Patent Application
20240274852
This application claims priority to the Chinese Patent Application No. 202211446542.2 filed with the China Patent Office on Nov. 21, 2022, entitled “Electrolyte Solutions and All-Vanadium Redox Flow Batteries”, the entire content of which is incorporated herein by reference in its entirety.
The present disclosure relates to a technical field of electrolyte solution preparation, and specifically relates to an electrolyte solution and an all-vanadium redox flow battery.
The all-vanadium redox flow battery is a redox flow battery in which vanadium ions of different valences are used as positive and negative active substances, and the active substances are dissolved in the supporting electrolyte and present in a liquid circulating flow state. As one of the new energy storage batteries, the all-vanadium redox flow battery has the characteristics of large capacity, high safety, long life, and resource saving, and can be widely used in renewable energy power generation, grid peak shaving, smart micro-grid, backup power, and other fields. The electrolyte solution is the storage carrier of electrical energy in the all-vanadium redox flow battery system, and its performance directly affects the electrode life, energy density and efficiency, system cost and other indicators of the system, and is related to the reliability of the battery system.
The long-term stable operation of the all-vanadium redox flow battery system depends on two factors: the stability of the battery material and the stability of the electrolyte solution. Frequent high-SOC operation (overcharging) of the battery will cause the system electrode material to oxidize and lose conductivity; high SOC electrolytes are prone to crystallization or precipitation at high temperatures; for electrolytes containing high-concentration HCl systems, a large amount of Cl2 evolution causes serious corrosion of battery-related materials and increasing system environmental risks. Therefore, reasonable control of chlorine gas generation during battery operation is an urgent problem to be solved.
This present disclosure provides an electrolyte solution that controls the amount of chlorine gas evolution by adjusting the concentration of chlorine ions in the electrolyte solution to solve the problem of excess chlorine gas evolution. Another object of the present disclosure is to provide an all-vanadium redox flow battery containing the above electrolyte solution.
In a first aspect, embodiments of the present disclosure provide an electrolyte solution, the electrolyte solution includes: a positive electrode electrolyte solution and a negative electrode electrolyte, the positive electrode electrolyte solution and negative electrode electrolyte solution include chloride ions, sulfate ions and vanadium ions; both the positive electrode electrolyte solution and the negative electrode electrolyte solution satisfy:
the c(Cl−) represents a concentration of the chloride ions, the c(SO42−) represents a concentration of the sulfate ions, and the c(Vn+) represents a concentration of the vanadium ions.
In some embodiments,
In some embodiments, the c(Cl−) and the c(SO42−) further satisfy:
In some embodiments, the c(Cl−) and the c(Vn+) further satisfy:
In some embodiments, the positive electrode electrolyte solution further includes phosphate ions, and the positive electrode electrolyte solution further satisfies:
In some embodiments, the c(PO43−) further satisfies:
In some embodiments, the negative electrode electrolyte solution further includes phosphite ions, and the negative electrode electrolyte solution further satisfies:
In some embodiments, the c(PO33−) further satisfies:
In some embodiments, the positive electrode electrolyte solution and the negative electrode electrolyte solution further include an additive, and the positive electrode electrolyte solution and the negative electrode electrolyte solution further satisfy:
In some embodiments, the additive satisfies at least one of the following features:
In some embodiments, the temperature stability range of the electrolyte solution is −30˜60° C.
In some embodiments, the chloride ions are provided by an acid or salt containing the chloride ions; the sulfate ions are provided by an acid or salt containing the sulfate; the vanadium ions are provided by a vanadate.
In a second aspect, embodiments of the present disclosure also provide an all-vanadium redox flow battery containing the above electrolyte solution.
Compared with the prior art, the electrolyte solution of this disclosure includes: a positive electrode electrolyte solution and a negative electrode electrolyte, the positive electrode electrolyte solution and negative electrode electrolyte solution include chloride ions, sulfate ions and vanadium ions; both the positive electrode electrolyte solution and negative electrode electrolyte solution satisfy: 2.9≤[c(Cl−)+c(SO42−)]/c(Vn+)≤3.6; c(Cl−) represents the concentration of chloride ions, c(SO42−) represents the concentration of sulfate ions, c(Vn+) represents the concentration of vanadium ions. When Cl−, SO42− and Vn+ in the electrolyte solution meet the appropriate concentration relationship, the Cl2 production rate can be greatly reduced, reducing the corrosion of battery materials. At the same time, a small amount of Cl2 evolved can compensate for the oxidation of the battery electrode carbon felt, and the electrode The carbon felt protects and reduces the risk level of chlorine-containing electrolytes operation environmental.
The present disclosure provides an electrolyte solution and all-vanadium redox flow battery. In order to make the purpose, technical solutions and effects of the present disclosure clear and definite, the present disclosure will be further described in detail below with reference to the accompanying drawings and examples. It should be understood that the specific embodiments described herein are only used to explain the present disclosure and are not used to limit the present disclosure.
