CN115799586B - High-performance vanadium battery electrolyte of sulfuric acid/hydrochloric acid mixed acid system and preparation method thereof - Google Patents
High-performance vanadium battery electrolyte of sulfuric acid/hydrochloric acid mixed acid system and preparation method thereof Download PDFInfo
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Abstract
The invention relates to the technical field of vanadium battery electrolyte, in particular to a sulfuric acid/hydrochloric acid mixed acid system high-performance vanadium battery electrolyte and a preparation method thereof. It includes positive pole electrolyte and negative pole electrolyte, wherein: the positive electrode electrolyte comprises the following raw materials: vanadium pentoxide, sulfuric acid solution, sulfur dioxide and chlorine gas; the negative electrode electrolyte comprises the following raw materials: vanadium pentoxide, sulfuric acid solution, metal reducing agent, ammonia water and chlorine gas; in the preparation of the anode electrolyte, chlorine is continuously introduced in the proportioning process of vanadyl sulfate powder and sulfuric acid solution, the chlorine reacts with water in the solution to generate hydrochloric acid, the tetravalent vanadium ion anode electrolyte of a sulfuric acid/hydrochloric acid system is prepared, and in the preparation of the cathode electrolyte, the chlorine is continuously introduced in the proportioning process of vanadyl hydroxide and sulfuric acid solution, the chlorine reacts with water in the solution to generate hydrochloric acid, and the trivalent vanadium ion cathode electrolyte of the sulfuric acid/hydrochloric acid system is prepared.
Description
Technical Field
The invention relates to the technical field of vanadium battery electrolyte, in particular to a sulfuric acid/hydrochloric acid mixed acid system high-performance vanadium battery electrolyte and a preparation method thereof.
Background
The all-vanadium redox flow battery is a novel high-efficiency environment-friendly energy storage battery taking vanadium ion solutions with different valence states as positive and negative active substances. Unlike traditional accumulator, vanadium cell has the advantages of great capacity, deep great current discharge, long service life, cyclic use of active matter, no cross pollution, environment friendship, etc. and may be used widely in intelligent power network peak regulating system, large scale photoelectric and wind power converting system, remote mountain area energy storing system, uninterrupted power source or emergency power source system, municipal transportation, military facility, etc.
In addition, in order to reduce the preparation cost of the all-vanadium electrolyte, the prior art adopts low-cost vanadium compounds such as V2O5 and the like as raw materials for preparation, and some initial researches are carried out. The method has the advantages that the dissolution process of vanadium compounds such as V2O5 and the like is studied in detail, and the reducing agent such as oxalic acid and the like is introduced into the sulfuric acid solution to prepare vanadium electrolyte in various valence states, so that the preparation cost of the vanadium electrolyte can be greatly reduced. However, the method has poor temperature adaptability and low stability, and cannot meet higher environmental requirements, so that the high-performance vanadium battery electrolyte of the sulfuric acid/hydrochloric acid mixed acid system is urgently needed to solve the defects in the prior art.
Disclosure of Invention
The invention aims to provide a high-performance vanadium battery electrolyte of a sulfuric acid/hydrochloric acid mixed acid system and a preparation method thereof, so as to solve the problems in the prior art.
In order to achieve the above purpose, in one aspect, the invention provides a sulfuric acid/hydrochloric acid mixed acid system high-performance vanadium battery electrolyte, comprising an anode electrolyte and a cathode electrolyte, wherein:
the positive electrode electrolyte comprises the following raw materials: vanadium pentoxide, sulfuric acid solution, sulfur dioxide and chlorine gas;
the negative electrode electrolyte comprises the following raw materials: vanadium pentoxide, sulfuric acid solution, metal reducing agent, ammonia water and chlorine gas.
As a further improvement of the technical scheme, the metal reducing agent is at least one selected from zinc powder, magnesium powder, iron powder and potassium powder.
