CN117276613A - All-vanadium battery electrolyte and preparation method thereof - Google Patents
All-vanadium battery electrolyte and preparation method thereof Download PDFInfo
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- CN117276613A CN117276613A CN202210660665.XA CN202210660665A CN117276613A CN 117276613 A CN117276613 A CN 117276613A CN 202210660665 A CN202210660665 A CN 202210660665A CN 117276613 A CN117276613 A CN 117276613A
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- 229910052720 vanadium Inorganic materials 0.000 title claims abstract description 223
- 239000003792 electrolyte Substances 0.000 title claims abstract description 132
- 238000002360 preparation method Methods 0.000 title claims abstract description 30
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims abstract description 149
- 238000000605 extraction Methods 0.000 claims abstract description 43
- 238000005406 washing Methods 0.000 claims abstract description 27
- 238000000034 method Methods 0.000 claims abstract description 22
- 239000002243 precursor Substances 0.000 claims abstract description 16
- 230000033116 oxidation-reduction process Effects 0.000 claims abstract description 10
- 230000008569 process Effects 0.000 claims abstract description 3
- 239000012074 organic phase Substances 0.000 claims description 39
- 239000002253 acid Substances 0.000 claims description 38
- 239000007788 liquid Substances 0.000 claims description 17
- 238000002156 mixing Methods 0.000 claims description 14
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 10
- 239000012071 phase Substances 0.000 claims description 9
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 claims description 8
- 239000003085 diluting agent Substances 0.000 claims description 6
- 238000001179 sorption measurement Methods 0.000 claims description 6
- 230000002378 acidificating effect Effects 0.000 claims description 4
- 229910000073 phosphorus hydride Inorganic materials 0.000 claims description 4
- 238000000746 purification Methods 0.000 claims description 4
- 239000003463 adsorbent Substances 0.000 claims description 2
- 238000005238 degreasing Methods 0.000 claims description 2
- 239000011347 resin Substances 0.000 claims description 2
- 229920005989 resin Polymers 0.000 claims description 2
- 229930195734 saturated hydrocarbon Natural products 0.000 claims description 2
- 239000002994 raw material Substances 0.000 abstract description 10
- 239000000243 solution Substances 0.000 description 133
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 28
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 26
- 239000000460 chlorine Substances 0.000 description 22
- 229910001456 vanadium ion Inorganic materials 0.000 description 19
- 230000000052 comparative effect Effects 0.000 description 17
- GNTDGMZSJNCJKK-UHFFFAOYSA-N divanadium pentaoxide Chemical compound O=[V](=O)O[V](=O)=O GNTDGMZSJNCJKK-UHFFFAOYSA-N 0.000 description 10
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 description 8
- 238000005868 electrolysis reaction Methods 0.000 description 5
- 150000002500 ions Chemical class 0.000 description 5
- 239000012535 impurity Substances 0.000 description 4
- 239000003350 kerosene Substances 0.000 description 4
- 230000001105 regulatory effect Effects 0.000 description 4
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 238000011068 loading method Methods 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 238000011160 research Methods 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
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 239000013543 active substance Substances 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000004146 energy storage Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 229940098779 methanesulfonic acid Drugs 0.000 description 2
- HLXXBLKUPMYKIC-UHFFFAOYSA-N methanesulfonic acid sulfuric acid Chemical compound CS(O)(=O)=O.OS(O)(=O)=O.OS(O)(=O)=O HLXXBLKUPMYKIC-UHFFFAOYSA-N 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000000638 solvent extraction Methods 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- FZUJWWOKDIGOKH-UHFFFAOYSA-N sulfuric acid hydrochloride Chemical compound Cl.OS(O)(=O)=O FZUJWWOKDIGOKH-UHFFFAOYSA-N 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- AFVFQIVMOAPDHO-UHFFFAOYSA-M Methanesulfonate Chemical compound CS([O-])(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-M 0.000 description 1
- NIPNSKYNPDTRPC-UHFFFAOYSA-N N-[2-oxo-2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 NIPNSKYNPDTRPC-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 239000006183 anode active material Substances 0.000 description 1
- 230000002238 attenuated effect Effects 0.000 description 1
- UNTBPXHCXVWYOI-UHFFFAOYSA-O azanium;oxido(dioxo)vanadium Chemical compound [NH4+].[O-][V](=O)=O UNTBPXHCXVWYOI-UHFFFAOYSA-O 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- QUXFOKCUIZCKGS-UHFFFAOYSA-N bis(2,4,4-trimethylpentyl)phosphinic acid Chemical compound CC(C)(C)CC(C)CP(O)(=O)CC(C)CC(C)(C)C QUXFOKCUIZCKGS-UHFFFAOYSA-N 0.000 description 1
- 239000006182 cathode active material Substances 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000002354 inductively-coupled plasma atomic emission spectroscopy Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 238000005272 metallurgy Methods 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 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
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M2300/00—Electrolytes
- H01M2300/0002—Aqueous electrolytes
- H01M2300/0005—Acid electrolytes
-
- 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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- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Sustainable Development (AREA)
- Sustainable Energy (AREA)
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
Abstract
The invention relates to an all-vanadium battery electrolyte and a preparation method thereof, wherein the all-vanadium battery electrolyte comprises a vanadium electrolyte and a supporting solution; the supporting solution is composed of CH 3 SO 3 H solution and HCl solution. The preparation method comprises the steps of sequentially extracting, washing and back-extracting vanadium-containing solution to obtain an electrolyte precursor of the all-vanadium battery; the precursor of the all-vanadium battery electrolyte is subjected to oil removal treatment and electrolytic oxidation reduction valence adjustment to obtain the all-vanadium battery electrolyte; the back extraction solution used for back extraction contains CH 3 SO 3 H and HCl. The electrolyte obtained by the invention has high vanadium concentration, high energy density, high charge and discharge efficiency, wide application temperature and good stability when being applied to the all-vanadium battery; the preparation method provided by the invention has the advantages of simple process, low cost and strong raw material adaptability.
