CN114447386A - Preparation method of all-vanadium redox flow battery electrolyte - Google Patents

Preparation method of all-vanadium redox flow battery electrolyte Download PDF

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Publication number
CN114447386A
CN114447386A CN202111567950.9A CN202111567950A CN114447386A CN 114447386 A CN114447386 A CN 114447386A CN 202111567950 A CN202111567950 A CN 202111567950A CN 114447386 A CN114447386 A CN 114447386A
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electrolyte
sulfuric acid
flow battery
preparation
thioacetamide
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CN202111567950.9A
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Chinese (zh)
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郑建伟
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Huaqin Energy Storage Technology Co ltd
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Shaanxi Huayin Technology Co ltd
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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
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B1/00—Electrolytic production of inorganic compounds or non-metals
    • C25B1/01—Products
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B9/00—Cells or assemblies of cells; Constructional parts of cells; Assemblies of constructional parts, e.g. electrode-diaphragm assemblies; Process-related cell features
    • C25B9/17—Cells comprising dimensionally-stable non-movable electrodes; Assemblies of constructional parts thereof
    • C25B9/19—Cells comprising dimensionally-stable non-movable electrodes; Assemblies of constructional parts thereof with diaphragms

Abstract

The invention relates to the technical field of batteries, and discloses a preparation method of an all-vanadium redox flow battery electrolyte, which comprises the following steps: mixing the solid V2O5After the mixture of the powder and thioacetamide is added with concentrated sulfuric acid and mixed, a uniformly dispersed solid solution is formed at 90-120 ℃, and the solid solution is used as a negative electrode electrolyte to obtain a 3.5-valent vanadium ion sulfuric acid solution at the negative electrode of an electrolytic cell. The preparation method of the all-vanadium redox flow battery electrolyte comprises the step of mixing solid V2O5Adding concentrated sulfuric acid into a mixture of the powder and thioacetamide, mixing the mixture with the concentrated sulfuric acid, forming uniformly dispersed solid solution at 90-120 ℃, taking the solid solution as a negative electrolyte, obtaining a 3.5-valent vanadium ion sulfuric acid solution at the negative electrode of an electrolytic cell, namely an all-vanadium redox flow battery electrolyte, using the thioacetamide as a chemical reducing agent, and combining an electrolytic reduction method to take the thioacetamide as a negativeThe electrode electrolyte can obtain the 3.5-valent vanadium ion sulfuric acid solution at the cathode of the electrolytic cell, the operation is simple and convenient, the cost is low, the trouble of a user is avoided, and the preparation of the user is convenient.