In another aspect, the invention provides a method for preparing the sulfuric acid/hydrochloric acid mixed acid system high-performance vanadium battery electrolyte, which comprises the following steps:
s1, adding vanadium pentoxide powder into sulfuric acid solution, and fully dissolving and activating to obtain vanadyl sulfate solution with alum ion;
s2, adding sulfur dioxide into a half of vanadyl sulfate solution to reduce to form vanadyl sulfate solution with tetravalent vanadium ions, dehydrating and drying to obtain vanadyl sulfate powder, adding the vanadyl sulfate powder into the sulfuric acid solution according to a proportion to dissolve, introducing chlorine, reacting the chlorine with water in the solution to generate hydrochloric acid and hypochlorous acid, and automatically decomposing the hypochlorous acid to form hydrochloric acid and oxygen, so that chloride ions are introduced into the electrolyte, volatilizing the oxygen in the air to obtain positive electrode electrolyte with a sulfuric acid/hydrochloric acid system, and improving the energy density and stability of the vanadium battery;
s3, adding a metal reducing agent into the rest half of vanadyl sulfate solution to prepare a divalent vanadium ion solution, filtering the divalent vanadium ion solution to remove the metal reducing agent, adding ammonia water to remove metal ions remained in the vanadium ion solution, enabling the ammonia water to react with the vanadium ions of the divalent vanadium ion solution to generate divalent vanadium hydroxide, and then enabling the divalent vanadium hydroxide to contact with air to generate trivalent vanadium hydroxide after oxidation reaction;
s4, filtering the vanadium hydroxide, repeatedly cleaning the filtered vanadium hydroxide by using distilled water, heating and concentrating the vanadium hydroxide by using steam, separating out crystals, finally adding the vanadium hydroxide crystals into sulfuric acid solution according to a proportion, introducing chlorine, reacting the chlorine with water in the solution to generate hydrochloric acid and hypochlorous acid, and automatically decomposing the hypochlorous acid to form hydrochloric acid and oxygen, so that chloride ions are introduced into the electrolyte, volatilizing the oxygen in the air, and slowly dissolving the vanadium hydroxide in a sulfuric acid/hydrochloric acid system to obtain a trivalent vanadium ion solution, namely the negative electrode electrolyte of the sulfuric acid/hydrochloric acid system.
Preferably, in the step S1, the activation ratio of the vanadium pentoxide powder added to the sulfuric acid solution is 1:2-2.5.
Preferably, in the step S1, the activation condition of the vanadium pentoxide powder is as follows: the temperature is 130-160 ℃, and the dissolution is carried out for 30-40min.
Preferably, in the step S2, the ratio of vanadyl sulfate powder to sulfuric acid solution is 1:2.
Preferably, in the step S2, the introducing time of the chlorine is 10-15min.
Preferably, in the step S4, the ratio of the vanadium hydroxide crystals to the sulfuric acid solution is 1:2.
Preferably, in the step S4, the introducing time of the chlorine is 10-15min.
Compared with the prior art, the invention has the beneficial effects that:
1. according to the preparation method of the sulfuric acid/hydrochloric acid mixed acid system high-performance vanadium battery electrolyte, when the positive electrode electrolyte is prepared, chlorine is continuously introduced in the proportioning process of vanadyl sulfate powder and sulfuric acid solution, the chlorine reacts with water in the solution to generate hydrochloric acid, the tetravalent vanadium ion positive electrode electrolyte of the sulfuric acid/hydrochloric acid system is prepared, when the negative electrode electrolyte is prepared, chlorine is continuously introduced in the proportioning process of vanadium hydroxide and sulfuric acid solution, the chlorine reacts with water in the solution to generate hydrochloric acid, and the trivalent vanadium ion negative electrode electrolyte of the sulfuric acid/hydrochloric acid system is prepared, and the sulfuric acid/hydrochloric acid system electrolyte has excellent stability through the addition of the hydrochloric acid.