Description
Technical Field
The invention relates to the field of vanadium batteries and preparation thereof, in particular to an all-vanadium battery electrolyte and a preparation method thereof.
Background
The all-vanadium battery is a novel green pollution-free chemical energy storage battery, realizes the storage and release of electric energy through the mutual conversion among vanadium ions in different valence states, has the advantages of high energy conversion rate, long theoretical service life, quick charge and discharge, mutually independent functions and capacities and the like, avoids the cross pollution caused by the mutual permeation of different types of active substances between the positive half battery and the negative half battery, and has good application prospects in the fields of renewable energy power storage, secondary energy storage, power grid peak regulation and the like.
The all-vanadium battery comprises a positive electrode and a negative electrode separated by a diaphragm, wherein the electrodes are composed of active substances and current collectors, the electrolyte generally takes sulfuric acid as supporting liquid, and the positive electrode electrolyte contains V 4+ /V 5+ Ion, negative electrode electrolyte contains V 2+ /V 3+ Ions. After the battery is charged, the positive electrode is V 5+ Ion solution with negative electrode V 2+ An ionic solution; after discharge, the positive electrode is V 4+ Ion solution with negative electrode V 3+ Ionic solution, inside of cell through H + Conducting electricity.
The energy density of the all-vanadium battery depends on the concentration of vanadium ions in the electrolyte, and the electrolyte with high vanadium concentration can realize high specific energy of the battery, but high-valence vanadium species can be hydrolyzed to generate precipitation phenomena due to concentration rise, temperature rise and the like. Vanadium ions of low valence, in particular V 4+ And V 3+ The vanadium-containing catalyst has certain solubility in sulfuric acid solution, but the vanadium concentration is more than 2mol/L at low temperature, and the vanadium-containing catalyst is easy to crystallize and precipitate. Therefore, the vanadium battery with the vanadium concentration more than 2mol/L is relatively unstable and difficult to operate; total vanadium concentration of electrolyte of all-vanadium battery is generally<2mol/L, the applicable temperature is limited within the range of 10-40 ℃, the specific energy of the battery is restricted from being improved, and the use temperature environment is restricted, so that the commercial application of the battery is hindered.
CN108054413B discloses a method for preparing a high-energy 3.5-valence sulfur-salt mixed acid system vanadium electrolyte, which comprises the steps of sequentially adding sulfuric acid and hydrochloric acid into a 3.5-valence vanadium mixture to prepare the hydrochloric acid-sulfuric acid system electrolyte. The method can effectively prevent vanadium ion from precipitating by adding hydrochloric acid, improve the stability of vanadium ion, and ensure H required by electrolyte conduction by adding sulfuric acid + The concentration of vanadium ions in the obtained electrolyte is 1.5-3.9mol/L, and no precipitate is generated when the electrolyte is placed at the temperature of-20-50 ℃ for more than 60 days. The electrolyte obtained by the method has high concentration of vanadium ions through the reaction with Cl in the solution - Stable coordination and Cl - Too high a concentration, HCl is easily volatilized or V is easily generated in the system 5+ Oxidation produces chlorine. Thus, the methodWith HCl and H 2 SO 4 As the supporting solution of the electrolyte, through intensive research, the most suitable vanadium concentration in the system is 2.5mol/L, and the vanadium battery electrolyte higher than 2.5mol/L needs higher concentration of Cl - Ion coordination is maintained, and HCl or Cl is easy to appear in battery operation 2 And (3) emission risk.
CN102227029a discloses a high-concentration vanadium electrolyte and a preparation method thereof, the method uses electrolyte containing tetravalent and pentavalent vanadium ions as an anode active material, uses electrolyte containing trivalent and divalent vanadium ions as a cathode active material, and simultaneously adds methanesulfonic acid into the electrolyte, wherein the total vanadium concentration in the electrolyte can reach 2-4mol/L. The electrolyte improves stability by adding the coordination of methylsulfonate and vanadium ions, but the methylsulfonic acid has high viscosity, and although the improvement effect of stable vanadium concentration is obvious, the electrolyte is influenced by viscosity and H + The influence of the concentration greatly influences the conductivity of the electrolyte, and the charge and discharge effects of the battery are poor.
CN102306820a discloses a method for preparing electrolyte for vanadium battery, which comprises adding sulfuric acid and methanesulfonic acid into positive electrode or negative electrode electrolyte of vanadium ion, wherein the concentration of vanadium in the obtained methanesulfonic acid-sulfuric acid system electrolyte can reach 0.8-5mol/L. In the method, the stability of the high-concentration vanadium electrolyte is enhanced mainly through coordination of the methylsulfonic acid and vanadium ions, but researches show that the methylsulfonic acid exceeds 1mol/L in a 3mol/L sulfuric acid system, the viscosity of the solution is obviously increased, and the conductivity is seriously attenuated. Therefore, the concentration of sulfuric acid and methylsulfonic acid is limited, the concentration of vanadium in the electrolyte is 2mol/L, which is the optimal working concentration of the battery, the vanadium concentration is further improved, and the working efficiency of the battery is not obviously improved.
CN103515641a discloses a trivalent vanadium ion electrolyte, a preparation method thereof and a vanadium battery, the method uses sulfuric acid solution containing vanadyl sulfate as a cathode, uses the sulfuric acid solution as an anode, performs constant-voltage electrolysis to obtain the trivalent vanadium ion electrolyte with the molar ratio of trivalent vanadium to all vanadium being greater than 0.98, the vanadium concentration is 1-3mol/L, and the electrolysis temperature is 20-40 ℃. In order to avoid the introduction of impurity ions, the process needs a high-purity vanadium raw material, and has high price, so that the production cost of the vanadium battery electrolyte is increased.