Description

Preparation method of all-vanadium redox flow battery electrolyte
Technical Field
The invention relates to the technical field of batteries, in particular to a preparation method of an all-vanadium redox flow battery electrolyte.
Background
Wind energy and solar energy are considered to be the cleanest renewable energy sources, but continuous and stable energy cannot be obtained due to the influence of natural factors, and large-scale energy storage technology must be applied for adjustment, however, the laggard energy storage technology becomes a bottleneck restricting the utilization of the two renewable energy sources, the all-vanadium redox flow battery is a novel energy storage battery, has the advantages of high energy conversion efficiency, long service life, convenient capacity adjustment, high safety, environmental friendliness and the like, can be used for the fields of solar energy, wind energy and other renewable energy sources and power grid peak clipping and valley filling and other standardized energy storage fields, and is one of the most promising energy storage devices, wherein the electrolyte is one of the most important components in the all-vanadium redox flow battery as a carrier of active substances, the performance and concentration of the electrolyte directly influence the performance and energy density of the battery, and how to obtain high-performance vanadium electrolyte becomes a hot spot for competitive research of researchers in various countries, the synthesis of the electrolyte of the all-vanadium redox flow battery mainly comprises two methods: chemical synthesis and electrolysis.
The chemical method mainly uses vanadium oxide or other vanadium salt as raw material, and heats and adds reducing agent (such as S, SO) in sulfuric acid solution with certain concentration2Etc.) to dissolve and reduce the vanadium compound into low-price and easily soluble vanadium compound, thereby preparing vanadium electrolyte with certain concentration2O5Or metavanadate is taken as a raw material, and V is added into the negative electrode area of the electrolytic cell2O5Or H of metavanadate2SO4Solution, positive electrode zone added with H of the same concentration2SO4Adding appropriate direct current V to two poles of the electrolytic cell2O5Or the metavanadate powder is reduced on the surface of the cathode by contacting with the cathode to prepare the all-vanadium redox flow battery electrolyte, the electrolytic method can continuously prepare a large amount of high-concentration vanadium electrolyte, the operation is simple and convenient, and the industrial production is easy to carry out.
Disclosure of Invention
Technical problem to be solved
Aiming at the defects of the prior art, the invention provides a preparation method of an all-vanadium redox flow battery electrolyte, which has the advantages of simple and convenient operation, low cost and the like, and solves the problems of high cost and complicated preparation method of the traditional method.
(II) technical scheme
In order to realize the purposes of simple and convenient operation and low cost, the invention provides the following technical scheme: a preparation method of an all-vanadium redox flow battery electrolyte comprises the following steps: mixing the solid V2O5And adding concentrated sulfuric acid into the mixture of the powder and thioacetamide, mixing, forming uniformly dispersed solid solution at 90-120 ℃, taking the solid solution as a cathode electrolyte, and obtaining a 3.5-valent vanadium ion sulfuric acid solution at the cathode of an electrolytic cell, namely the electrolyte of the all-vanadium flow battery.
Preferably, said V2O5The weight ratio of the powder to the thioacetamide is 50:1-100: 1.
Preferably, said V2O5The solid-to-liquid ratio of the mixture of powder and thioacetamide to sulfuric acid was 100 g: 100ml-100 g: 200 ml.
Preferably, the positive electrode and the negative electrode of the electrolytic cell both adopt lead electrodes, and the diaphragm of the electrolytic cell is a Nafion diaphragm.
Preferably, the electrolytic current of the electrolytic cell is 10mA/cm2-40mA/cm 2.
Preferably, the electrolyte of the positive electrode in the electrolytic cell is a sulfuric acid solution with the volume of 5-8 mol/L, and the volumes of the electrolyte of the positive electrode and the electrolyte of the negative electrode are the same.
(III) advantageous effects
Compared with the prior art, the invention provides a preparation method of an all-vanadium redox flow battery electrolyte, which has the following beneficial effects:
1. the preparation method of the all-vanadium redox flow battery electrolyte comprises the step of mixing solid V2O5The method is characterized in that a uniformly dispersed solid solution is formed at 90-120 ℃ after a mixture of powder and thioacetamide is added and mixed, the solid solution is used as a cathode electrolyte, a 3.5-valent vanadium ion sulfuric acid solution is obtained at the cathode of an electrolytic cell, namely the electrolyte of the all-vanadium redox flow battery, thioacetamide is used as a chemical reducing agent, and the solid solution is used as the cathode electrolyte by combining an electrolytic reduction method, so that the 3.5-valent vanadium ion sulfuric acid solution is obtained at the cathode of the electrolytic cell.
2. The electrolyte of the all-vanadium redox flow batteryPreparation process by mixing solid V2O5The method comprises the steps of adding concentrated sulfuric acid into a mixture of powder and thioacetamide, mixing the mixture with the concentrated sulfuric acid, forming a uniformly dispersed solid solution at 90-120 ℃, using the solid solution as a cathode electrolyte, obtaining a 3.5-valent vanadium ion sulfuric acid solution at the cathode of an electrolytic cell, namely an all-vanadium redox flow battery electrolyte, using the thioacetamide as a chemical reducing agent, combining an electrolytic reduction method, using the thioacetamide as the cathode electrolyte, obtaining the 3.5-valent vanadium ion sulfuric acid solution at the cathode of the electrolytic cell, and using water-soluble thioacetamide to replace a traditional insoluble sulfur simple substance, so that the uniform dispersion of the thioacetamide reducing agent in the solution can be ensured, and the reduction efficiency is improved.
Drawings
FIG. 1 is a preparation method of an all-vanadium redox flow battery electrolyte provided by the invention and a performance test chart of the electrolyte in comparative example 1;
FIG. 2 is a diagram of performance test of an electrolyte in comparative example 2 of a preparation method of an electrolyte of an all-vanadium redox flow battery provided by the invention;
FIG. 3 is an electrolyte performance test chart of the preparation method of the electrolyte of the all-vanadium redox flow battery in example 1 of the invention;
FIG. 4 is an electrolyte performance test chart of embodiment 2 of a preparation method of an electrolyte of an all-vanadium redox flow battery according to the present invention;
fig. 5 is a performance test chart of an electrolyte in embodiment 3 of a preparation method of an electrolyte of an all-vanadium redox flow battery according to the present invention.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Comparative example 1