2. In the preparation method of the sulfuric acid/hydrochloric acid mixed acid system high-performance vanadium battery electrolyte, sulfuric acid is used for activating vanadium pentoxide, vanadyl sulfate is prepared by a reduction method, and trivalent vanadium ions are prepared by a metal reducing agent and an ammonia method, so that the preparation process of the electrolyte is reasonable, and the obtained solution has good charge and discharge performance through a charge and discharge test.
Drawings
Fig. 1 is an overall flow diagram of the present invention.
Detailed Description
The following description of the embodiments of the present invention will be made clearly and completely with reference to the accompanying drawings, in which it is apparent that the embodiments described are only some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
The embodiment of the invention provides a sulfuric acid/hydrochloric acid mixed acid system high-performance vanadium battery electrolyte, which comprises an anode electrolyte and a cathode electrolyte, wherein:
the positive electrode electrolyte comprises the following raw materials: vanadium pentoxide, sulfuric acid solution, sulfur dioxide and chlorine.
The negative electrode electrolyte comprises the following raw materials: vanadium pentoxide, sulfuric acid solution, metal reducing agent, ammonia water and chlorine gas.
On the basis of the above, the method comprises the following steps:
in the positive electrode electrolyte: the purity of the vanadium pentoxide is more than or equal to 98 percent; the sulfuric acid solution is analytically pure, and the concentration is more than or equal to 98%; sulfur dioxide is analytically pure;
in the negative electrode electrolyte: the purity of the vanadium pentoxide is more than or equal to 98 percent; the concentration of the sulfuric acid solution is 64.3%; the metal oxidant is chemically pure; ammonia is chemically pure.
The metal reducing agent is at least one selected from zinc powder, magnesium powder, iron powder and potassium powder.
According to the embodiment of the invention, as shown in fig. 1, the invention also provides a preparation method for preparing the sulfuric acid/hydrochloric acid mixed acid system high-performance vanadium battery electrolyte, which comprises the following specific steps:
firstly, adding vanadium pentoxide powder into sulfuric acid solution according to the proportion of 1:2-2.5, fully dissolving for 30-40min and activating at the temperature of 130-160 ℃ to obtain vanadyl sulfate solution with alum oxide ions;
step two, adding sulfur dioxide into a half of vanadyl sulfate solution to reduce to form vanadyl sulfate solution with tetravalent vanadium ions, dehydrating and drying to obtain vanadyl sulfate powder, adding the vanadyl sulfate powder into the sulfuric acid solution to dissolve according to the ratio of 1:2, introducing chlorine for 10-15min, reacting the chlorine with water in the solution to generate hydrochloric acid and hypochlorous acid, and automatically decomposing the hypochlorous acid to form hydrochloric acid and oxygen, so that chloride ions are introduced into the electrolyte, volatilizing the oxygen in the air to prepare positive electrode electrolyte with a sulfuric acid/hydrochloric acid system, and improving the energy density and stability of the vanadium battery;
step three, adding a metal reducing agent into the rest half of vanadyl sulfate solution to prepare a divalent vanadium ion solution, filtering the divalent vanadium ion solution to remove the metal reducing agent, adding ammonia water to remove metal ions remained in the vanadium ion solution, enabling the ammonia water to react with the vanadium ions of the divalent vanadium ion solution to generate divalent vanadium hydroxide, and then contacting with air to generate trivalent vanadium hydroxide after oxidation reaction;
and fourthly, filtering vanadium hydroxide, repeatedly cleaning the filtered vanadium hydroxide by adopting distilled water, heating and concentrating the vanadium hydroxide by using steam, separating out crystals, finally adding the vanadium hydroxide crystals into sulfuric acid solution according to the ratio of 1:2, introducing chlorine for 10-15min, reacting the chlorine with water in the solution to generate hydrochloric acid and hypochlorous acid, and automatically decomposing the hypochlorous acid to form hydrochloric acid and oxygen, so that chloride ions are introduced into the electrolyte, volatilizing the oxygen in the air, and slowly dissolving the vanadium hydroxide in a sulfuric acid/hydrochloric acid system to obtain trivalent vanadium ion solution, namely the negative electrolyte of the sulfuric acid/hydrochloric acid system.