CN105006585a discloses a method for preparing electrolyte for all-vanadium redox flow battery, which uses oxalic acid and other reducing agents to reduce part of vanadium pentoxide, then adds stabilizer, and places the mixture in an electrolytic tank for constant current electrolysis to obtain mixed electrolyte of 3-valence vanadium and 4-valence vanadium, and the total vanadium concentration is 1.0-5.0mol/L. The method also needs vanadium pentoxide with purity of more than 99.5 percent as a raw material, however, the high-purity vanadium raw material has high price, which is not beneficial to the large-scale production of the electrolyte.
According to the comprehensive research, the problems of low vanadium concentration and small applicable temperature range of the electrolyte of the all-vanadium battery are generally found, and the energy density of the vanadium battery is not improved. Although there have been studies in which stability of an electrolyte is improved by changing a system of a supporting solution, such as a hydrochloric acid-sulfuric acid system, a methanesulfonic acid-sulfuric acid system, etc., there is a decrease in conductivity or a decrease in Cl due to an increase in viscosity of the electrolyte - And the problems of excessively high release of harmful gases and the like, and the optimized vanadium ion concentration is still below 2.5mol/L. In addition, as can be seen from the preparation method of the electrolyte, the existing all-vanadium battery electrolyte needs to adopt high-purity vanadium products such as vanadyl sulfate, vanadic anhydride and the like, so that the cost is high, the complexity of the preparation process is increased, and the industrial application of the all-vanadium battery electrolyte is not facilitated.
Therefore, the high-stability high-concentration all-vanadium battery electrolyte and the preparation method thereof have important significance.
Disclosure of Invention
Aiming at the problems, the invention aims to provide the all-vanadium battery electrolyte and the preparation method thereof, and compared with the prior art, the all-vanadium battery electrolyte provided by the invention has the advantages of high vanadium concentration, good stability and wide applicable temperature range; the preparation method provided by the invention does not need to adopt a high-purity vanadium raw material or prepare a high-purity solid vanadium raw material by metallurgy, and can obtain the electrolyte with high vanadium concentration by only adopting a vanadium-containing feed liquid and performing valence-adjusting extraction, so that the production cost is low.
In order to achieve the aim of the invention, the invention adopts the following technical scheme:
in a first aspect, the present invention provides an all-vanadium battery electrolyte comprising a vanadium electrolyte and a supporting solution;
the supporting solution is composed of CH 3 SO 3 H solution and HCl solution.
The electrolyte of the all-vanadium battery provided by the invention adopts CH 3 SO 3 The supporting solution consisting of H solution and HCl solution can be prepared by CH 3 SO 3 The H and the HCl cooperatively regulate the viscosity and the stability of the electrolyte, so that the vanadium concentration is increased, the temperature application range is enlarged, and the specific energy of the battery is further improved.
The electrolyte adopts CH 3 SO 3 H and HCl as supporting solutions, compared with H 2 SO 4 And/or CH 3 SO 3 Electrolyte taking H as supporting liquid and H 2 SO 4 And CH (CH) 3 SO 3 H is the electrolyte for supporting the solution, so that the stability of the electrolyte is enhanced, the temperature application range of the electrolyte is enlarged, the viscosity of the electrolyte is effectively controlled, and the conductivity is improved.
Preferably, the vanadium concentration in the electrolyte of the all-vanadium battery is 2.5-5mol/L, for example, 2.5mol/L, 2.6mol/L, 2.8mol/L, 3mol/L, 3.2mol/L, 3.4mol/L, 3.6mol/L, 3.8mol/L, 4mol/L, 4.5mol/L or 5mol/L, but not limited to the recited values, other non-recited values in the numerical range are equally applicable, and 3-4mol/L is preferred.
Preferably, CH in the supporting solution 3 SO 3 - The concentration of (C) is 5-10mol/L, and may be, for example, 5mol/L, 6mol/L, 7mol/L or 10mol/L, but is not limited to the values recited, and other values not recited in the numerical range are equally applicable.
Preferably, cl in the supporting solution - The concentration of (C) is 1-5mol/L, and may be, for example, 1mol/L, 2mol/L, 3mol/L, 4mol/L or 5mol/L, but is not limited to the values recited, and other values not recited in the numerical range are equally applicable.
Preferably, CH in the supporting solution 3 SO 3 - And Cl - The molar ratio of (2) to (1) to (10) to (1) is, for example, 1:1, 2:1, 5:1 or 10:1, but is not limited to the values recited, and other values not recited in the numerical range are equally applicable.
Preferably, free H in the supporting solution + The concentration of (C) is 1-4mol/L, and may be, for example, 1mol/L, 2mol/L, 3mol/L or 4mol/L, but is not limited to the values recited, and other values not recited in the numerical range are equally applicable.
Other additives which are beneficial to improving the performance of the electrolyte can be added into the electrolyte of the all-vanadium battery, for example, sulfuric acid, phosphoric acid and the like.
In a second aspect, the invention also provides a preparation method of the electrolyte of the all-vanadium battery, which comprises the following steps:
(1) Extracting the extractant solution and the vanadium-containing solution to obtain a vanadium-loaded organic phase;
(2) Washing the vanadium-loaded organic phase obtained in the step (1) to obtain a purified vanadium-loaded organic phase;
(3) Carrying out back extraction on the purified vanadium loaded organic phase and the back extraction solution obtained in the step (2) to obtain an electrolyte precursor of the all-vanadium battery;
the back extraction solution contains CH 3 SO 3 A mixed acid solution of H and HCl;
(4) And (3) sequentially carrying out oil removal treatment and electrolytic oxidation reduction valence adjustment on the electrolyte precursor of the all-vanadium battery, thus obtaining the electrolyte of the all-vanadium battery.