Solid bodyV2O5The mixture of the powder and the elemental sulfur is added with concentrated sulfuric acid and mixed to form uniformly dispersed solid solution at 90 ℃; v2O5The weight ratio of the powder to the thioacetamide is 50:1, V2O5The solid-to-liquid ratio of the powder and sulfur mixture to sulfuric acid was 100 g: 100 ml; after being uniformly mixed for 5 hours, a solution 1 is obtained, and the solution is used for assembling an all-vanadium redox flow battery to carry out performance test so as to evaluate the performance of the electrolyte, and the figure 1 shows.
The test conditions of the all-vanadium redox flow battery are as follows: the positive electrode and the negative electrode are 800cm2 carbon felt electrodes, the prepared solution is adopted for the positive electrode and the negative electrode, the charge and discharge circulation is carried out by adopting the current density of 80mA/cm2, the charge cut-off condition is that the voltage is not higher than 1.5V, the discharge cut-off condition is that the voltage is not lower than 0.1V, and all the following battery tests adopt the method.
Comparative example 2
Solid V2O5The mixture of the powder and the sulfur is added with concentrated sulfuric acid and mixed to form a uniformly dispersed solid solution at 120 ℃; v2O5The weight ratio of the powder to the sulfur is 100: 1; v2O5The solid-to-liquid ratio of the powder and sulfur mixture to sulfuric acid was 100 g: 200 ml; the positive electrode and the negative electrode of the electrolytic cell are lead electrodes, the electrolytic current of the electrolytic cell is 10mA/cm2, the positive electrolyte in the electrolytic cell is 5mol/L sulfuric acid solution, the volumes of the positive electrolyte and the negative electrolyte are the same, the diaphragm of the electrolytic cell is a Nafion diaphragm, a solution 2 is obtained after 5 hours of electrolysis, and the solution is assembled into an all-vanadium flow galvanic battery for performance test to evaluate the performance of the electrolyte, as shown in figure 2.
Example 1
Solid V2O5The mixture of the powder and thioacetamide is mixed with concentrated sulfuric acid to form uniformly dispersed solid solution V at 120 deg.C2O5The weight ratio of the powder to the thioacetamide is 100:1, V2O5The solid-to-liquid ratio of the mixture of powder and thioacetamide to sulfuric acid was 100 g: 200ml, adopting lead electrodes for the anode and the cathode of the electrolytic cell, controlling the electrolytic current of the electrolytic cell to be 10mA/cm2, controlling the anode electrolyte in the electrolytic cell to be 5mol/L sulfuric acid solution, controlling the volumes of the anode electrolyte and the cathode electrolyte to be the same, controlling the diaphragm of the electrolytic cell to be a Nafion diaphragm, electrolyzing for 5 hours to obtain a solution 3, and usingThis solution was assembled into an all vanadium redox flow battery for performance testing to evaluate electrolyte performance, see fig. 3.
Example 2
Solid V2O5The mixture of the powder and thioacetamide is added with concentrated sulfuric acid and mixed to form a uniformly dispersed solid solution at 90 ℃; v2O5The weight ratio of the powder to the thioacetamide is 80:1, V2O5The solid-to-liquid ratio of the mixture of powder and thioacetamide to sulfuric acid was 100 g: 150ml, lead electrodes are adopted for the positive electrode and the negative electrode of the electrolytic cell, the electrolytic current of the electrolytic cell is 20mA/cm2, the positive electrolyte in the electrolytic cell is 5mol/L sulfuric acid solution, the volumes of the positive electrolyte and the negative electrolyte are the same, the diaphragm of the electrolytic cell is a Nafion diaphragm, a solution 4 is obtained after 3 hours of electrolysis, and the all-vanadium flow galvanic battery is assembled by the solution for performance test to evaluate the electrolyte performance, which is shown in figure 4.
Example 3
Solid V2O5The mixture of the powder and thioacetamide is mixed with concentrated sulfuric acid to form a uniformly dispersed solid solution V at 90 DEG C2O5The weight ratio of the powder to the thioacetamide is 80:1, V2O5The solid-to-liquid ratio of the mixture of powder and thioacetamide to sulfuric acid is 100 g: 150ml, lead electrodes are adopted for the positive electrode and the negative electrode of the electrolytic cell, the electrolytic current of the electrolytic cell is 40mA/cm2, the positive electrolyte in the electrolytic cell is 5mol/L sulfuric acid solution, the volumes of the positive electrolyte and the negative electrolyte are the same, the diaphragm of the electrolytic cell is a Nafion diaphragm, a solution 5 is obtained after 3 hours of electrolysis, and the all-vanadium flow galvanic battery is assembled by the solution for performance test to evaluate the performance of the electrolyte, which is shown in figure 5.
Performance comparison table:
serial number Solutions of Coulombic efficiency (%) Voltage efficiency (%) Energy efficiency (%)
1 1 90 80 72
2 2 90 85 77
3 3 92 90 83
4 4 99 90 89
5 5 96 88 85
The data in the table show that the performance of the obtained electrolyte is obviously lower than that of the electrolyte obtained by adopting thioacetamide as the reducing agent, no matter the elemental sulfur is adopted as the reducing agent, a chemical method or an electrolytic method is adopted.
The invention has the beneficial effects that: the preparation method of the all-vanadium redox flow battery electrolyte comprises the step of mixing solid V2O5After adding concentrated sulfuric acid into a mixture of powder and thioacetamide, mixing the mixture at 90-120 ℃ to form uniformly dispersed solid solution, taking the solid solution as cathode electrolyte, obtaining 3.5-valent vanadium ion sulfuric acid solution at the cathode of an electrolytic cell, namely all-vanadium redox flow battery electrolyte, using thioacetamide as a chemical reducing agent, combining an electrolytic reduction method, taking the thioacetamide as the cathode electrolyte, and obtaining the 3.5-valent vanadium ion sulfuric acid solution at the cathode of the electrolytic cell2O5The method comprises the steps of adding concentrated sulfuric acid into a mixture of powder and thioacetamide, mixing the mixture with the concentrated sulfuric acid, forming a uniformly dispersed solid solution at 90-120 ℃, using the solid solution as a cathode electrolyte, obtaining a 3.5-valent vanadium ion sulfuric acid solution at the cathode of an electrolytic cell, namely an all-vanadium redox flow battery electrolyte, using the thioacetamide as a chemical reducing agent, combining an electrolytic reduction method, using the thioacetamide as the cathode electrolyte, obtaining the 3.5-valent vanadium ion sulfuric acid solution at the cathode of the electrolytic cell, and using water-soluble thioacetamide to replace a traditional insoluble sulfur simple substance, so that the uniform dispersion of the thioacetamide reducing agent in the solution can be ensured, and the reduction efficiency is improved.
Although embodiments of the present invention have been shown and described, it will be appreciated by those skilled in the art that changes, modifications, substitutions and alterations can be made in these embodiments without departing from the principles and spirit of the invention, the scope of which is defined in the appended claims and their equivalents.

