CN116207318A - All-vanadium redox flow battery electrolyte and preparation method thereof - Google Patents
All-vanadium redox flow battery electrolyte and preparation method thereof Download PDFInfo
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/18—Regenerative fuel cells, e.g. redox flow batteries or secondary fuel cells
- H01M8/184—Regeneration by electrochemical means
- H01M8/188—Regeneration by electrochemical means by recharging of redox couples containing fluids; Redox flow type batteries
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- 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
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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
Abstract
The invention discloses an all-vanadium redox flow battery electrolyte and a preparation method thereof, and belongs to the field of all-vanadium redox flow battery electrolyte preparation. The preparation raw materials of the electrolyte of the all-vanadium redox flow battery comprise: vanadium pentoxide, thiourea, sodium dodecyl sulfonate, absolute ethanol, thiourea dioxide, sodium chloride, boric acid, sulfuric acid, tributyl phosphate and perfluorobutyl sulfonic acid. The preparation method of the electrolyte of the all-vanadium redox flow battery comprises the following steps: preparing a primary reduction solution, performing secondary reduction and preparing an electrolyte of the all-vanadium redox flow battery. The prepared electrolyte of the all-vanadium redox flow battery has the advantages of good stability, strong energy storage capacity, wide temperature application range and the like. The problems of poor stability, narrow temperature application range and complex, expensive and energy-consuming electrolyte temperature control device are solved.
Description
Technical Field
The invention relates to the field of preparation of all-vanadium redox flow battery electrolyte, in particular to an all-vanadium redox flow battery electrolyte and a preparation method thereof.
Background
The all-vanadium redox flow battery is a high-efficiency rechargeable fuel battery with the maximum standard mode, the most advanced technology and the closest industrialization in the current world, has the advantages of high power, low cost, long service life, no pollution and the like, and has good application prospects in the fields of photovoltaic power generation, wind power generation, communication base stations, traffic municipal administration, military power storage and the like. The all-vanadium redox flow battery performs electrochemical reaction through the circulating flow of the electrode from bottom to top of vanadium electrolyte with different valence states, thereby realizing the mutual conversion of chemical energy and electric energy.
The positive and negative electrolytes of all-vanadium redox flow batteries are usually VOSO respectively 4 、V 2 (SO 4 ) 3 The concentration and the volume of the electrolyte of the all-vanadium redox flow battery determine the capacity of the battery as a storage place of the battery electric energy, and meanwhile, the stability and the temperature adaptability of the electrolyte of the all-vanadium redox flow battery determine the service life and the application range of the battery. The main methods for preparing the electrolyte of the all-vanadium redox flow battery at present are a physical dissolution method, a chemical reduction method and an electrolytic method. The physical dissolution method is to directly dissolve the high-purity VOSO 4 Dissolving solid in sulfuric acid
The electrolyte is obtained, the concentration of the electrolyte is small, and the electrolyte is difficult to produce and prepare on a large scale. The electrolysis method is a method suitable for large-scale production, but V with high purity is needed for producing vanadium electrolyte 2 O 5 As a raw material, and electrolytic method has a slow reaction rate and high requirements for equipment, and thus is difficult to realize. The chemical reduction method is to reduce high-valence vanadium oxide or vanadate by using a reducing agent to prepare an electrolyte. Common reducing agents are oxalic acid, elemental sulfur, sulfurous acid, organic carboxylic acids or alcohols, etc., V being brought to high temperature 2 O 5 The electrolyte of the all-vanadium redox flow battery prepared by the method has high concentration, strong energy storage capacity and poor stability. The high-concentration all-vanadium redox flow battery electrolyte is easy to hydrolyze and separate out V when the temperature is higher than 40 DEG C 2 O 5 Precipitation, at a temperature below 10deg.C, is prone to saturation precipitation of V 2 (SO 4 ) 3 The crystallization has narrow temperature application range, and a complex, expensive and energy-consuming electrolyte temperature control device is required to be equipped. Therefore, a preparation method of the high-concentration all-vanadium redox flow battery electrolyte with high stability and wide temperature application range is urgently needed to solve the problems that the temperature application range of the all-vanadium redox flow battery electrolyte is narrow, and a complex, expensive and energy-consuming electrolyte temperature control device is needed to be equipped.