In the invention, chlorine is continuously introduced in the proportioning process of vanadyl sulfate powder and sulfuric acid solution, chlorine reacts with water in the solution to generate hydrochloric acid, thereby preparing tetravalent vanadium ion positive electrode electrolyte with better stability of sulfuric acid/hydrochloric acid system.
The high-performance vanadium battery electrolyte of the sulfuric acid/hydrochloric acid mixed acid system provided by the invention is further described by the following specific examples according to different process conditions.
Example 1
Adding vanadium pentoxide powder into sulfuric acid solution according to the proportion of 1:2, and fully dissolving and activating for 40min at the temperature of 130 ℃ to obtain vanadyl sulfate solution with alum ion;
step two, adding sulfur dioxide into a half of vanadyl sulfate solution to reduce to form vanadyl sulfate solution with tetravalent vanadium ions, dehydrating and drying to obtain vanadyl sulfate powder, adding the vanadyl sulfate powder into the sulfuric acid solution to dissolve according to the ratio of 1:2, introducing chlorine for 10min, reacting the chlorine with water in the solution to generate hydrochloric acid and hypochlorous acid, and automatically decomposing the hypochlorous acid to form hydrochloric acid and oxygen, so that chloride ions are introduced into the electrolyte, and volatilizing the oxygen in the air to obtain the positive electrolyte with a sulfuric acid/hydrochloric acid system;
step three, adding a metal reducing agent into the rest half of vanadyl sulfate solution to prepare a divalent vanadium ion solution, filtering the divalent vanadium ion solution to remove the metal reducing agent, adding ammonia water to remove metal ions remained in the vanadium ion solution, enabling the ammonia water to react with the vanadium ions of the divalent vanadium ion solution to generate divalent vanadium hydroxide, and then contacting with air to generate trivalent vanadium hydroxide after oxidation reaction;
and fourthly, filtering the vanadium hydroxide, repeatedly cleaning the filtered vanadium hydroxide by adopting distilled water, heating and concentrating the vanadium hydroxide by using steam, separating out crystals, finally adding the vanadium hydroxide crystals into a sulfuric acid solution according to the ratio of 1:2, introducing chlorine for 10min, reacting the chlorine with water in the solution to generate hydrochloric acid and hypochlorous acid, and automatically decomposing the hypochlorous acid to form hydrochloric acid and oxygen, so that chloride ions are introduced into the electrolyte, volatilizing the oxygen in the air, and slowly dissolving the vanadium hydroxide in a sulfuric acid/hydrochloric acid system to obtain a trivalent vanadium ion solution, namely the negative electrolyte of the sulfuric acid/hydrochloric acid system.