The source of the vanadium-containing solution is not particularly limited, and may be, for example, a vanadium-containing solution produced in the metallurgical industry, a vanadium-containing solution produced by acid-dissolving vanadium pentoxide, or a vanadium-containing solution such as vanadyl sulfate or ammonium vanadate.
In the invention, the oil removal treatment is to further remove an oil phase in the electrolyte by using an adsorbent; the electrolytic oxidation-reduction valence adjustment is to place the prepared electrolyte in an electrolytic tank, and adjust vanadium to the required valence through oxidation-reduction treatment by electrolysis.
The invention adopts solvent extraction-back extraction technology to sequentially extract, wash and back extract vanadium-containing solution, thus obtaining electrolyte, and CH is contained on the basis 3 SO 3 On one hand, the mixed acid solution of H and HCl is used as a back extraction solution, and on the other hand, high-purity vanadium raw materials are not required, so that the production cost is reduced, and the preparation process is simplified; on the other hand by CH 3 SO 3 The viscosity of the electrolyte is cooperatively regulated by H and HCl, so that the stability of the electrolyte is enhanced, the temperature application range is enlarged, and the specific energy of the battery is improved.
Preferably, the vanadium in the vanadium-containing solution in step (1) is tetravalent, and the vanadium concentration is 1-30g/L, for example, 1g/L, 5g/L, 10g/L, 15g/L, 20g/L or 30g/L, but not limited to the recited values, and other non-recited values in the numerical range are equally applicable.
In the invention, vanadium in the vanadium-containing solution is generally regulated to be tetravalent before preparation, which is more favorable for extraction by a solvent extraction method, and the valence of the vanadium-containing solution containing tetravalent vanadium is not required to be regulated.
Preferably, the extractant solution of step (1) contains an extractant and a diluent.
Preferably, the extractant is an acidic phosphine extractant, and may be any one or a combination of at least two of P204, P507 or Cyanex 272.
Preferably, the diluent is a saturated hydrocarbon, which may be kerosene, for example.
Preferably, the extractant solution in step (1) has a volume percentage of 10-30%, for example 10%, 15%, 20%, 25% or 30%, but not limited to the values recited, and other values not recited in the range are equally applicable.
Preferably, the ratio of the volume of the extractant solution to the volume of the vanadium-containing solution is (0.1-2): 1, which may be, for example, 0.1:1, 1:1, 1.2:1, 1.5:1, 1.8:1 or 2:1, but is not limited to the recited values, as other non-recited values within the range of values are equally applicable.
Preferably, the temperature of the extraction in step (1) is 10-40 ℃, for example, 10 ℃, 20 ℃, 25 ℃, 30 ℃, 35 ℃ or 40 ℃, but not limited to the values listed, other non-listed values within the range are equally applicable, and the extraction is generally performed at room temperature.
Preferably, the mixing time of the two phases in the extraction is 2-5min, for example, 2min, 3min, 4min or 5min, but not limited to the recited values, and other non-recited values in the range of values are equally applicable.
Preferably, the pH of the extraction is 1.5-2, which may be, for example, 1.5, 1.6, 1.7, 1.8, 1.9 or 2, but is not limited to the recited values, and other non-recited values within the range of values are equally applicable.
Preferably, the extraction comprises continuous countercurrent extraction.
The extraction stage number is not particularly limited, and can be adjusted according to actual working conditions, and is generally 1-10 stages.
Preferably, the washing liquid of the washing in the step (2) comprises an acid liquid, which may be, for example, HCl solution and/or H 2 SO 4 A solution.
Preferably, the concentration of the acid solution is 0.5 to 5mol/L, for example, 0.5mol/L, 1mol/L, 2mol/L, 3mol/L, 4mol/L or 5mol/L, but not limited to the recited values, and other values not recited in the numerical range are equally applicable.
Preferably, the volume ratio of the wash solution to the vanadium-loaded organic phase is (0.05-1): 1, which may be, for example, 0.05:1, 0.1:1, 0.2:1, 0.5:1, 0.8:1 or 1:1, but is not limited to the recited values, as other non-recited values within the range of values are equally applicable.
Preferably, the washing comprises a continuous countercurrent washing.
The washing stage number is not particularly limited, and can be adjusted according to actual working conditions, and is generally 1-10 stages.
Preferably, step (3) is performed by mixing CH in the acid solution 3 SO 3 - The concentration of (C) is 5-10mol/L, and may be, for example, 5mol/L, 6mol/L, 7mol/L or 10mol/L, but is not limited to the values recited, and other values not recited in the numerical range are equally applicable.
The invention preferably controls CH in the mixed acid solution 3 SO 3 - The concentration of (2) is in a specific range, the stability of the electrolyte can be improved, and the viscosity of the electrolyte can be controlled, so that the conductivity can be improved.
Preferably, cl in the mixed acid solution - The concentration of (C) is 1-5mol/L, and may be, for example, 1mol/L, 2mol/L, 3mol/L, 4mol/L or 5mol/L, but is not limited to the values recited, and other values not recited in the numerical range are equally applicable.
Preferably, CH in the mixed acid solution 3 SO 3 - And Cl - The molar ratio of (2) to (1) to (10) to (1) is, for example, 1:1, 2:1, 3:1, 5:1 or 10:1, but is not limited to the values recited, and other values not recited in the range are equally applicable.
