CN116031459A - High-stability vanadium ion electrolyte - Google Patents
High-stability vanadium ion electrolyte Download PDFInfo
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- CN116031459A CN116031459A CN202210979048.6A CN202210979048A CN116031459A CN 116031459 A CN116031459 A CN 116031459A CN 202210979048 A CN202210979048 A CN 202210979048A CN 116031459 A CN116031459 A CN 116031459A
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Abstract
The invention discloses a high-stability vanadium ion electrolyte, which comprises vanadium sulfate, sulfuric acid, water and an additive, wherein the additive comprises at least one of alkali metal salt, hydroxyl-containing substances and a surfactant, the alkali metal salt comprises potassium sulfate, dipotassium hydrogen phosphate, sodium dihydrogen phosphate, pyrophosphoric acid, potassium pyrophosphate and sodium pyrophosphate, and the hydroxyl-containing substances comprise: ethanol, glycerol, polyethylene glycol, acetic acid, oxalic acid, phosphoric acid, sulfuric acid, and surfactants comprising: dodecyl trimethyl ammonium chloride, dodecyl trimethyl ammonium bromide, cetyl Trimethyl Ammonium Chloride (CTAC), cetyl Trimethyl Ammonium Bromide (CTAB), dodecyl dimethyl betaine; the novel additive combination is added into the vanadium ion electrolyte, the precipitation of V (V) and the oxidation of V (II) are effectively inhibited by utilizing the synergistic effect among the additive components, the stability of the electrolyte is greatly improved, the obtained vanadium ion electrolyte is used for a vanadium battery, and the charge and discharge performance and the cycle stability of the vanadium battery are effectively improved.
Description
Technical Field
The invention relates to a vanadium ion electrolyte with high stability, and belongs to the field of manufacturing of flow batteries.
Background
An all-vanadium ion flow battery (vanadium battery for short) is a flow battery which takes vanadium ion solution as active material and electrolyte. The vanadium battery has the advantages of deep large-current charge and discharge, high energy conversion rate, long cycle life and the like, can be used for preparing a megawatt battery pack, and is applied to the field of high-power long-time power storage and supply, so that the vanadium battery is widely valued. The vanadium ion electrolyte is the core of the whole battery, and the properties such as viscosity, conductivity, stability and the like have great influence on the performance of the vanadium battery.
In general, vanadium ion electrolytes can be classified into a positive electrode electrolyte and a negative electrode electrolyte, wherein the positive electrode electrolyte is composed of VO 2+ (V)) and VO 2+ (V (IV)) and the negative electrode electrolyte consists of V 3+ (V (III)) and V 2+ (V (II)) is formed. In the charging and discharging process of the vanadium battery, the valence state of vanadium ions in the electrolyte is changed as follows:
and (3) a positive electrode:
and (3) a negative electrode:
after the vanadium battery is charged, the V (II) content in the negative electrode electrolyte and the V (V) content in the positive electrode electrolyte are increased. V (II) and V (V) are unstable in the electrolyte, and V (II) is extremely easily oxidized to V (III) in an open system; v (V) generates orange V at above room temperature 2 O 5 And the sedimentation speed is increased along with the temperature rise. The unstable phenomena of the vanadium ion electrolyte can cause the content of active substances in the electrolyte to be reduced, so that the capacity of the battery is reduced, the charge and discharge efficiency is reduced, the cycle life is shortened, and meanwhile, the precipitated sediment in the electrolyte can influence the properties of the electrolyte such as viscosity and conductivity and the like, thereby seriously influencing the performance of the vanadium battery.