Example 2
Step one, adding vanadium pentoxide powder into sulfuric acid solution according to the proportion of 1:2.2, and fully dissolving and activating for 38min at the temperature of 140 ℃ to prepare vanadyl sulfate solution with alum ions;
step two, adding sulfur dioxide into a half of vanadyl sulfate solution to reduce to form vanadyl sulfate solution with tetravalent vanadium ions, dehydrating and drying to obtain vanadyl sulfate powder, adding the vanadyl sulfate powder into the sulfuric acid solution to dissolve according to the ratio of 1:2, introducing chlorine for 12min, reacting the chlorine with water in the solution to generate hydrochloric acid and hypochlorous acid, and automatically decomposing the hypochlorous acid to form hydrochloric acid and oxygen, so that chloride ions are introduced into the electrolyte, volatilizing the oxygen in the air to prepare anode electrolyte with a sulfuric acid/hydrochloric acid system, and improving the energy density and stability of the vanadium battery;
step three, adding a metal reducing agent into the rest half of vanadyl sulfate solution to prepare a divalent vanadium ion solution, filtering the divalent vanadium ion solution to remove the metal reducing agent, adding ammonia water to remove metal ions remained in the vanadium ion solution, enabling the ammonia water to react with the vanadium ions of the divalent vanadium ion solution to generate divalent vanadium hydroxide, and then contacting with air to generate trivalent vanadium hydroxide after oxidation reaction;
and fourthly, filtering the vanadium hydroxide, repeatedly cleaning the filtered vanadium hydroxide by adopting distilled water, heating and concentrating the vanadium hydroxide by using steam, separating out crystals, finally adding the vanadium hydroxide crystals into a sulfuric acid solution according to the ratio of 1:2, introducing chlorine for 12min, reacting the chlorine with water in the solution to generate hydrochloric acid and hypochlorous acid, and automatically decomposing the hypochlorous acid to form hydrochloric acid and oxygen, so that chloride ions are introduced into the electrolyte, volatilizing the oxygen in the air, and slowly dissolving the vanadium hydroxide in a sulfuric acid/hydrochloric acid system to obtain a trivalent vanadium ion solution, namely the negative electrolyte of the sulfuric acid/hydrochloric acid system.
Example 3
Firstly, adding vanadium pentoxide powder into sulfuric acid solution according to the proportion of 1:2.4, and fully dissolving and activating for 33min at the temperature of 150 ℃ to obtain vanadyl sulfate solution with alum ion;
step two, adding sulfur dioxide into a half of vanadyl sulfate solution to reduce to form vanadyl sulfate solution with tetravalent vanadium ions, dehydrating and drying to obtain vanadyl sulfate powder, adding the vanadyl sulfate powder into the sulfuric acid solution to dissolve according to the ratio of 1:2, introducing chlorine for 14min, reacting the chlorine with water in the solution to generate hydrochloric acid and hypochlorous acid, and automatically decomposing the hypochlorous acid to form hydrochloric acid and oxygen, so that chloride ions are introduced into the electrolyte, volatilizing the oxygen in the air to prepare anode electrolyte with a sulfuric acid/hydrochloric acid system, and improving the energy density and stability of the vanadium battery;
step three, adding a metal reducing agent into the rest half of vanadyl sulfate solution to prepare a divalent vanadium ion solution, filtering the divalent vanadium ion solution to remove the metal reducing agent, adding ammonia water to remove metal ions remained in the vanadium ion solution, enabling the ammonia water to react with the vanadium ions of the divalent vanadium ion solution to generate divalent vanadium hydroxide, and then contacting with air to generate trivalent vanadium hydroxide after oxidation reaction;
and fourthly, filtering the vanadium hydroxide, repeatedly cleaning the filtered vanadium hydroxide by adopting distilled water, heating and concentrating the vanadium hydroxide by using steam, separating out crystals, finally adding the vanadium hydroxide crystals into a sulfuric acid solution according to the ratio of 1:2, introducing chlorine for 14min, reacting the chlorine with water in the solution to generate hydrochloric acid and hypochlorous acid, and automatically decomposing the hypochlorous acid to form hydrochloric acid and oxygen, so that chloride ions are introduced into the electrolyte, volatilizing the oxygen in the air, and slowly dissolving the vanadium hydroxide in a sulfuric acid/hydrochloric acid system to obtain a trivalent vanadium ion solution, namely the negative electrolyte of the sulfuric acid/hydrochloric acid system.