The invention preferably controls CH in the mixed acid solution 3 SO 3 - And Cl - The ratio of the molar amounts of (c) is in a specific range, and the viscosity of the electrolyte can be controlled while improving the stability of the electrolyte, thereby improving the conductivity.
Preferably, the temperature of the back extraction in the step (3) is 10 to 40 ℃, for example, 10 ℃, 20 ℃, 22 ℃, 24 ℃, 26 ℃, 28 ℃, 30 ℃, 35 ℃ or 40 ℃, but not limited to the values listed, and other values not listed in the range are applicable, and the back extraction is generally carried out at room temperature.
Preferably, the mixing time of the two phases in the back extraction is 2-5min, for example, 2min, 2.2min, 2.4min, 2.6min, 2.8min, 3min, 3.5min, 4min, 4.5min or 5min, but not limited to the recited values, and other non-recited values in the range of values are equally applicable.
Preferably, the stripping comprises continuous countercurrent stripping.
The number of the back extraction stages is not particularly limited, and can be adjusted according to actual working conditions, and is generally 1-10 stages.
Preferably, the degreasing treatment comprises adsorption with an adsorption resin and/or activated carbon.
As a preferred technical solution of the second aspect of the present invention, the preparation method includes the following steps:
(1) Mixing an extractant and a diluent to obtain an extractant solution, wherein the extractant comprises an acidic phosphine extractant, and the volume percentage of the extractant in the extractant solution is 10-30%;
continuously countercurrent extracting the extractant solution and the vanadium-containing solution for 2-5min at the temperature of 10-40 ℃ and the pH value of 1.5-2, wherein vanadium in the vanadium-containing solution is tetravalent, the vanadium concentration is 1-30g/L, and the volume ratio of the extractant solution to the vanadium-containing solution is (0.1-2): 1, so as to obtain a vanadium-loaded organic phase;
(2) Carrying out continuous countercurrent washing on the vanadium-loaded organic phase obtained in the step (1), wherein washing liquid comprises acid liquor, the concentration of the acid liquor is 0.5-5mol/L, the volume ratio of the washing liquid to the vanadium-loaded organic phase is (0.05-1): 1, and the purified vanadium-loaded organic phase is obtained;
(3) Carrying out back extraction on the vanadium-loaded organic phase obtained in the step (2) after purification and a back extraction solution, wherein the back extraction solution contains CH 3 SO 3 H and HCl in a mixed acid solution of CH 3 SO 3 - The concentration of (2) is 5-10mol/L, cl in the mixed acid solution - The concentration of (2) is 1-5mol/L, and CH in the mixed acid solution 3 SO 3 - And Cl - The molar ratio of the components is 1:1-10:1, and the electrolyte precursor of the all-vanadium battery is obtained;
(4) And (3) sequentially carrying out oil removal treatment and electrolytic oxidation reduction valence adjustment on the electrolyte precursor of the all-vanadium battery, thus obtaining the electrolyte of the all-vanadium battery.
Compared with the prior art, the invention has the following beneficial effects:
(1) The electrolyte of the all-vanadium battery provided by the invention adopts CH 3 SO 3 The mixed solution of H and HCl is used as a supporting solution and is passed through CH 3 SO 3 - The stability of vanadium ions in each valence state is enhanced, and the conductivity of the electrolyte is enhanced by the strong acidity and low viscosity of HCl, so that the optimized concentration of the vanadium electrolyte reaches 2.89-4.94mol/L, the temperature application range is expanded to-10-60 ℃, and the conductivity can reach 132mS/cm or more, and under the preferable condition, 165mS/cm or more can be achieved.
(2) The preparation method provided by the invention takes the vanadium-containing solution as a raw material, adopts a solvent extraction method to prepare the electrolyte, does not need to adopt a high-purity vanadium-containing raw material, does not need to metallurgically prepare a solid vanadium raw material, has a simple preparation process and low cost, and can be used for industrial production of the electrolyte of the all-vanadium battery.
Detailed Description
The technical scheme of the invention is further described by the following specific embodiments. It will be apparent to those skilled in the art that the examples are merely to aid in understanding the invention and are not to be construed as a specific limitation thereof.
Example 1
The embodiment provides a preparation method of an all-vanadium battery electrolyte, which comprises the following steps:
(1) Mixing P204 with kerosene to obtain an extractant solution, wherein the volume percentage of P204 in the extractant solution is 20%;
carrying out 3-level continuous countercurrent extraction on the extractant solution and the vanadium-containing solution at the temperature of 25 ℃ and the pH value of 1.7, wherein the mixing time of two phases in contact is 3.5min, and the volume ratio of the extractant solution to the vanadium-containing solution is 1:1, so as to obtain a vanadium-loaded organic phase;
the vanadium-containing solution is a vanadium-containing sulfuric acid solution obtained in the metallurgical industry, and 15g/LV is obtained through treatment 4+ And main impurity elements Na 28g/L, cr 1.3g/L, si 0.1.1 g/L and Al 0.3g/L;
(2) Carrying out 3-stage continuous countercurrent washing on the vanadium-loaded organic phase obtained in the step (1), wherein the washing liquid is 2.7mol/L H 2 SO 4 The volume ratio of the washing liquid to the vanadium-loaded organic phase is 0.1:1, so that a purified vanadium-loaded organic phase is obtained;
(3) Loading the purified vanadium obtained in the step (2) with an organic phase and CH 3 SO 3 Carrying out 4-level continuous countercurrent back extraction on a mixed acid solution of H and HCl at the temperature of 25 ℃, wherein the volume ratio of a loaded organic phase to a back extraction solution is 10:1, the mixing time of two-phase contact is 3.5min, and the mixed acid is solubleCH in liquid 3 SO 3 - At a concentration of 10mol/L, cl - At a concentration of 1mol/L, CH 3 SO 3 - And Cl - The molar ratio of (2) is 10:1; obtaining the electrolyte precursor of the all-vanadium battery;
(4) And (3) sequentially carrying out oil removal treatment and electrolytic oxidation reduction valence adjustment on the electrolyte precursor of the all-vanadium battery by adopting activated carbon adsorption to obtain the electrolyte of the all-vanadium battery.