Disclosure of Invention
In view of the above, the invention aims to provide an electrolyte of an all-vanadium redox flow battery and a preparation method thereof, so as to solve the problems of poor stability, narrow temperature application range and need to be equipped with a complicated, expensive and energy-consuming electrolyte temperature control device of the high-concentration all-vanadium redox flow battery.
The invention solves the technical problems by the following technical means:
the preparation raw materials of the all-vanadium redox flow battery electrolyte comprise: vanadium pentoxide, thiourea, sodium dodecyl sulfonate, absolute ethanol, thiourea dioxide, sodium chloride, boric acid, sulfuric acid, tributyl phosphate and perfluorobutyl sulfonic acid.
The invention also provides a preparation method of the electrolyte of the all-vanadium redox flow battery, which comprises the following steps:
(1) Preparing a primary reducing solution: dissolving thiourea and sodium dodecyl sulfate in absolute ethyl alcohol, adding deionized water, and stirring for 30-40min to obtain primary reduction solution;
(2) Primary reduction: adding vanadium pentoxide into the primary reduction solution, performing ultrasonic dispersion for 10-20min under the condition of 60-80kHz, and then heating and stirring to obtain a reduction suspension;
(3) Secondary reduction: adding tributyl phosphate and perfluorobutyl sulfonic acid into the reduction suspension, uniformly mixing, adding thiourea dioxide for full dissolution, pouring into a reaction kettle, and heating for reaction to obtain secondary reduction slurry;
(4) Preparing an electrolyte of the all-vanadium redox flow battery: and adding sulfuric acid, boric acid and sodium chloride into the secondary reduction slurry, and stirring until the precipitate completely disappears to obtain the electrolyte of the all-vanadium redox flow battery.
Further, the temperature of heating and stirring in the step (2) is 80-120 ℃ and the time is 10-20min.
Still further, the temperature of the heating reaction in the step (3) is 140-180 ℃ and the time is 10-15min.
Further, in the step (1), the mass ratio of thiourea, sodium dodecyl sulfonate, absolute ethyl alcohol and deionized water is (1-2): (0.2-0.4): (1-2): (2-4).
Still further, the mass ratio of the vanadium pentoxide to the primary reduction solution in the step (2) is (1-2): (2-3).
Still further, the mass ratio of tributyl phosphate, perfluorobutyl sulfonic acid, thiourea dioxide and the reduction suspension in the step (3) is (0.02-0.04): (0.02-0.04): (0.01-0.03): (1-3).
Still further, in the step (4), the mass ratio of the secondary reduction slurry, sodium chloride, sulfuric acid and boric acid is (1-2): (0.2-0.4): (2.0-3.0): (0.1-0.3).
According to the invention, thiourea and dodecyl sulfonic acid are dissolved in absolute ethyl alcohol, water is added to prepare a primary reduction solution, vanadium pentoxide is added into the primary reduction solution, and the vanadium pentoxide is reduced under the reduction effect of thiourea and the micelle effect of dodecyl sulfonic acid to obtain a reduction suspension. The reduction suspension contains a large amount of tetravalent vanadium ions, and the suspension is VS 4 . Tributyl phosphate and perfluorobutyl sulfonic acid are added into the reduction suspension, and then uniformly mixed with thiourea dioxide, so that the reduction effect is effectively prevented from being deteriorated due to elemental sulfur in the oxidation-reduction process, and the secondary reduction slurry is obtained by reaction under the conditions of high temperature and high pressure, and the suspension VS in the obtained secondary reduction slurry is obtained 4 Partial conversion to V 2 S 3 Particles forming VS 4 And V 2 S 3 And a coexistence system. Subsequent addition of sulfuric acid, boric acid and sodium chloride successfully completed VS 4 Conversion to VOSO 4 ，V 2 S 3 Conversion to V 2 (SO 4 ) 3 And S is 2- With SO 4 2+ Also coexist in the system, VOSO under the system 4 And V 2 (SO 4 ) 3 The concentration is high, the stability is good, and the energy storage capacity of the electrolyte of the all-vanadium redox flow battery is high.