The applicant found that due to the high temperature (the temperature inside the container in tropical areas will exceed 50 degrees Celsius), in order to avoid easy precipitation of V2O5 by the positive electrode electrolyte solution at high temperatures, the temperature range of stable use of the electrolyte solution is narrowed, and the battery system is equipped with auxiliary equipment for refrigeration, heating, and ventilation, which will consume power and reduce the overall efficiency of the battery system. Therefore, expanding the temperature range of safe use of the electrolyte solution can effectively reduce the cost of auxiliary equipment and its power consumption, and improve the overall efficiency while reducing the cost of the battery system. Moreover, once the heat exchange equipment fails, the high and low temperature resistance of the electrolyte solution itself is particularly important for the overall stability of the battery system. The higher the concentration of vanadium ions in the electrolyte, the higher the energy density of the corresponding system and the higher the cost performance, but the narrower the safe temperature range, the higher the risk of 5-valent vanadium precipitation at high temperatures. The temperature stable range of the traditional pure sulfuric acid system electrolyte solution is smaller, while the energy density of the mixed acid system electrolyte solution of sulfuric acid and hydrochloric acid is greatly improved, but it will produce harmful chlorine gas during battery operation. In addition, the low pressure in the plateau area causes the evolved Cl2 to be difficult to dissolve back into the electrolyte solution. The highly volatile HCl in the solution is continuously circulated to the magnetic pump, resulting in the aggravation of gas binding, and shutdown of the pump leads to the lack of reactants in the battery and overcharging and burning. The evolution rate of Cl2 is accelerated due to high Cl− concentration, and the pressure of the tank increases the risk of Cl2 escaping from the system. How to reduce the amount of Cl2 evolved while maintaining its high temperature performance is an urgent problem to be solved for mixed acid electrolytes. At the same time, its excessively high HCl concentration leads to serious low-temperature precipitation problems of the negative electrode trivalent solution (it is very easy to produce VCl3 crystallization), blocking pipelines and causing the system to fail to operate, which affects the further industrialization of this technology. Therefore, for all-vanadium redox flow battery electrolyte, its reasonable control of Cl2 evolution has become an urgent problem to be solved.
Based on the above problems, embodiments of the present disclosure provide an electrolyte solution for an all-vanadium redox flow battery. The electrolyte solution includes: a positive electrode electrolyte solution and a negative electrode electrolyte, the positive electrode electrolyte solution and negative electrode electrolyte solution include chloride ions, sulfate ions and vanadium ions; both the positive electrode electrolyte solution and negative electrode electrolyte solution satisfy:
In some embodiments, c(Cl−) satisfies: 1.5 mol/L≤c(Cl−)≤6.5 mol/L; the value of c(Cl−) can be any one or the range between any two of 1.5 mol/L, 2.0 mol/L, 2.5 mol/L, 3.0 mol/L, 3.5 mol/L, 4.0 mol/L, 4.5 mol/L, 5.5 mol/L, 6.0 mol/L and 6.5 mol/L. It is noted that the specific value of c(Cl−) is only given as an example, provided that any value or the range between any two values within the range of 1.5˜6.5 mol/L is within the protection scope of this disclosure.
In some embodiments, c(Cl−) further satisfies: 2.5 mol/L≤c(Cl−)≤5.5 mol/L; c(Cl−) further satisfies: 3.0 mol/L≤c(Cl−)≤5.0 mol/L; c(Cl−) most preferably satisfies: 3.5 mol/L≤c(Cl−) 4.5 mol/L.
In some embodiments, c(SO42−) satisfies: 0.5 mol/L≤c(SO42−)≤5.5 mol/L; the value of c(SO42−) can be any one or the range between any two of 0.5 mol/L, 1.0 mol/L, 1.5 mol/L, 2.0 mol/L, 2.5 mol/L, 3.0 mol/L, 3.5 mol/L, 4.0 mol/L, 4.5 mol/L, 5.0 mol/L and 5.5 mol/L. It is noted that the specific value of c(SO42−) is only given as an example, provided that any value or the range between any two values in the range of 0.5˜5.5 mol/L is within the protection scope of this disclosure.
In some embodiments, c(SO42−) further satisfies: 1.5 mol/L≤c(SO42−)≤4.5 mol/L; c(SO42−) further satisfies: 1.5 mol/L≤c(SO42−)≤3.5 mol/L; c(SO42−) most preferably satisfies: 1.5 mol/L≤c(SO42−)≤2.5 mol/L.
In some embodiments, c(Vn+) satisfies: 1.6 mol/L≤c(Vn+)≤2.65 mol/L; the value of c(Vn+) can be any one or the range between any two of 1.6 mol/L, 1.7 mol/L, 1.8 mol/L, 1.9 mol/L, 2.0 mol/L, 2.1 mol/L, 2.2 mol/L, 2.3 mol/L, 2.4 mol/L, 2.5 mol/L, 2.6 mol/L. It is noted that the specific value of c(Vn+) is only given as an example, provided that any value or the range between any two values within the range of 1.6˜2.65 mol/L is within the protection scope of this disclosure.