The embodiment also provides the all-vanadium battery electrolyte obtained by the preparation method, wherein the total yield of vanadium is 98.7% after the vanadium-containing solution is extracted, washed and back extracted, and the concentration of vanadium in the all-vanadium battery electrolyte is 4.94mol/L, CH 3 SO 3 - At a concentration of 10mol/L, cl - The concentration of (C) is 1mol/L, H + The concentration of (C) is 1.12mol/L, CH 3 SO 3 - And Cl - The molar ratio of (2) is 10:1.
Example 2
The embodiment provides a preparation method of an all-vanadium battery electrolyte, which comprises the following steps:
(1) Mixing P507 with kerosene to obtain an extractant solution, wherein the volume percentage of P507 in the extractant solution is 10%;
carrying out 3-stage continuous countercurrent extraction on an extractant solution and a vanadium-containing solution at the temperature of 10 ℃ and the pH value of 1.8 for 5min, wherein the volume ratio of the extractant solution to the vanadium-containing solution is 0.1:1, so as to obtain a vanadium-loaded organic phase;
the vanadium-containing solution is as follows: placing a mixture of vanadium pentoxide and sulfuric acid into a cathode chamber of an electrolytic tank, and adding sulfuric acid into an anode chamber of the electrolytic tank for electrolysis to prepare a tetravalent vanadium ion solution, wherein the main components of the tetravalent vanadium ion solution comprise tetravalent vanadium 1g/L, and main impurity elements of Na 105mg/L, fe 23mg/L and Ca38mg/L;
(2) Carrying out 3-stage continuous countercurrent washing on the vanadium-loaded organic phase obtained in the step (1), wherein washing liquid of the washing is 0.5mol/L H 2 SO 4 The volume ratio of the washing liquid to the vanadium-loaded organic phase is 1:1, and the purified vanadium-loaded organic phase is obtainedAn organic phase;
(3) Loading the purified vanadium obtained in the step (2) with an organic phase and CH 3 SO 3 Carrying out 4-level continuous countercurrent back extraction on a mixed acid solution of H and HCl at the temperature of 40 ℃, wherein the volume ratio of a loaded organic phase to a back extraction solution after purification is 15:1, the mixing time of two-phase contact is 2min, and CH in the mixed acid solution 3 SO 3 - At a concentration of 5mol/L, cl - Is 5mol/L, CH 3 SO 3 - And Cl - The molar ratio of the components is 1:1, and the electrolyte precursor of the all-vanadium battery is obtained;
(4) And (3) sequentially carrying out oil removal treatment and electrolytic oxidation reduction valence adjustment on the electrolyte precursor of the all-vanadium battery by adopting activated carbon adsorption to obtain the electrolyte of the all-vanadium battery.
The embodiment also provides the all-vanadium battery electrolyte obtained by the preparation method, wherein the total yield of vanadium is 99.2% after the vanadium-containing solution is extracted, washed and back extracted, and the concentration of vanadium in the all-vanadium battery electrolyte is 3.89mol/L and CH 3 SO 3 - At a concentration of 5mol/L, cl - Is 5mol/L, H + The concentration of (C) is 2.21mol/L, CH 3 SO 3 - And Cl - The molar ratio of (2) is 1:1.
Example 3
The embodiment provides a preparation method of an all-vanadium battery electrolyte, which comprises the following steps:
(1) Mixing P204 with kerosene to obtain an extractant solution, wherein the volume percentage of P204 in the extractant solution is 30%;
carrying out 3-level continuous countercurrent extraction on the extractant solution and the vanadium-containing solution at the temperature of 40 ℃ and the pH value of 2, wherein the mixing time of two-phase contact is 2min, and the volume ratio of the extractant solution to the vanadium-containing solution is 1.5:1, so as to obtain a vanadium-loaded organic phase;
the vanadium-containing solution is a vanadium-containing solution obtained in the metallurgical industry, is a tetravalent vanadium 30g/L chloridizing solution, and comprises the following main impurities: na 51g/L, cr 2.0g/L, si 0.1.1 g/L, al 0.2g/L;
(2) Carrying out 3-level continuous countercurrent washing on the vanadium-loaded organic phase obtained in the step (1), wherein washing liquid obtained in the step (1) is 5mol/L HCl solution, and the volume ratio of the washing liquid to the vanadium-loaded organic phase is 0.05:1, so as to obtain a purified vanadium-loaded organic phase;
(3) Loading the purified vanadium obtained in the step (2) with an organic phase and CH 3 SO 3 Carrying out 4-level continuous countercurrent back extraction on a mixed acid solution of H and HCl at the temperature of 10 ℃, wherein the volume ratio of a load organic phase to a back extraction solution after purification is 6:1, the mixing time of two-phase contact is 5min, and CH in the mixed acid solution 3 SO 3 - At a concentration of 6mol/L, cl - At a concentration of 3mol/L, CH 3 SO 3 - And Cl - The molar ratio of the components is 2:1, and the electrolyte precursor of the all-vanadium battery is obtained;
(4) And (3) sequentially carrying out oil removal treatment and electrolytic oxidation reduction valence adjustment on the electrolyte precursor of the all-vanadium battery by adopting activated carbon adsorption to obtain the electrolyte of the all-vanadium battery.