VO in the system 2 + Hydrolyzing and separating out V under high temperature condition 2 O 5 During precipitation, S 2- Has a reducing effect in the system, and VO is recovered 2 + Reduction to VO 2+ At the same time S 2- Hydrolysis and VO also occur 2 + Generates competition, thereby making V 2 O 5 The precipitation is slow under the high temperature condition. In addition, the electrolyte also contains dodecyl sulfonic acid, which can also effectively improve VO 2 + Is delayed in V under high temperature conditions 2 O 5 Is precipitated. S in the system under low temperature condition 2- And absolute ethyl alcohol effectively improve V 2 (SO 4 ) 3 Solubility of V 2 (SO 4 ) 3 The crystallization is not easy to separate out. At S 2- Under the combined action of dodecyl sulfonic acid and absolute ethyl alcohol, the application range of the electrolyte temperature of the all-vanadium redox flow battery is widened.
The beneficial effects are that:
1. the electrolyte of the all-vanadium redox flow battery prepared by the invention has the advantages of good stability, strong energy storage capacity, wide temperature application range and the like.
2. The vanadium pentoxide is successfully and fully reduced under the conditions of respectively heating and stirring and high-temperature reaction by thiourea and thiourea dioxide, and V under the high-temperature condition is delayed under the action of absolute ethyl alcohol and sodium dodecyl sulfonate 2 O 5 Is precipitated and V is improved 2 (SO 4 ) 3 Solubility of V 2 (SO 4 ) 3 The crystallization is not easy to separate out.
3. The electrolyte of the all-vanadium redox flow battery can not precipitate at the temperature of-10 ℃ to 60 ℃, meanwhile, the energy efficiency of the electrolyte of the all-vanadium redox flow battery can reach 98.6 percent, the cycle number when the discharge capacity is reduced to 70 percent of the initial discharge capacity can reach 352 times, and the conductivity is 681.2mS/cm.
Detailed Description
The present invention will be described in detail with reference to the following specific examples:
example 1: preparation of electrolyte of all-vanadium redox flow battery
(1) Preparing a primary reducing solution: respectively weighing 0.15kg of thiourea and 0.03kg of sodium dodecyl sulfate, dissolving in 0.15kg of absolute ethyl alcohol, adding 0.3kg of deionized water, and stirring for 35min to obtain a primary reduction solution;
(2) Primary reduction: weighing 0.15kg of vanadium pentoxide, adding into 0.25kg of primary reduction solution, performing ultrasonic dispersion for 15min under the condition of 70kHz, heating to 100 ℃, and stirring for 15min to obtain reduction suspension;
(3) Secondary reduction: adding 0.003kg of tributyl phosphate and 0.003kg of perfluorobutyl sulfonic acid into 0.2kg of reduction suspension, uniformly mixing, adding 0.002kg of thiourea dioxide for full dissolution, pouring into a reaction kettle, and heating to 160 ℃ for reaction for 12min to obtain secondary reduction slurry;
(4) Preparing an electrolyte of the all-vanadium redox flow battery: weighing 0.15kg of secondary reduction slurry, adding 0.25kg of sulfuric acid, 0.03kg of boric acid and 0.03kg of sodium chloride, and stirring until the precipitate completely disappears to obtain the all-vanadium redox flow battery electrolyte.
Example 2: preparation of electrolyte of all-vanadium redox flow battery
(1) Preparing a primary reducing solution: respectively weighing 0.2kg of thiourea and 0.02kg of sodium dodecyl sulfate, dissolving in 0.1kg of absolute ethyl alcohol, adding 0.2kg of deionized water, and stirring for 30min to obtain a primary reduction solution;
(2) Primary reduction: weighing 0.1kg of vanadium pentoxide, adding into 0.3kg of primary reduction solution, performing ultrasonic dispersion for 20min under the condition of 60kHz, heating to 120 ℃, and stirring for 10min to obtain reduction suspension;
(3) Secondary reduction: adding 0.002kg of tributyl phosphate and 0.002kg of perfluorobutyl sulfonic acid into 0.1kg of reduction suspension, uniformly mixing, adding 0.001kg of thiourea dioxide for full dissolution, pouring into a reaction kettle, heating to 140 ℃, and reacting for 15min to obtain secondary reduction slurry;
(4) Preparing an electrolyte of the all-vanadium redox flow battery: weighing 0.1kg of secondary reduction slurry, adding 0.2kg of sulfuric acid, 0.01kg of boric acid and 0.02kg of sodium chloride, and stirring until the precipitate completely disappears to obtain the all-vanadium redox flow battery electrolyte.
