社 | Electrolyte solution for battery and redox flow battery |
| CN111342102A (en) * | 2020-04-03 | 2020-06-26 | 武汉科技大学 | Preparation method of vanadium battery electrolyte based on vanadium compound |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0829104B1 (en) * | 1995-05-03 | 2003-10-08 | Pinnacle VRB Limited | Method of preparing a high energy density vanadium electrolyte solution for all-vanadium redox cells and batteries |
| GB2486719B (en) * | 2010-12-23 | 2013-02-13 | Acal Energy Ltd | Fuel cells |
| CN106463755B (en) * | 2014-06-13 | 2019-07-02 | 株式会社Lg化学 | Vanadium solution, the electrolyte comprising the vanadium solution, the secondary cell comprising the electrolyte and the method for preparing the vanadium solution |
| ES2837255T3 (en) * | 2015-04-14 | 2021-06-29 | Lockheed Martin Energy Llc | Flow battery balance cells that have a bipolar membrane for simultaneous modification of a negative electrolyte solution and a positive electrolyte solution |
-
2021
- 2021-11-30 CN CN202111439787.8A patent/CN114142074B/en active Active
Patent Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6143443A (en) * | 1993-11-17 | 2000-11-07 | Pinnacle Arb Limited | Stabilized electrolyte solutions, methods of preparation thereof and redox cells and batteries containing stabilized electrolyte solutions |
| CN101110481A (en) * | 2006-07-19 | 2008-01-23 | 中国科学院金属研究所 | Method for preparing all vanadium ion redox flow battery electrolyte |
| CN102110836A (en) * | 2011-01-26 | 2011-06-29 | 上海林洋储能科技有限公司 | High-reliability vanadium ion electrolyte |
| CN102170007A (en) * | 2011-03-29 | 2011-08-31 | 华中科技大学 | Anode electrolyte of highly stable full-vanadium fluid battery and preparation method thereof |
| CN104269572A (en) * | 2014-10-13 | 2015-01-07 | 四川长虹电源有限责任公司 | Preparation method of vanadium redox flow battery electrolyte optimized by compound stabilizer |
| CN107210475A (en) * | 2015-01-21 | 2017-09-26 | 洛克希德马丁尖端能量存储有限公司 | For electrolyte solution solid buffer material and use its flow battery group |
| JP2019023955A (en) * | 2017-07-21 | 2019-02-14 | 三菱瓦斯化学株式会社 | Positive electrode electrolyte and redox flow battery |
| JP2019129037A (en) * | 2018-01-23 | 2019-08-01 | 三菱瓦斯化学株式会社 | Electrolyte solution for battery and redox flow battery |
| CN109065931A (en) * | 2018-08-02 | 2018-12-21 | 大连融科储能技术发展有限公司 | Electrolyte of vanadium redox battery additive and its preparation method and application |
| CN111342102A (en) * | 2020-04-03 | 2020-06-26 | 武汉科技大学 | Preparation method of vanadium battery electrolyte based on vanadium compound |
Also Published As
| Publication number | Publication date |
|---|---|
| CN114142074A (en) | 2022-03-04 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101635363B (en) | Vanadium ion redox flow battery electrolyte, preparation method thereof and battery thereof | |
| CN103326055B (en) | Zinc cathode electrolyte applied to redox battery | |
| CN101621122B (en) | Preparation method of lithium iron phosphate compound material | |
| CN105576240A (en) | Nano barium sulfate carbon composite material and preparation method and application therefor | |
| CN102881931A (en) | Phosphorus-containing all-vanadium redox flow battery anode electrolyte | |
| CN103872370A (en) | Flow battery | |
| CN115732727A (en) | All-iron flow battery negative electrode electrolyte | |
| CN114142074B (en) | Method for improving stability of vanadium battery electrolyte | |
| CN106654333A (en) | Electrolyte stabilizing agent for all-vanadium redox flow battery and preparation method for electrolyte stabilizing agent | |
| CN102618859A (en) | Impregnation liquid special for lead-calcium alloyed grid | |
| CN102881932B (en) | Vanadium redox flow battery electrolyte containing manganese | |
| CN108123159A (en) | A kind of method for improving all-vanadium flow battery electrolyte liquid stability | |
| CN102723519A (en) | Lead liquid flow battery electrolyte | |
| CN114388859B (en) | Negative electrode electrolyte for all-iron flow battery | |
| CN113140808B (en) | Water-based battery | |
| CN106340664B (en) | Full electrolyte of vanadium redox battery and preparation method thereof | |
| CN111261910B (en) | Positive electrode electrolyte for alkaline zinc-iron flow battery and application | |
| CN112952173B (en) | Neutral zinc-iron flow battery with food-grade electrolyte | |
| CN108123161B (en) | Colloid electrolyte of vanadium battery and vanadium battery | |
| CN113328124A (en) | Cathode electrolyte for all-iron flow battery | |
| CN114142075B (en) | Preparation method of vanadium redox flow battery electrolyte | |
| CN114551954B (en) | Negative electrode electrolyte for zinc-iron flow battery | |
| CN111200146B (en) | Negative electrode electrolyte for alkaline zinc-based flow battery and preparation and application thereof | |
| CN102082274B (en) | Surface treatment process of battery current collector | |
| CN107768702A (en) | The minimizing technology of copper ion in a kind of V electrolyte |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| EE01 | Entry into force of recordation of patent licensing contract | ||
| EE01 | Entry into force of recordation of patent licensing contract |
Application publication date: 20220304 Assignee: SICHUAN PAN YAN TECHNOLOGY Co.,Ltd. Assignor: Chengdu advanced metal material industry technology Research Institute Co.,Ltd. Contract record no.: X2024980001678 Denomination of invention: Methods for improving the stability of vanadium battery electrolyte Granted publication date: 20231027 License type: Common License Record date: 20240131 |