The embodiment also provides the all-vanadium battery electrolyte obtained by the preparation method, wherein the total yield of vanadium is 98.3% after the vanadium-containing solution is extracted, washed and back extracted, and the concentration of vanadium in the all-vanadium battery electrolyte is 2.89mol/L, CH 3 SO 3 - At a concentration of 6mol/L, cl - The concentration of (C) is 3mol/L, H + The concentration of (C) is 3.21mol/L, CH 3 SO 3 - And Cl - The molar ratio of (2) to (1).
Example 4
This example provides a method for preparing an electrolyte of an all-vanadium battery, which differs from example 1 only in that CH in a mixed acid solution is controlled 3 SO 3 - And Cl - Is constant while adjusting the total molar mass of HCl and CH 3 SO 3 H is added in an amount to enable CH in the mixed acid solution 3 SO 3 - And Cl - The molar ratio of (2) is 0.5:1, i.e. CH 3 SO 3 - The molar concentration of (C) was adjusted to 3.7mol/L, cl - The molar concentration of (C) was adjusted to 7.3mol/L.
Example 5
This example provides a method for preparing an electrolyte of an all-vanadium battery, which differs from example 1 only in that CH in a mixed acid solution is controlled 3 SO 3 - And Cl - The total molar weight is unchanged, and HCl and CH are simultaneously regulated 3 SO 3 H is added in an amount to enable CH in the mixed acid solution 3 SO 3 - And Cl - The molar ratio of the two components is 11:1, namely CH 3 SO 3 - The molar concentration of (C) was adjusted to 10.1mol/L, cl - The molar concentration of (C) was adjusted to 0.9mol/L.
Comparative example 1
This comparative example provides an all-vanadium battery electrolyte which differs from example 1 only in that the support solution is replaced with H 2 SO 4 Solution, and adjust H 2 SO 4 The concentration of the solution is the concentration of the supporting solution under the optimal condition, namely the H 2 SO 4 The concentration of the solution was 5mol/L.
Comparative example 2
This comparative example provides an all-vanadium battery electrolyte which differs from example 1 only in that the supporting solution is replaced with CH 3 SO 3 H solution, and adjust CH 3 SO 3 The concentration of the H solution is the concentration of the supporting solution under the optimal condition, namely the CH 3 SO 3 The concentration of the H solution was 9mol/L.
Comparative example 3
This comparative example provides an all-vanadium battery electrolyte which differs from example 1 only in that the supporting solution is replaced with an HCl solution, and the concentration of the HCl solution is adjusted to be the concentration of the supporting solution under the optimal condition, i.e., the concentration of the HCl solution is 9mol/L.
Comparative example 4
This comparative example provides an all-vanadium battery electrolyte which differs from example 1 only in that the support solution is replaced with H 2 SO 4 And CH (CH) 3 SO 3 H mixed acid solution and adjust H 2 SO 4 And CH (CH) 3 SO 3 The concentration of H being the concentration of the supporting solution under optimal conditions, i.e. H 2 SO 4 At a concentration of 4.5mol/L, CH 3 SO 3 The concentration of H was 2.5mol/L.
The vanadium concentration in the all-vanadium battery electrolytes prepared in examples 1 to 5 and comparative examples 1 to 4 was measured by ICP-AES, and the results are shown in Table 1.
The operating temperatures of all vanadium battery electrolytes prepared in examples 1 to 5 and comparative examples 1 to 4 were measured using constant temperature static sampling observation, and the results are shown in table 1.
The conductivities of all vanadium cell electrolytes prepared in examples 1 to 5 and comparative examples 1 to 4 were measured using a beijing-family conductivity meter, and the results are shown in table 1.
TABLE 1
From table 1, the following points can be seen:
(1) The vanadium concentration of the electrolyte of the all-vanadium battery provided by the invention is high, and can reach 2.89-4.94mol/L, so that the energy density of the all-vanadium battery can be greatly improved; the applicable temperature range of the electrolyte of the all-vanadium battery provided by the invention can be expanded to-10-60 ℃, and the extreme environment requirements of high temperature and severe cold can be met; the electrolyte of the all-vanadium battery prepared by the invention also has good conductivity, can overcome the influence of the increase of the solution viscosity on the electrochemical performance, has the conductivity of more than 132mS/cm and can reach more than 165mS/cm under the better condition.
(2) As can be seen from a combination of the data from example 1 and examples 4-5, CH in example 1 3 SO 3 - And Cl - The molar ratio of 10:1, although higher vanadium concentrations can be achieved in example 4 than in examples 4-5 of 0.5:1 and 11:1, respectively, the system of example 4 is extremely unstable and gas is generated; while the vanadium concentration and conductivity in example 5 are lower than those in example 1, it can be seen that the present invention preferably controls CH 3 SO 3 - And Cl - Is of the mole of (2)The ratio of the molar quantity can enhance the stability of vanadium ions in various valence states and enhance the conductivity of the electrolyte.
(3) As can be seen from a combination of the data of comparative examples 1 and comparative examples 1 to 4, the support solutions in comparative examples 1 to 4 were replaced with H under the optimum concentration conditions, respectively 2 SO 4 Solution, CH 3 SO 3 H solution, HCl solution and H 2 SO 4 And CH (CH) 3 SO 3 The mixed acid solution of H, the vanadium concentration in the embodiment 1 is obviously higher than that of the comparative examples 1-4, the conductivity is obviously higher than that of the comparative examples 1, 2 and 4, and the applicable temperature range of the embodiment 1 is obviously higher than that of the comparative examples 1-2, so that the invention shows that the vanadium battery electrolyte and the preparation method thereof can improve the vanadium concentration and the conductivity, and simultaneously greatly expand the temperature application range.