Example 3: preparation of electrolyte of all-vanadium redox flow battery
(1) Preparing a primary reducing solution: respectively weighing 0.1kg of thiourea and 0.04kg of sodium dodecyl sulfate, dissolving in 0.2kg of absolute ethyl alcohol, adding 0.4kg of deionized water, and stirring for 40min to obtain a primary reduction solution;
(2) Primary reduction: weighing 0.2kg of vanadium pentoxide, adding into 0.2kg of primary reduction solution, performing ultrasonic dispersion for 10min under the condition of 80kHz, heating to 80 ℃ and stirring for 20min to obtain reduction suspension;
(3) Secondary reduction: adding 0.004kg of tributyl phosphate and 0.004kg of perfluorobutyl sulfonic acid into 0.3kg of reduction suspension, uniformly mixing, adding 0.003kg of thiourea dioxide for full dissolution, pouring into a reaction kettle, heating to 180 ℃, and reacting for 10min to obtain secondary reduction slurry;
(4) Preparing an electrolyte of the all-vanadium redox flow battery: weighing 0.2kg of secondary reduction slurry, adding 0.3kg of sulfuric acid, 0.03kg of boric acid and 0.04kg of sodium chloride, and stirring until the precipitate completely disappears to obtain the all-vanadium redox flow battery electrolyte.
Comparative example 1: preparation of electrolyte of all-vanadium redox flow battery
This comparative example is to be compared with example 1, except that in step (1) of comparative example 1, thiourea is replaced with elemental sulfur, and the remaining steps are the same as example 1, and step (1) is specifically as follows:
(1) Preparing a primary reducing solution: respectively weighing 0.15kg of elemental sulfur and 0.03kg of sodium dodecyl sulfate, dissolving in 0.15kg of absolute ethyl alcohol, adding 0.3kg of deionized water, and stirring for 35min to obtain a primary reduction solution;
comparative example 2: preparation of electrolyte of all-vanadium redox flow battery
This comparative example is to be compared with example 1, except that sodium dodecyl sulfate is not added in step (1) of comparative example 2, but sodium dodecyl sulfate is replaced with thiourea, and the remaining steps are the same as example 1, and step (1) is specifically as follows:
(1) Preparing a primary reducing solution: 0.18kg of thiourea is weighed and dissolved in 0.15kg of absolute ethyl alcohol, and 0.3kg of deionized water is added and stirred for 35min to prepare a primary reduction solution.
Comparative example 3: preparation of electrolyte of all-vanadium redox flow battery
This comparative example is to be compared with example 1, except that the absolute ethanol is not added in step (1) of comparative example 3, but is replaced with deionized water, and the rest of the steps are the same as in example 1, and step (1) is specifically as follows:
(1) Preparing a primary reducing solution: respectively weighing and uniformly mixing 0.15kg of thiourea and 0.03kg of sodium dodecyl sulfonate, adding 0.45kg of deionized water, and stirring for 35min to obtain a primary reduction solution.
Comparative example 4: preparation of electrolyte of all-vanadium redox flow battery
This comparative example is to be compared with example 1, except that thiourea dioxide is replaced with elemental sulfur in step (3) of comparative example 3, and the remaining steps are the same as example 1, and step (3) is specifically as follows:
(3) Secondary reduction: adding 0.003kg of tributyl phosphate and 0.003kg of perfluorobutyl sulfonic acid into 0.2kg of reduction suspension, uniformly mixing, adding 0.002kg of elemental sulfur for full dissolution, pouring into a reaction kettle, and heating to 160 ℃ for reaction for 12min to obtain secondary reduction slurry;
comparative example 5: preparation of electrolyte of all-vanadium redox flow battery
This comparative example is in contrast to example 1, except that in step (2) of comparative example 5, heating is not performed, but stirring is performed at normal temperature, and the remaining steps are the same as example 1, and step (2) is specifically as follows:
(2) Primary reduction: weighing 0.15kg of vanadium pentoxide, adding into 0.25kg of primary reduction solution, performing ultrasonic dispersion for 15min at 70kHz, and stirring for 15min at normal temperature to obtain reduction suspension.