In some embodiments, under high SOC conditions, the VO2+ content is greater than 90%, and high-concentration VO2+ will react with Cl− at a certain rate to generate Cl2. The reaction formula is: 2VO2++2Cl−+4H+→Cl2+2VO2++2H2O. It can be seen that chlorine gas will be produced under high SOC, and Cl− can improve the stability of VO2+ at high temperatures. However, after the range of 2.9≤[c(Cl−)+c(SO42−)]/c(Vn+)≤3.6 is limited, the generation amount of Cl2 can be controlled within a certain range. At the same time, a certain amount of chlorine gas evolved can compensate for the oxidation of the battery electrode carbon felt and avoid the oxidation of the carbon felt electrode due to insufficient substrate VO2+ from overcharging. Based on the above principle, the battery charging open circuit voltage OCV can be expanded from 1.50V to 1.54V, and the system discharge energy density can be increased by more than 20%. In addition, under the controlled Cl− concentration of 1.5˜6.5 mol/L, it will also avoid environmental dangers caused by gas binding of the circulation pump and increase in system pressure due to high-rate evolution of Cl2.
In some embodiments, c(Cl−) and c(SO42−) further satisfy: 0.4≤c(Cl−)/c(SO42−)≤3.1. It is noted that as long as the range of c(Cl−)/c(SO42−) is any value in the range of 0.4˜3.1 or a range between any two values, it is within the protection scope of this disclosure. For the electrolyte, Cl− and SO42− are symbols of the mixed acid system, and the ratio between the two determines the stability of the electrolyte solution. When Cl− and SO42− coexist and reach the above ratio, on the one hand, HCl saturated vapor pressure can be reduced; on the other hand, since SO42− and Cl− can bind with Vn+ to form two salts with different spatial structures, it can alleviate the decrease in electrolyte solution stability caused by the structure of a single acid group bound with vanadium ions at high temperatures when it reaches the upper limit of solubility.
In some embodiments, c(Cl−) and c(Vn+) further satisfy: 0.5≤c(Cl−)/c(Vn+)≤3.0. It is noted that as long as the range of c(Cl−)/c(Vn+) is any value in the range of 0.5˜3.0 or a range between any two values, it is within the protection scope of this disclosure. For the electrolyte, the proportional relationship between c(Cl−) and c(Vn+) can further reflect the situation of chlorine precipitation. This is because under the appropriate ratio of Cl− and Vn+, after the Cl− bound by Vn+ is removed in the solution, there is still free H+ to maintain the conductivity and solubility of the solution, so as to further maintain the battery efficiency and high-temperature stability of the battery. When the ratio of Cl− and Vn+ is within the above range, it can be ensured that Cl− has strong complexing ability, and there is still residual Cl− to provide H+ and evolve a certain amount of chlorine gas, and the electrode is protected by a certain amount of chlorine gas evolved.
In some embodiments, the positive electrode electrolyte solution further includes phosphate ions, and the positive electrode electrolyte solution further satisfies: 2.9≤[c(Cl−)+c(SO42−)+c(PO43−)]/c(Vn+)≤3.7; c(PO43−) represents the concentration of the phosphate ions. When Cl−, SO42−, PO43− and Vn+ in the electrolyte solution meet the above range, the electrolyte solution can protect the electrode performance, and the phosphate ions further improve the stability to Vn+, so as to greatly reduce the evolution rate of the chlorine gas. The stabilizing effect of phosphate ions on Vn+ is due to its binding with [VO2(H2O)3]+, which inhibits the deprotonation process of vanadium ions at high temperatures. The complexation reaction is:
At the same time, at high temperatures, the HCl-containing electrolyte solution Cl− and VO2+ generate soluble VO2Cl to avoid the generation of insoluble V2O5. Under the control of the positive electrode relationship formula 2.9≤[c(Cl−)+c(SO42−)+c(PO43−)]/c(Vn+)≤3.7, low-concentration free HCl further reduces the Cl2 production rate, which greatly reduces the corrosion resistance requirements of battery materials. At the same time, it reduces the risk level of the operation environment of the HCl-containing electrolyte, and the tolerance of HCl-containing batteries to plateau areas can be further improved.
In some embodiments, c(PO43−) further satisfies: 0.01 mol/L≤c(PO43−)≤0.15 mol/L; the value of c(PO43−) can be any one or the range between any two of 0.01 mol/L, 0.02 mol/L, 0.03 mol/L, 0.04 mol/L, 0.05 mol/L, 0.06 mol/L, 0.07 mol/L, 0.08 mol/L, 0.09 mol/L, 0.10 mol/L/, 0.11 mol/L, 0.12 mol/L, 0.13 mol/L, 0.14 mol/L and 0.15 mol/L. It is noted that the specific value of c(PO43−) is only given as an example, provided that any value or the range between any two values within the range of 0.01˜0.15 mol/L is within the protection scope of this disclosure.
In some embodiments, c(PO43−) further satisfies: 0.02≤c (PO43−)/c(Vn+)≤0.06. By limiting the proportional relationship between PO43− and Vn+, excessive generation of insoluble VOPO4 precipitation can be avoided, while too low PO43− cannot form an effective spatial configuration and results in no protective effect.