Claims (6)

1. All-vanadium redox flow battery electrolyteThe preparation method is characterized by comprising the following steps: mixing the solid V2O5And adding concentrated sulfuric acid into the mixture of the powder and thioacetamide, mixing, forming uniformly dispersed solid solution at 90-120 ℃, taking the solid solution as a cathode electrolyte, and obtaining a 3.5-valent vanadium ion sulfuric acid solution at the cathode of an electrolytic cell, namely the electrolyte of the all-vanadium flow battery.
2. The preparation method of the electrolyte of the all-vanadium flow battery according to claim 1, characterized by comprising the following steps: the V is2O5The weight ratio of the powder to the thioacetamide is 50:1-100: 1.
3. The preparation method of the electrolyte of the all-vanadium flow battery according to claim 1, characterized by comprising the following steps: the V is2O5The solid-to-liquid ratio of the mixture of powder and thioacetamide to sulfuric acid was 100 g: 100ml-100 g: 200 ml.
4. The preparation method of the electrolyte of the all-vanadium flow battery according to claim 1, characterized by comprising the following steps: the positive and negative electrodes of the electrolytic cell are lead electrodes, and the diaphragm of the electrolytic cell is a Nafion diaphragm.
5. The preparation method of the electrolyte of the all-vanadium flow battery according to claim 1, characterized by comprising the following steps: the electrolytic current of the electrolytic cell is 10mA/cm2-40mA/cm 2.
6. The preparation method of the electrolyte of the all-vanadium flow battery according to claim 1, characterized by comprising the following steps: the positive electrolyte in the electrolytic cell is a sulfuric acid solution with the concentration of 5-8 mol/L, and the volumes of the positive electrolyte and the negative electrolyte are the same.
CN202111567950.9A 2021-12-21 2021-12-21 Preparation method of all-vanadium redox flow battery electrolyte Pending CN114447386A (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN116387583A (en) * 2023-06-06 2023-07-04 北京普能世纪科技有限公司 All-vanadium redox flow battery capacity recovery method

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN116387583A (en) * 2023-06-06 2023-07-04 北京普能世纪科技有限公司 All-vanadium redox flow battery capacity recovery method
CN116387583B (en) * 2023-06-06 2023-09-19 北京普能世纪科技有限公司 All-vanadium redox flow battery capacity recovery method

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