Comparative example 6: preparation of electrolyte of all-vanadium redox flow battery
This comparative example is in contrast to example 1, except that in step (3) of comparative example 6, the temperature-rising reaction is not performed, but the reaction is stirred at room temperature, and the remaining steps are the same as those of example 1, and step (3) is specifically as follows:
(3) Secondary reduction: 0.003kg of tributyl phosphate and 0.003kg of perfluorobutyl sulfonic acid are added into 0.2kg of reduction suspension, and after being uniformly mixed, 0.002kg of thiourea dioxide is added for full dissolution, and the mixture is stirred and reacted for 12min at normal temperature to obtain secondary reduction slurry.
Comparative example 7: preparation of electrolyte of all-vanadium redox flow battery
The comparative example is the most commonly used chemical reduction method for preparing the electrolyte of the all-vanadium redox flow battery in the current research
Weighing 0.5kg of vanadium pentoxide, putting into a beaker, adding 1.0kg of concentrated sulfuric acid for mixing, adding 2.0kg of deionized water, putting the beaker into a constant-temperature water bath kettle, setting the temperature to 80 ℃, slowly adding 3.5kg of oxalic acid while stirring, and continuing stirring until the solution becomes a uniform blue solution after the addition is completed to prepare the all-vanadium redox flow battery electrolyte.
Experiment one: all-vanadium redox flow battery electrolyte thermal stability test
The electrolyte solutions of all vanadium redox flow batteries prepared in example 1, comparative examples 1 to 6 and comparative example 7 were placed in an incubator at-30 deg.c, -10 deg.c, 60 deg.c and 80 deg.c for 3 days, respectively, and then the precipitate was collected after filtration, and the precipitate was weighed after air-drying, and the supernatant was collected, and the concentration of vanadium ions in the supernatant was measured by precipitation, and the results of three repetitions of the experiment are shown in table 1.
TABLE 1
Experiment II: all-vanadium redox flow battery electrolyte performance test
All indexes of the electrolyte of the all-vanadium redox flow battery prepared in the example 1 and the comparative example 7 are detected, and the obtained detection results are shown in the following table 2:
TABLE 2
Analysis of results:
as can be seen from comparison of the data of example 1 and comparative example 7 in Table 1, the electrolyte of the all-vanadium redox flow battery prepared in example 1 of the present invention has better stability, no precipitation occurs at-10 ℃ and 60 ℃, and the concentration of vanadium ions in the supernatant is 1.58mol/L and 1.62mol/L, respectively. Only 80.1g and 37.6g of precipitate were precipitated at-30℃and 80℃and the concentration of vanadium ions in the supernatant was 1.39mol/L and 1.51mol/L, respectively. The data of example 1 and comparative example 7 in table 2 show that the energy efficiency of the electrolyte of the all-vanadium redox flow battery prepared in example 1 is 98.6%, which is improved by 4.5% compared with comparative example 7; the cycle time for reducing the discharge capacity to the initial 70% can reach 352 times, and the discharge capacity is increased by 113 times compared with comparative example 7; the conductivity was 681.2mS/cm, which was 86.7mS/cm higher than that of comparative example 7.
As can be seen from comparison of examples 1 and comparative examples 1 to 4 in Table 1, comparative examples 1 to 4 were obtained with no thiourea in step (1), no sodium dodecyl sulfate in step (1), no absolute ethyl alcohol in step (1) and no thiourea dioxide in step (3), respectively, and the stability of the electrolyte of the all-vanadium redox flow battery was lowered, and the concentration of vanadium ions in the supernatant was also significantly lowered. The method shows that thiourea, sodium dodecyl sulfate and absolute ethyl alcohol are needed for preparing the primary reduction solution, the effect of the primary reduction in the step (2) is influenced due to the lack of any one of the thiourea, the sodium dodecyl sulfate and the absolute ethyl alcohol, and the stability of the prepared electrolyte of the all-vanadium redox flow battery is reduced, and the concentration of vanadium ions in the electrolyte is reduced. In addition, the electrolyte system enables VO to be realized without adding sodium dodecyl sulfonate and absolute ethyl alcohol 2 + Is reduced so that V under high temperature conditions 2 O 5 Fast precipitation, V under low temperature condition 2 (SO 4 ) 3 Is reduced in solubility, V 2 (SO 4 ) 3 And (3) quick crystallization and precipitation. The step (3) is not added with thiourea dioxide, so that the stability of the electrolyte of the all-vanadium redox flow battery is reduced and the concentration of vanadium ions in the electrolyte is reduced due to the influence on the secondary reduction effect.