In some embodiments, c(PO43−) further satisfies:
[c(Cl−)+c(SO42−)+c(PO43−)−0.8×c(Vn+)]≥4.2 mol/L; 0.8×c(Vn+) represents the average molar concentration of acid group ions bound by vanadium ions in the positive electrode electrolyte solution. When the above range is met, it can be ensured that after the total acid groups are bound by vanadium ions, there will still be a controllable concentration of free acid to provide H+ to ensure the high temperature solubility, stability and conductivity of the solution.
In some embodiments, the negative electrode electrolyte solution further includes phosphite ions, and the negative electrode electrolyte solution further satisfies: 2.9≤[c(Cl−)+c(SO42−)+c(PO33−)]/c(Vn+)≤3.7; c(PO33−) represents the concentration of the phosphite ions. Since an excessively high H+ concentration in the solution will increase the risk of V3+ precipitation, when the negative electrode solution satisfies the above formula, the H+ provided by the free acid groups must meet this value range. At the same time, phosphite ions can stabilize trivalent vanadium ions at low temperatures in the negative electrode of the electrolyte, and in the reducing environment of the negative electrode, phosphorous acid can exist stably without being oxidized.
In some embodiments, c(PO33−) further satisfies: 0.01 mol/L≤c(PO33−)≤0.15 mol/L; the value of c(PO33−) can be any one or the range between any two of 0.01 mol/L, 0.02 mol/L, 0.03 mol/L, 0.04 mol/L, 0.05 mol/L, 0.06 mol/L, 0.07 mol/L, 0.08 mol/L, 0.09 mol/L, 0.10 mol/L/, 0.11 mol/L, 0.12 mol/L, 0.13 mol/L, 0.14 mol/L and 0.15 mol/L. It is noted that the specific value of c(PO33−) is only given as an example, provided that any value or the range between any two values within the range of 0.01˜0.15 mol/L is within the protection scope of this disclosure.
In some embodiments, c(PO33−) further satisfies: 0.03≤c(PO33−)/c(Vn+)≤0.1; when c(PO33−) and c(Vn+) meet the above range, the low-temperature stabilization effect of phosphite ions can be further improved to prevent excessive PO33− concentration from increasing the viscosity of the negative electrode solution and reducing the conductivity of the solution and increasing the electrochemical reaction resistance of the battery.
In some embodiments, c(PO33−) further satisfies:
[c(Cl−)+c(SO42−)+c(PO33−)−1.5×c(Vn+)]≤4.5 mol/L; 1.5×c(Vn+) represents the average molar concentration of acid group ions bound by vanadium ions in the negative electrode electrolyte solution. If the above range is satisfied, after the total acid groups in the solution are bound by vanadium ions, the H+ precipitated by the remaining free acid groups is not enough to affect the stability of the vanadium ions.
In some embodiments, the positive electrode electrolyte solution and negative electrode electrolyte solution further include an additive, and the positive electrode electrolyte solution and negative electrode electrolyte solution further satisfy: 2.9≤[c(Cl−)+c(SO42−)+c(A)]/c(Vn+)≤3.7; c(A) represents a concentration of the additive.
In some embodiments, for the electrolyte solution system containing Cl−, if the concentration of Cl− in the system is too high, a large amount of Cl2 will be generated, and the additive cannot be added in the presence of the high concentration of Cl2 because the additive is easily oxidized and decomposed, but the low-rate production of Cl2 in this disclosure allows the additive to be added safely and exist stably. At the same time, the generation of Cl2 of the electrolyte solution containing Cl− in the positive electrode compensates to protect the positive carbon felt electrode from oxidation. High charging capacity will bring the risk of high-temperature precipitation caused by the increase in positive SOC, and the addition of the additive can maintain stability and further avoid the danger caused by increasing the open circuit voltage.
In some embodiments, the additive satisfies: the concentration of additive c(A) satisfies: 0.02 mol/L≤c(A)≤0.2 mol/L; the value of c(A) can be any one or a range between any two of 0.02 mol/L, 0.05 mol/L, 0.1 mol/L, 0.15 mol/L and 0.2 mol/L. It is noted that the specific value of c(A) is only given as an example, provided that any value or the range between any two values within the range of 0.02˜0.2 mol/L is within the protection scope of this disclosure.
In some embodiments, the additive is one or more of additives containing —OH, —COOH or —NH2 functional group. When the Cl− concentration is in the range of 1.5˜6.5 mol/L, the addition of the additive can effectively maintain high-temperature stability, and the temperature range is wider, and the battery operating temperature window can reach −15° C.˜ 60° C. This is because —COOH or —NH2 group can be adsorbed on the surface of vanadium ions or bound by vanadium ions, forming a structure with a three-dimensional effect, which enhances the repulsive force between vanadium hydrated ions and makes them more dispersed, thereby preventing vanadium ions from colliding with each other, inhibiting the generation of precipitation, and improving the stability of the electrolyte solution. The thermal stabilization mechanism is as follows:
The increase in the effective hydroxyl functional group —OH can provide more active sites for electron transfer, so that the hydroxyl compound can effectively improve the electrochemical activity of the electrolyte solution. In addition, the additive can improve the reversibility of the VO2+/VO2+ electrode process. —COOH or —NH2 can improve the electron mass transfer process in the VO2+/VO2+ electrode process, improve the electrochemical activity, increase the utilization rate of the electrolyte, and improve the battery efficiency and overall performance.