Several methods have been proposed to improve the stability of vanadium ion electrolytes. Patent CN1598063A discloses a method for preparing a solution of vanadyl sulfate in waterAdding Na 2 SO 4 The stability of the additive such as emulsifier OP is improved by adopting a method of adding the additive. However, the emulsifier OP is easily oxidized under strong oxidation conditions to lose effect; meanwhile, due to homoionic effect, na 2 SO 4 After excessive addition, VSO is promoted 4 Precipitation, thereby reducing its stability. Patent CN1507103 discloses a method for adding stabilizers such as alcohols, organic acids, salts or high molecular compounds to vanadium electrolytes, which can prevent V (ii) from precipitating or separating out beyond the limit concentration, and can form colloid or maintain the solution state. However, this method is only aimed at preventing precipitation or precipitation at high concentrations of V (II), but is not concerned with the charge-discharge performance of the battery and oxidation of V (II). Patent CN1719655a discloses a method of using sulfuric acid, water and ethanol as supporting electrolyte, and adding sodium sulfate, sodium pyrophosphate, sodium fluosilicate or hydrogen peroxide as stabilizer to the electrolyte to improve the stability of the electrolyte. Analysis shows that although ethanol can reduce the solution viscosity and improve the stability and conductivity of the solution, ethanol is easily oxidized by high-valence vanadium during charge and discharge, so that the efficiency of the battery is reduced, and thus the method needs to be further improved.
In summary, the unstable phenomena such as V (V) precipitation and V (II) oxidation in the vanadium ion electrolyte seriously affect the performance of the vanadium battery, and restrict the development and application of the vanadium battery, but the existing method for improving the stability of the vanadium ion electrolyte has some limitations and cannot meet the requirements. Therefore, a new electrolyte formula system is urgently needed, the stability of the electrolyte is improved, and the service performance of the vanadium battery is enhanced.
Disclosure of Invention
The invention provides a high-stability vanadium ion electrolyte which is used for overcoming the defects that the performance of a vanadium battery is seriously influenced and the development and the application of the vanadium ion electrolyte are restricted due to unstable phenomena such as V (V) precipitation, V (II) oxidation and the like in the vanadium ion electrolyte in the prior art.
In order to solve the technical problems, the invention provides the following technical scheme:
the invention discloses a high-stability vanadium ion electrolyte which comprises vanadium sulfate, sulfuric acid, water and an additive, wherein the additive comprises at least one of alkali metal salt, hydroxyl-containing substances and a surfactant.
The alkali metal salt comprises potassium sulfate, dipotassium hydrogen phosphate, sodium dihydrogen phosphate, disodium hydrogen phosphate, pyrophosphoric acid, potassium pyrophosphate, sodium acid pyrophosphate, potassium tripolyphosphate, sodium metaphosphate, sodium trimetaphosphate, potassium hexametaphosphate;
the hydroxyl-containing material comprises: ethanol, glycerol, polyethylene glycol, acetic acid, oxalic acid, phosphoric acid and sulfuric acid;
the surfactant comprises: dodecyl trimethyl ammonium chloride, dodecyl trimethyl ammonium bromide, cetyl Trimethyl Ammonium Chloride (CTAC), cetyl Trimethyl Ammonium Bromide (CTAB), dodecyl dimethyl betaine.
Further, the content of the additive in the vanadium ion electrolyte is 0 to 1mol L -1 。
Further, the additive is contained in both the positive electrode electrolyte and the negative electrode electrolyte.
Further, the additive keeps the vanadium ion electrolyte in a liquid state or forms a micro-emulsion state, and can prevent precipitation or precipitation of vanadium ions.
Further, the total vanadium concentration in the vanadium ion electrolyte is 1 to 2.5mol L -1 Sulfuric acid concentration is 2-3.5 mol L -1 。
The beneficial effects achieved by the invention are as follows: the novel additive combination is added into the vanadium ion electrolyte, the precipitation of V (V) and the oxidation of V (II) are effectively inhibited by utilizing the synergistic effect among the additive components, the stability of the electrolyte is greatly improved, and the obtained vanadium ion electrolyte is used for a vanadium battery, so that the charge and discharge performance and the circulation stability of the vanadium battery can be effectively improved.
Detailed Description
The following description of the preferred embodiments of the present invention is provided for the purpose of illustration and explanation only and is not intended to limit the present invention.
A vanadium ion electrolyte with high stability comprises vanadium sulfate, sulfuric acid, water and an additive, wherein the additive comprises at least one of alkali metal salt, hydroxyl-containing substance and surfactant.