Example 4
Adding vanadium pentoxide powder into sulfuric acid solution according to the proportion of 1:2.5, and fully dissolving for 30min for activation at 160 ℃ to prepare vanadyl sulfate solution with alum ion;
step two, adding sulfur dioxide into a half of vanadyl sulfate solution to reduce to form vanadyl sulfate solution with tetravalent vanadium ions, dehydrating and drying to obtain vanadyl sulfate powder, adding the vanadyl sulfate powder into the sulfuric acid solution to dissolve according to the ratio of 1:2, introducing chlorine for 15min, reacting the chlorine with water in the solution to generate hydrochloric acid and hypochlorous acid, and automatically decomposing the hypochlorous acid to form hydrochloric acid and oxygen, so that chloride ions are introduced into the electrolyte, volatilizing the oxygen in the air to prepare anode electrolyte with a sulfuric acid/hydrochloric acid system, and improving the energy density and stability of the vanadium battery;
step three, adding a metal reducing agent into the rest half of vanadyl sulfate solution to prepare a divalent vanadium ion solution, filtering the divalent vanadium ion solution to remove the metal reducing agent, adding ammonia water to remove metal ions remained in the vanadium ion solution, enabling the ammonia water to react with the vanadium ions of the divalent vanadium ion solution to generate divalent vanadium hydroxide, and then contacting with air to generate trivalent vanadium hydroxide after oxidation reaction;
and fourthly, filtering the vanadium hydroxide, repeatedly cleaning the filtered vanadium hydroxide by adopting distilled water, heating and concentrating the vanadium hydroxide by using steam, separating out crystals, finally adding the vanadium hydroxide crystals into a sulfuric acid solution according to the ratio of 1:2, introducing chlorine for 15min, reacting the chlorine with water in the solution to generate hydrochloric acid and hypochlorous acid, and automatically decomposing the hypochlorous acid to form hydrochloric acid and oxygen, so that chloride ions are introduced into the electrolyte, volatilizing the oxygen in the air, and slowly dissolving the vanadium hydroxide in a sulfuric acid/hydrochloric acid system to obtain a trivalent vanadium ion solution, namely the negative electrolyte of the sulfuric acid/hydrochloric acid system.
Table 1 examples 1-4 process conditions
Test examples
In this test example, the positive and negative electrolytes provided in examples 1 to 4 were sealed in a glass bottle, and then placed in an organic glass frame, and the organic glass frame containing the positive and negative electrolytes was left to stand in a constant temperature water bath at 50 ℃ for stability test. Each electrolyte is tested for 7 days at most, and the chlorine ion concentration of the electrolyte is detected after the test days because the electrolyte is likely to volatilize hydrogen chloride at high temperature;
after testing, the electrolyte provided by the embodiment 1-4 of the invention keeps the concentration of chloride ions unchanged under the test of 7 days, and can stably work at the temperature of minus 30-50 ℃, which proves that the electrolyte of the sulfuric acid/hydrochloric acid system prepared by the invention has better stability.
The foregoing has shown and described the basic principles, principal features and advantages of the invention. It will be understood by those skilled in the art that the present invention is not limited to the above-described embodiments, and that the above-described embodiments and descriptions are only preferred embodiments of the present invention, and are not intended to limit the invention, and that various changes and modifications may be made therein without departing from the spirit and scope of the invention as claimed. The scope of the invention is defined by the appended claims and equivalents thereof.