In some embodiments, the additive may include any one or a combination of more of glycerol, succinic acid, aminomethanesulfonic acid, methanesulfonic acid, glutamic acid, oxalic acid, etc.
In some embodiments, the temperature stability range of the electrolyte solution is −30˜60° C. The temperature stability range of the electrolyte solution is determined by the Cl-concentration. When the Cl− concentration is in the range of 1.5˜6.5 mol/L, the temperature stability range of the electrolyte solution is widened to −30˜60° C., which can greatly save investment in thermal management equipment, and reduce auxiliary power consumption and improve energy efficiency of the battery system. The preferred temperature stability range of the electrolyte solution is −15˜60° C.; the negative electrode electrolyte solution (trivalent solution) is stable for at least 7 days at an ambient temperature of −15° C.; the positive electrode electrolyte solution (5-valent solution) is stable for at least 10 days at an ambient temperature of 60° C.
In some embodiments, the chloride ions are provided by a chloride ion-containing acid or salt; the sulfate ions are provided by a sulfate-containing acid or salt; the vanadium ions are provided by a vanadate.
In some embodiments, the chloride ions are provided by hydrochloric acid, the sulfate ions are provided by sulfuric acid, and the vanadium ions are provided by multi-stage purified ammonium vanadate.
The all-vanadium redox flow energy storage battery includes a battery stack and an electrolyte solution storage tank. The battery stack and the liquid storage tank are connected by a liquid inlet pipeline and a liquid outlet pipeline. The liquid inlet pipeline is equipped with a circulation pump.
The battery stack consists of an ion diaphragm, guide plates, carbon felt electrodes, flow channel frames and fastening end plates in series.
Theoretically, only H+ is allowed to pass through, and the cross-mixing of vanadium ions in different valence states in the positive and negative electrode electrolytes is inhibited. Therefore, a cation exchange membrane with good conductivity and selective permeability is preferred, and a perfluorosulfonic acid ion exchange membrane can also be used. Improving the hydrophilicity, selective permeability and service life of the ion exchange membrane is one of the ways to improve the efficiency of the vanadium battery.
To achieve large-capacity energy storage in an all-vanadium redox flow battery, several single cells must be connected in series or parallel. In this way, except for the terminal electrodes, basically all electrodes must be made into bipolar electrodes. Due to the strong oxidizing properties of VO2+ and the strong acidic property of the electrolyte solution containing sulfuric acid and hydrochloric acid, electrode materials for the vanadium battery must be resistant to strong oxidation and strong acidity, at the same time, they must have low resistance, good conductivity, high mechanical strength, good electrochemical property and other characteristics. The vanadium battery electrode materials are mainly carbon, such as graphite, carbon cloth, carbon felt, etc.; bipolar plates are mostly made of composite materials, such as conductive polymers, polymer composites, etc.
After the materials of each part of the battery stack are assembled in sequence, they are connected to the corresponding inlets and outlets of the positive and negative electrode electrolyte solution storage tanks, and the all-vanadium redox flow battery is assembled.
Referring to
The obtained mixed acid electrolyte solution includes a positive electrode electrolyte solution and a negative electrode electrolyte, and the positive electrode electrolyte solution is controlled to contain 1.9 mol SO42−, 3.9 mol Cl− and 2.0 mol Vn+; the negative electrode electrolyte solution is controlled to contain 1.9 mol SO42−, 3.9 mol Cl− and 2.0 mol Vn+.
The specific preparation method is the same as that in Example 1, except that the preset ion concentration ratio is different, so that the positive electrode electrolyte solution contains 1.9 mol SO42−, 4.1 mol Cl− and 2.0 mol Vn+; the negative electrode electrolyte solution contains 1.9 mol SO42−, 4.1 mol Cl− and 2.0 mol Vn+.
The specific preparation method is the same as that in Example 1, except that the preset ion concentration ratio is different, so that the positive electrode electrolyte solution contains 1.9 mol SO42−, 4.3 mol Cl− and 2.0 mol Vn+; the negative electrode electrolyte solution contains 1.9 mol SO42−, 4.3 mol Cl− and 2.0 mol Vn+.
The specific preparation method is the same as that in Example 1, except that the preset ion concentration ratio is different, so that the positive electrode electrolyte solution contains 1.9 mol SO42−, 4.5 mol Cl− and 2.0 mol Vn+; the negative electrode electrolyte solution contains 1.9 mol SO42−, 4.5 mol Cl− and 2.0 mol Vn+.
The specific preparation method is the same as that in Example 1, except that the preset ion concentration ratio is different, so that the positive electrode electrolyte solution contains 1.9 mol SO42−, 4.7 mol Cl− and 2.0 mol Vn+; the negative electrode electrolyte solution contains 1.9 mol SO42−, 4.7 mol Cl− and 2.0 mol Vn+.