The alkali metal salt comprises potassium sulfate, dipotassium hydrogen phosphate, sodium dihydrogen phosphate, disodium hydrogen phosphate, pyrophosphoric acid, potassium pyrophosphate, sodium acid pyrophosphate, potassium tripolyphosphate, sodium metaphosphate, sodium trimetaphosphate, potassium hexametaphosphate;
the hydroxyl-containing material comprises: ethanol, glycerol, polyethylene glycol, acetic acid, oxalic acid, phosphoric acid and sulfuric acid;
the surfactant comprises: dodecyl trimethyl ammonium chloride, dodecyl trimethyl ammonium bromide, cetyl Trimethyl Ammonium Chloride (CTAC), cetyl Trimethyl Ammonium Bromide (CTAB), dodecyl dimethyl betaine.
The content of the additive in the vanadium ion electrolyte is 0-1 mol L -1 。
The additive is contained in both the positive electrode electrolyte and the negative electrode electrolyte.
The total vanadium concentration in the vanadium ion electrolyte is 1 to 2.5mol L -1 Sulfuric acid concentration is 2-3.5 mol L -1 。
The additive can keep the vanadium ion electrolyte in a liquid state or form a microemulsion state, and can prevent precipitation or precipitation of vanadium ions.
The performance of the electrolyte was tested by using a small simulated vanadium battery charge and discharge experiment at different temperatures of 0, 25 and 45 ℃. The battery electrode adopts graphite felt, the current collecting material adopts graphite plate, the conductive diaphragm adopts activated Nafion proton membrane, the polyethylene plate is used for manufacturing a liquid flow frame plate, and the electrode area is 30mm multiplied by 35mm. Electrolyte in the positive and negative electrode liquid storage tanks enters positive and negative electrode chambers of the battery through a pump. The charge-discharge current density is 80mAcm -2 The charge cutoff voltage was 1.7V, and the discharge cutoff voltage was 1.0V.
Comparative example
Taking the total vanadium concentration as 1.4mol L -1 Sulfuric acid concentration of 2.8mol L -1 V (IV): v (III) =1: 1 (without additives) 40mL of each vanadium ion electrolyte, respectively placed in a moldAnd (3) carrying out charge and discharge experiments in a positive electrode liquid storage tank and a negative electrode liquid storage tank of the vanadium redox battery, wherein the experimental results are shown in a table.
Example 1
Potassium dihydrogen phosphate: analytically pure;
sodium sulfate: analytically pure.
Taking the total vanadium concentration as 1.4mol L -1 Sulfuric acid concentration of 2.8mol L -1 V (IV): v (III) =1: 1 (without additives) and 0.1g of monopotassium phosphate and 2g of sodium sulfate are added into 80mL of blank (without additives) vanadium ion electrolyte, the obtained electrolyte is divided into two parts equally, and the two parts are respectively placed into a positive electrode liquid storage tank and a negative electrode liquid storage tank of a simulated vanadium battery for charge and discharge experiments, and the experimental results are shown in a table.
Example 2
Phosphoric acid: analytically pure;
polyethylene glycol: analytically pure.
Taking the total vanadium concentration as 1.4mol L -1 Sulfuric acid concentration of 2.8mol L -1 V (IV): v (III) =1: 1 (without additives) 40mL of vanadium ion electrolyte, 0.1mL of 1mol L was added -1 Placing the H3PO4 solution in a positive electrode liquid storage tank of a simulated vanadium cell, and taking the total vanadium concentration to be 1.4mol L -1 Sulfuric acid concentration of 2.8mol L -1 V (IV): v (III) =1: 1 (without additives), adding 0.1g of polyethylene glycol into 40mL of blank (without additives) vanadium ion electrolyte, placing into a negative electrode liquid storage tank of a simulated vanadium battery, and carrying out charge-discharge experiments, wherein the experimental results are shown in a table.
Example 3
Sodium sulfate: analytically pure;
CTAB: analytically pure;
glycerol: analytically pure;
sodium hexametaphosphate: analytically pure.