In conclusion, the vanadium concentration of the electrolyte of the all-vanadium battery provided by the invention is high, the stability is good, the applicable temperature range is wide, the conductivity is good, and the preparation method of the electrolyte of the all-vanadium battery provided by the invention is low in cost, simple to operate and applicable to industrialization.
The applicant declares that the above is only a specific embodiment of the present invention, but the scope of the present invention is not limited thereto, and it should be apparent to those skilled in the art that any changes or substitutions that are easily conceivable within the technical scope of the present invention disclosed by the present invention fall within the scope of the present invention and the disclosure.
Claims (10)
1. An all-vanadium battery electrolyte is characterized by comprising a vanadium electrolyte and a supporting solution;
the supporting solution is composed of CH 3 SO 3 H solution and HCl solution.
2. The all-vanadium battery electrolyte according to claim 1, wherein the vanadium concentration in the all-vanadium battery electrolyte is 2.5-5mol/L, preferably 3-4mol/L;
preferably, CH in the supporting solution 3 SO 3 - The concentration of (2) is 5-10mol/L;
preferably, cl in the supporting solution - The concentration of (2) is 1-5mol/L;
preferably, CH in the supporting solution 3 SO 3 - And Cl - The molar ratio of (2) is 1:1-10:1;
preferably, free H in the supporting solution + The concentration of (C) is 1-4mol/L.
3. A method for preparing the electrolyte of the all-vanadium battery according to claim 1 or 2, comprising the following steps:
(1) Extracting the extractant solution and the vanadium-containing solution to obtain a vanadium-loaded organic phase;
(2) Washing the vanadium-loaded organic phase obtained in the step (1) to obtain a purified vanadium-loaded organic phase;
(3) Carrying out back extraction on the purified vanadium loaded organic phase and the back extraction solution obtained in the step (2) to obtain an electrolyte precursor of the all-vanadium battery;
the back extraction solution contains CH 3 SO 3 A mixed acid solution of H and HCl;
(4) And (3) sequentially carrying out oil removal treatment and electrolytic oxidation reduction valence adjustment on the electrolyte precursor of the all-vanadium battery, thus obtaining the electrolyte of the all-vanadium battery.
4. The method according to claim 3, wherein the vanadium in the vanadium-containing solution in the step (1) is tetravalent and the vanadium concentration is 1-30g/L.
5. The method according to claim 3 or 4, wherein the extractant solution of step (1) contains an extractant and a diluent;
preferably, the extractant is an acidic phosphine extractant;
preferably, the diluent is a saturated hydrocarbon;
preferably, in the extractant solution, the volume percentage of the extractant is 10-30%;
preferably, the ratio of the volume of the extractant solution to the volume of the vanadium-containing solution is (0.1-2): 1.
6. The process according to any one of claims 3 to 5, wherein the extraction temperature in step (1) is 10 to 40 ℃;
preferably, the mixing time of the two-phase contact during the extraction is 2-5min;
preferably, the pH of the extraction is 1.5-2;
preferably, the extraction comprises continuous countercurrent extraction.
7. The method of any one of claims 3-6, wherein the washed wash liquor of step (2) comprises an acid liquor;
preferably, the concentration of the acid liquor is 0.5-5mol/L;
preferably, the volume ratio of the washing liquid to the vanadium-loaded organic phase is (0.05-1): 1;
preferably, the washing comprises a continuous countercurrent washing.
8. The method according to any one of claims 3 to 7, wherein CH in the mixed acid solution of step (3) 3 SO 3 - The concentration of (2) is 5-10mol/L;
preferably, cl in the mixed acid solution - The concentration of (2) is 1-5mol/L;
preferably, CH in the mixed acid solution 3 SO 3 - And Cl - The molar ratio of (2) is 1:1-10:1.
9. The method of any one of claims 3 to 8, wherein the degreasing treatment of step (4) comprises adsorption with an adsorbent resin and/or activated carbon.
10. The preparation method according to any one of claims 3 to 9, characterized in that the preparation method comprises the steps of:
(1) Mixing an extractant and a diluent to obtain an extractant solution, wherein the extractant comprises an acidic phosphine extractant, and the volume percentage of the extractant in the extractant solution is 10-30%;
continuously countercurrent extracting the extractant solution and the vanadium-containing solution for 2-5min at the temperature of 10-40 ℃ and the pH value of 1.5-2, wherein vanadium in the vanadium-containing solution is tetravalent, the vanadium concentration is 1-30g/L, and the volume ratio of the extractant solution to the vanadium-containing solution is (0.1-2): 1, so as to obtain a vanadium-loaded organic phase;
(2) Carrying out continuous countercurrent washing on the vanadium-loaded organic phase obtained in the step (1), wherein washing liquid comprises acid liquor, the concentration of the acid liquor is 0.5-5mol/L, the volume ratio of the washing liquid to the vanadium-loaded organic phase is (0.05-1): 1, and the purified vanadium-loaded organic phase is obtained;
(3) Carrying out back extraction on the vanadium-loaded organic phase obtained in the step (2) after purification and a back extraction solution, wherein the back extraction solution contains CH 3 SO 3 H and HCl in a mixed acid solution of CH 3 SO 3 - The concentration of (2) is 5-10mol/L, cl in the mixed acid solution - The concentration of (2) is 1-5mol/L, and CH in the mixed acid solution 3 SO 3 - And Cl - The molar ratio of the components is 1:1-10:1, and the electrolyte precursor of the all-vanadium battery is obtained;
(4) And (3) sequentially carrying out oil removal treatment and electrolytic oxidation reduction valence adjustment on the electrolyte precursor of the all-vanadium battery, thus obtaining the electrolyte of the all-vanadium battery.
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