The specific preparation method is the same as that in Example 1, except that the preset ion concentration ratio is different, so that the positive electrode electrolyte solution contains 1.9 mol SO42−, 4.9 mol Cl− and 2.0 mol Vn+; the negative electrode electrolyte solution contains 1.9 mol SO42−, 4.9 mol Cl− and 2.0 mol Vn+.
The specific preparation method is the same as that in Example 1, except that the preset ion concentration ratio is different, so that the positive electrode electrolyte solution contains 1.9 mol SO42−, 5.1 mol Cl− and 2.0 mol Vn+; the negative electrode electrolyte solution contains 1.9 mol SO42−, 5.1 mol Cl− and 2.0 mol Vn+.
The specific preparation method is the same as that in Example 1, except that the preset ion concentration ratio is different, so that the positive electrode electrolyte solution contains 1.9 mol SO42−, 5.3 mol Cl− and 2.0 mol Vn+; the negative electrode electrolyte solution contains 5.3 mol SO42−, 4.7 mol Cl− and 2.0 mol Vn+.
The specific preparation method is the same as that in Example 1, except that the preset ion concentration ratio is different, so that the positive electrode electrolyte solution is controlled to contain 1.3 mol SO42−, 4.0 mol Cl− and 1.8 mol Vn+; the negative electrode electrolyte solution contains 1.3 mol SO42−, 4.0 mol Cl− and 1.8 mol Vn+.
The specific preparation method is the same as that in Example 1, except that the preset ion concentration ratio is different, so that the positive electrode electrolyte solution contains 1.8 mol SO42−, 4.0 mol Cl− and 1.8 mol Vn+; the negative electrode electrolyte solution contains 1.8 mol SO42−, 4.0 mol Cl− and 2.0 mol Vn+.
The specific preparation method is the same as that in Example 1, except that the preset ion concentration ratio is different, so that the positive electrode electrolyte solution contains 2.1 mol SO42−, 4.0 mol Cl− and 1.8 mol Vn+; the negative electrode electrolyte solution contains 2.1 mol SO42−, 4.0 mol Cl− and 2.0 mol Vn+.
The specific preparation method is the same as that in Example 1, except that the preset ion concentration ratio is different, so that the positive electrode electrolyte solution contains 2.4 mol SO42−, 4.0 mol Cl− and 1.8 mol Vn+; the negative electrode electrolyte solution contains 2.4 mol SO42−, 4.0 mol Cl− and 2.0 mol Vn+.
The specific preparation method is the same as that in Example 1, except that the preset ion concentration ratio is different, so that the positive electrode electrolyte solution contains 2.2 mol SO42−, 4.5 mol Cl− and 1.87 mol Vn+; the negative electrode electrolyte solution contains 2.2 mol SO42−, 4.5 mol Cl− and 1.87 mol Vn+.
The specific preparation method is the same as that in Example 1, except that the preset ion concentration ratio is different, so that the positive electrode electrolyte solution contains 2.2 mol SO42−, 4.5 mol Cl− and 1.95 mol Vn+; the negative electrode electrolyte solution contains 2.2 mol SO42−, 4.5 mol Cl− and 1.95 mol Vn+.
The specific preparation method is the same as that in Example 1, except that the preset ion concentration ratio is different, so that the positive electrode electrolyte solution contains 2.2 mol SO42−, 4.5 mol Cl− and 2.05 mol Vn+; the negative electrode electrolyte solution contains 2.2 mol SO42−, 4.5 mol Cl− and 2.05 mol Vn+.
The specific preparation method is the same as that in Example 1, except that the preset ion concentration ratio is different, so that the positive electrode electrolyte solution contains 2.2 mol SO42−, 4.5 mol Cl− and 2.20 mol Vn+; the negative electrode electrolyte solution contains 2.2 mol SO42−, 4.5 mol Cl− and 2.20 mol Vn+.
The specific preparation method is the same as that in Example 1, except that the preset ion concentration ratio is different, so that the positive electrode electrolyte solution contains 2.2 mol SO42−, 4.5 mol Cl− and 2.30 mol Vn+; the negative electrode electrolyte solution contains 2.2 mol SO42−, 4.5 mol Cl− and 2.30 mol Vn+.
The specific preparation method is the same as that in Example 1, except that the preset ion concentration ratio is different, so that the positive electrode electrolyte solution contains 3.2 mol SO42−, 1.5 mol Cl− and 1.6 mol Vn+; the negative electrode electrolyte solution contains 3.2 mol SO42−, 1.5 mol Cl− and 1.6 mol Vn+.
The specific preparation method is the same as that in Example 1, except that the preset ion concentration ratio is different, so that the positive electrode electrolyte solution contains 2.5 mol SO42−, 6.5 mol Cl− and 2.6 mol Vn+; the negative electrode electrolyte solution contains 2.5 mol SO42−, 6.5 mol Cl− and 2.6 mol Vn+.