Taking the total vanadium concentration as 1.4mol L -1 Sulfuric acid concentration of 2.8mol L -1 V (IV): v (III) =1: 1 (without additives), adding 3g sodium sulfate and 0.01g CTAB into 40mL of blank (without additives) vanadium ion electrolyte, placing into a positive electrode liquid storage tank of a simulated vanadium cell, and taking the total vanadium concentration to be 1.4mol L -1 Sulfuric acid concentration of 2.8mol L -1 V (IV): v (III) =1: 1 (without additives) 40mL of vanadium ion electrolyte, addAnd (3) adding 0.1g of sodium hexametaphosphate and 1g of glycerol into a negative electrode liquid storage tank of the simulated vanadium battery, and carrying out charge and discharge experiments, wherein the experimental results are shown in a table.
Table: charge and discharge experimental results of small-sized simulated vanadium battery at different temperatures
According to the invention, the novel additive combination is added into the vanadium ion electrolyte, so that the composition system of the vanadium ion electrolyte is changed, the stability of the electrolyte is greatly improved, and the obtained vanadium ion electrolyte is used for a vanadium battery, and the charge and discharge performance and the cycle stability of the vanadium battery at different temperatures can be effectively improved.
Finally, it should be noted that: the foregoing description is only a preferred embodiment of the present invention, and the present invention is not limited thereto, but it is to be understood that modifications and equivalents of some of the technical features described in the foregoing embodiments may be made by those skilled in the art, although the present invention has been described in detail with reference to the foregoing embodiments. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (5)
1. The vanadium ion electrolyte with high stability is characterized by comprising vanadium sulfate salt, sulfuric acid, water and an additive, wherein the additive comprises at least one of alkali metal salt, hydroxyl-containing substance and surfactant.
The alkali metal salt comprises potassium sulfate, dipotassium hydrogen phosphate, sodium dihydrogen phosphate, disodium hydrogen phosphate, pyrophosphoric acid, potassium pyrophosphate, sodium acid pyrophosphate, potassium tripolyphosphate, sodium metaphosphate, sodium trimetaphosphate, potassium hexametaphosphate;
the hydroxyl-containing material comprises: ethanol, glycerol, polyethylene glycol, acetic acid, oxalic acid, phosphoric acid and sulfuric acid;
the surfactant comprises: dodecyl trimethyl ammonium chloride, dodecyl trimethyl ammonium bromide, cetyl Trimethyl Ammonium Chloride (CTAC), cetyl Trimethyl Ammonium Bromide (CTAB), dodecyl dimethyl betaine.
2. The high-stability vanadium ion electrolyte according to claim 1, wherein the content of the additive in the vanadium ion electrolyte is 0 to 1mol -1 。
3. The high stability vanadium ion electrolyte of claim 1 wherein the additive is contained in both the positive electrolyte and the negative electrolyte.
4. The high stability vanadium ion electrolyte according to claim 1, wherein the additive maintains the vanadium ion electrolyte in a liquid state or forms a microemulsion state and prevents precipitation or precipitation of vanadium ions.
5. The high-stability vanadium ion electrolyte according to claim 1, wherein the total vanadium concentration in the vanadium ion electrolyte is 1 to 2.5mol -1 Sulfuric acid concentration is 2-3.5 mol L -1 。
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| Application Number | Priority Date | Filing Date | Title |
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| CN202210979048.6A CN116031459A (en) | 2022-08-16 | 2022-08-16 | High-stability vanadium ion electrolyte |
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| CN202210979048.6A CN116031459A (en) | 2022-08-16 | 2022-08-16 | High-stability vanadium ion electrolyte |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116504994A (en) * | 2023-06-28 | 2023-07-28 | 杭州德海艾科能源科技有限公司 | All-vanadium redox flow battery negative electrode dual-function additive and preparation method and application thereof |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116504994A (en) * | 2023-06-28 | 2023-07-28 | 杭州德海艾科能源科技有限公司 | All-vanadium redox flow battery negative electrode dual-function additive and preparation method and application thereof |
| CN116504994B (en) * | 2023-06-28 | 2023-09-29 | 杭州德海艾科能源科技有限公司 | All-vanadium redox flow battery negative electrode dual-function additive and preparation method and application thereof |
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