Claims (4)
1. The preparation method of the sulfuric acid-hydrochloric acid mixed acid system vanadium battery electrolyte is characterized by comprising the following steps of:
s1, adding vanadium pentoxide powder into sulfuric acid solution, and fully dissolving and activating to obtain vanadyl sulfate solution with alum ion;
s2, adding sulfur dioxide into a half of vanadyl sulfate solution to reduce to form vanadyl sulfate solution with tetravalent vanadium ions, dehydrating and drying to obtain vanadyl sulfate powder, adding the vanadyl sulfate powder into the sulfuric acid solution to dissolve, introducing chlorine, reacting the chlorine with water in the solution to generate hydrochloric acid and hypochlorous acid, and automatically decomposing the hypochlorous acid to form hydrochloric acid and oxygen, so that chloride ions are introduced into the electrolyte, volatilizing the oxygen in the air, and preparing the positive electrode electrolyte with a sulfuric acid hydrochloric acid system;
s3, adding a metal reducing agent into the rest half of vanadyl sulfate solution to prepare a divalent vanadium ion solution, filtering the divalent vanadium ion solution to remove the metal reducing agent, adding ammonia water to remove the metal ions of the reducing agent remained in the vanadium ion solution, enabling the ammonia water to react with the vanadium ions of the divalent vanadium ion solution to generate divalent vanadium hydroxide, and then enabling the divalent vanadium hydroxide to contact with air to generate trivalent vanadium hydroxide after oxidation reaction;
s4, filtering vanadium hydroxide, repeatedly cleaning the filtered vanadium hydroxide by using distilled water, heating the vanadium hydroxide by using water vapor, concentrating the heated vanadium hydroxide to separate out crystals, finally adding the vanadium hydroxide crystals into sulfuric acid solution, introducing chlorine, reacting the chlorine with water in the solution to generate hydrochloric acid and hypochlorous acid, and automatically decomposing the hypochlorous acid to form hydrochloric acid and oxygen, so that chloride ions are introduced into the electrolyte, volatilizing the oxygen in the air, and slowly dissolving the vanadium hydroxide in a sulfuric acid hydrochloric acid system to obtain trivalent vanadium ion solution, namely the anode electrolyte of the sulfuric acid hydrochloric acid system;
wherein the electrolyte comprises a positive electrode electrolyte and a negative electrode electrolyte;
the metal reducing agent is at least one selected from zinc powder, magnesium powder, iron powder and potassium powder.
2. The method for preparing the sulfuric acid-hydrochloric acid mixed acid system vanadium redox battery electrolyte according to claim 1, which is characterized by comprising the following steps: in the step S1, the activation conditions of the vanadium pentoxide powder are as follows: the temperature is 130-160 ℃, and the dissolution is carried out for 30-40min.
3. The method for preparing the sulfuric acid-hydrochloric acid mixed acid system vanadium redox battery electrolyte according to claim 1, which is characterized by comprising the following steps: in the step S2, the introducing time of the chlorine is 10-15min.
4. The method for preparing the sulfuric acid-hydrochloric acid mixed acid system vanadium redox battery electrolyte according to claim 1, which is characterized by comprising the following steps: in the step S4, the introducing time of the chlorine is 10-15min.
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| CN103199293A (en) * | 2013-04-01 | 2013-07-10 | 胡国良 | Preparation method of vanadium sulfate solution for vanadium cell |
| CN104852073A (en) * | 2015-04-09 | 2015-08-19 | 深圳市万越新能源科技有限公司 | Method for preparing positive electrolyte of all-vanadium redox flow battery through chemical synthesis method |
| CN111342102A (en) * | 2020-04-03 | 2020-06-26 | 武汉科技大学 | Preparation method of vanadium battery electrolyte based on vanadium compound |
| CN114566628A (en) * | 2022-03-04 | 2022-05-31 | 合肥工业大学 | Preparation method of anode material of phytic acid doped polypyrrole @ vanadate water-based zinc ion battery |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103199293A (en) * | 2013-04-01 | 2013-07-10 | 胡国良 | Preparation method of vanadium sulfate solution for vanadium cell |
| CN104852073A (en) * | 2015-04-09 | 2015-08-19 | 深圳市万越新能源科技有限公司 | Method for preparing positive electrolyte of all-vanadium redox flow battery through chemical synthesis method |
| CN111342102A (en) * | 2020-04-03 | 2020-06-26 | 武汉科技大学 | Preparation method of vanadium battery electrolyte based on vanadium compound |
| CN114566628A (en) * | 2022-03-04 | 2022-05-31 | 合肥工业大学 | Preparation method of anode material of phytic acid doped polypyrrole @ vanadate water-based zinc ion battery |
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