The specific preparation method is the same as that in Example 1, except that the preset ion concentration ratio is different, so that the positive electrode electrolyte solution contains 2.2 mol SO42−, 2.5 mol Cl− and 1.60 mol Vn+; the negative electrode electrolyte solution contains 2.2 mol SO42−, 2.5 mol Cl− and 2.20 mol Vn+.
The specific preparation method is the same as that in Example 1, except that the preset ion concentration ratio is different, so that the positive electrode electrolyte solution contains 4.0 mol SO42−, 4.5 mol Cl− and 2.65 mol Vn+; the negative electrode electrolyte solution contains 4.0 mol SO42−, 4.5 mol Cl− and 2.65 mol Vn+.
The specific preparation method is the same as that in Example 1, except that the preset ion concentration ratio is different, and PO43− is added to the positive electrode electrolyte, so that the positive electrode electrolyte solution contains 1.9 mol SO42−, 3.9 mol Cl−, 0.04 mol PO43− and 2.0 mol Vn+; the negative electrode electrolyte solution is controlled to contain 1.9 mol SO42−, 3.9 mol Cl− and 2.0 mol Vn+.
The specific preparation method is the same as that in Example 1, except that the preset ion concentration ratio is different, and PO43− is added to the positive electrode electrolyte, so that the positive electrode electrolyte solution contains 1.9 mol SO42−, 3.9 mol Cl−, 0.08 mol PO43− and 2.0 mol Vn+; the negative electrode electrolyte solution is controlled to contain 1.9 mol SO42−, 3.9 mol Cl− and 2.0 mol Vn+.
The specific preparation method is the same as that in Example 1, except that the preset ion concentration ratio is different, and PO43− is added to the positive electrode electrolyte, so that the positive electrode electrolyte solution contains 1.9 mol SO42−, 5.3 mol Cl−, 0.12 mol PO43− and 2.0 mol Vn+; the negative electrode electrolyte solution is controlled to contain 1.9 mol SO42−, 3.9 mol Cl− and 2.0 mol Vn+.
The specific preparation method is the same as that in Example 1, except that the preset ion concentration ratio is different, and PO33− is added to the negative electrode electrolyte, so that the positive electrode electrolyte solution contains 1.9 mol SO42−, 3.9 mol Cl−, and 2.0 mol Vn+; t the negative electrode electrolyte solution is controlled to contain 1.9 mol SO42−, 3.9 mol Cl−, 0.06 mol PO33− and 2.0 mol Vn+.
The specific preparation method is the same as that in Example 1, except that the preset ion concentration ratio is different, and PO33− is added to the negative electrode electrolyte, so that the positive electrode electrolyte solution contains 1.9 mol SO42−, 3.9 mol Cl−, and 2.0 mol Vn+; the negative electrode electrolyte solution is controlled to contain 1.9 mol SO42−, 3.9 mol Cl-0.13 mol PO33− and 2.0 mol Vn+.
The specific preparation method is the same as that in Example 1, except that the preset ion concentration ratio is different, and PO33− is added to the negative electrode electrolyte, so that the positive electrode electrolyte solution contains 1.9 mol SO42−, 5.3 mol Cl−, and 2.0 mol Vn+; the negative electrode electrolyte solution is controlled to contain 1.9 mol SO42−, 5.3 mol Cl−, 0.2 mol PO33− and 2.0 mol Vn+.
The specific preparation method is the same as that in Example 1, except that the preset ion concentration ratio is different, and the additive glycerol is added to the electrolyte, so that the positive electrode electrolyte solution contains 1.9 mol SO42−, 3.9 mol Cl−, 2.0 mol Vn+ and 0.02 mol glycerol; the negative electrode electrolyte solution is controlled to contain 1.9 mol SO42− 3.9 mol Cl−, and 2.0 mol Vn+.
The specific preparation method is the same as that in Example 1, except that the preset ion concentration ratio is different, and the additive succinic acid is added to the electrolyte, so that the positive electrode electrolyte solution contains 1.9 mol SO42−, 5.3 mol Cl−, 2.0 mol Vn+ and 0.2 mol succinic acid; the negative electrode electrolyte solution is controlled to contain 1.9 mol SO42−, 5.3 mol Cl−, 2.0 mol Vn+ and 0.02 mol succinic acid.
The specific preparation method is the same as that in Example 1, except that the preset ion concentration ratio is different, so that the positive electrode electrolyte solution contains 2.0 mol SO42−, 4.6 mol Cl− and 2.25 mol Vn+; the negative electrode electrolyte solution contains 2.11 mol SO42−, 4.33 mol Cl− and 1.8 mol Vn+.
The specific preparation method is the same as that in Example 1, except that no chlorine is added, so that the positive electrode electrolyte solution contains 1.9 mol SO42− and 2.0 mol Vn+; the negative electrode electrolyte solution is controlled to contain 1.9 mol SO42− and 2.0 mol Vn+.
The specific preparation method is the same as that in Example 1, except that the preset ion concentration ratio is different, so that the positive electrode electrolyte solution contains 1.9 mol SO42−, 2.5 mol Cl− and 2.0 mol Vn+; the negative electrode electrolyte solution is controlled to contain 1.9 mol SO42−, 2.5 mol Cl− and 2.0 mol Vn+.