As can be seen from comparison of example 1 and comparative examples 5 to 6 in table 1, comparative examples 5 to 6 are respectively carried out in step (2) without heating and stirring, and in step (3) without heating reaction, and the effects of primary reduction in step (2) and secondary reduction in step (3) are correspondingly affected, so that the stability of the electrolyte of the all-vanadium redox flow battery is reduced, and the concentration of vanadium ions in the electrolyte is reduced. The method shows that the step (2) and the step (3) have a synergistic effect, and vanadium ions can be fully reduced by a step-by-step reduction method to prepare the electrolyte of the all-vanadium redox flow battery with high stability and wide temperature application range.
The above embodiments are only for illustrating the technical solution of the present invention and not for limiting the same, and although the present invention has been described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that modifications and equivalents may be made thereto without departing from the spirit and scope of the technical solution of the present invention, which is intended to be covered by the scope of the claims of the present invention. The technology, shape, and construction parts of the present invention, which are not described in detail, are known in the art.
Claims (8)
1. The all-vanadium redox flow battery electrolyte is characterized by comprising the following raw materials: vanadium pentoxide, thiourea, sodium dodecyl sulfonate, absolute ethanol, thiourea dioxide, sodium chloride, boric acid, sulfuric acid, tributyl phosphate and perfluorobutyl sulfonic acid.
2. The preparation method of the all-vanadium redox flow battery electrolyte is characterized by comprising the following steps of:
(1) Preparing a primary reducing solution: dissolving thiourea and sodium dodecyl sulfate in absolute ethyl alcohol, adding deionized water, and stirring for 30-40min to obtain primary reduction solution;
(2) Primary reduction: adding vanadium pentoxide into the primary reduction solution, performing ultrasonic dispersion, and heating and stirring to obtain a reduction suspension;
(3) Secondary reduction: adding tributyl phosphate and perfluorobutyl sulfonic acid into the reduction suspension, uniformly mixing, adding thiourea dioxide, fully dissolving, pouring into a reaction kettle, and heating for reaction to obtain secondary reduction slurry;
(4) Preparing an electrolyte of the all-vanadium redox flow battery: and adding sulfuric acid, boric acid and sodium chloride into the secondary reduction slurry, and stirring until the precipitate completely disappears to obtain the electrolyte of the all-vanadium redox flow battery.
3. The method for preparing the electrolyte of the all-vanadium redox flow battery according to claim 2, wherein the heating and stirring temperature in the step (2) is 80-120 ℃ for 10-20min.
4. The method for preparing the electrolyte of the all-vanadium redox flow battery according to claim 3, wherein the temperature of the heating reaction in the step (3) is 140-180 ℃ and the time is 10-15min.
5. The method for preparing the electrolyte of the all-vanadium redox flow battery according to claim 2, wherein in the step (1), the mass ratio of thiourea, sodium dodecyl sulfate, absolute ethyl alcohol and deionized water is (1-2): (0.2-0.4): (1-2): (2-4).
6. The method for preparing the electrolyte of the all-vanadium redox flow battery according to claim 5, wherein the mass ratio of the vanadium pentoxide to the primary reducing solution in the step (2) is (1-2): (2-3).
7. The method for preparing the electrolyte of the all-vanadium redox flow battery according to claim 6, wherein in the step (3), the mass ratio of tributyl phosphate, perfluorobutyl sulfonic acid, thiourea dioxide and the reduction suspension is (0.02-0.04): (0.02-0.04): (0.01-0.03): (1-3).
8. The method for preparing the electrolyte of the all-vanadium redox flow battery according to claim 7, wherein the mass ratio of the secondary reduction slurry to the sodium chloride to the sulfuric acid to the boric acid in the step (4) is (1-2): (0.2-0.4): (2.0-3.0): (0.1-0.3).
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| CN117594823B (en) * | 2024-01-19 | 2024-04-09 | 浙江聚合储能科技有限公司 | Spliced liquid flow frame plate assembly and preparation method thereof |
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