The specific preparation method is the same as that in Example 1, except that the preset ion concentration ratio is different, so that the positive electrode electrolyte solution contains 1.9 mol SO42−, 6.5 mol Cl− and 2.0 mol Vn+; the negative electrode electrolyte solution is controlled to contain 1.9 mol SO42−, 6.5 mol Cl− and 2.0 mol Vn+.
The specific preparation method is the same as that in Example 1, except that the preset ion concentration ratio is different, so that the positive electrode electrolyte solution contains 0.488 mol SO42−, 6.898 mol Cl− and 2.56 mol Vn+; the negative electrode electrolyte solution contains 0.615 mol SO42−, 7.655 mol Cl− and 1.941 mol Vn+.
The performance of the electrolytes of Examples 1-31 and Comparative examples 1-4 is tested or the electrolytes are prepared into all-vanadium redox flow batteries and the performance of the batteries is tested. See Tables 1 to 3 for specific test data.
The tests of all-vanadium redox flow batteries include the followings.
Battery efficiency test: A 5 W single battery is used, and a mode of constant current charging+constant voltage charging+constant current discharging is used. The current density of the constant current charging is 110 mA/cm2, the cut-off voltage is 1.6 V, and then constant voltage charging is performed at a voltage of 1.6 V, until the open circuit voltage of the battery is 1.54 V. Finally, the constant current discharging is performed at a constant current of 110 mA/cm2 to a cut-off voltage of 1 V.
EE=discharging Wh/charging Wh×100%; CE=discharging Ah/charging Ah×100%.
Cl2 evolution rate test: for a single battery with different active materials ratios, NaOH solution is used to collect the gas in the upper layer of the positive electrode electrolyte solution after two charging and discharging cycles, then ion chromatography is used to test the Cl-concentration in the NaOH collection solution, and the Cl2 production rate in a unit time is obtained.
Accelerated test of electrode corrosion: a 5 W single battery is used, and a mode of constant current charging+constant voltage charging+constant current discharging is used. The current density of the constant current charging is 110 mA/cm2, the cut-off voltage is 1.8 V, and then constant voltage charging is performed at a voltage of 1.8 V, until the open circuit voltage of the battery is 1.7 V. Finally, the constant current discharging is performed at a constant current of 110 mA/cm2 to a cut-off voltage of 1 V.
After 50 cycles of charging and discharging, an AC impedance instrument was used to test the resistance change of the battery at the end of the discharging and the battery was opened to observe the corrosion of the electrodes.
Referring to Table 1 and Table 2, it can be seen that for Examples 1-8 and Comparative Examples 1-3, when the concentrations of vanadium ions and sulfate ions remain unchanged, the production amount of Cl2 gradually increases with the increase of the chloride ion concentration, but at the same time, it has a significant protective effect on the electrode. Referring further to
Regarding Examples 9-12, when the concentrations of vanadium ions and chloride ions remain unchanged, the energy density of the battery gradually increases with the increase of the concentration of sulfate ions, and the energy efficiency increases. When the concentration of sulfate ions increases to 2.1 mol/L, the energy density no longer increases significantly, and the change in energy efficiency is also close to stable.
Regarding Examples 13-17, when the concentrations of sulfate ions and chloride ions remain unchanged, the energy density of the battery gradually increases with the increase of the concentration of vanadium ions, but when the concentration of vanadium ions increases to 2.2 mol/L, the upward trend becomes flat. It can be seen that the increase in viscosity caused by the concentration of vanadium ions increases the concentration polarization of the solution, making it difficult to further increase the energy density. At the same time, it can be seen from the energy efficiency that after the concentration of vanadium ions reaches 2.1 mol/L, the efficiency appears an inflection point and begins to decrease.
Referring to Table 3, for Example 30 and Comparative Example 4, it can be seen that: when the Vn+ concentration in the mixed acid solution is too high, that is, when it cannot meet the range of 2.9≤[c(Cl−)+c(SO42−)]/c(Vn+)≤3.6, the mass transfer resistance caused by the increase in viscosity of the solution cannot continue to increase the energy density of the solution. At the same time, the further increase of Cl− results in the evolution of a large amount of Cl2, which makes the system circulation pump severely gas bound and difficult to operate stably.
The electrolyte solution and all-vanadium redox flow battery provided by the embodiments of this disclosure have been introduced in detail above. Specific examples are used in this disclosure to illustrate the principles and implementation of this disclosure. The description of the above embodiments is only to help understand the technical solution and its core ideas of this disclosure. Those skilled in the art should understand that they can still modify the technical solutions recorded in the foregoing embodiments, or make equivalent substitutions for some of the technical features. However, these modifications or substitutions do not cause the essence of the corresponding technical solutions to depart from the scope of the technical solutions of the embodiments of the present disclosure.
| Number | Date | Country | Kind |
|---|---|---|---|
| 202211446542.2 | Nov 2022 | CN | national |
| Filing Document | Filing Date | Country | Kind |
|---|---|---|---|
| PCT/CN2023/115989 | 8/30/2023 | WO |
