CN115692808A - All-vanadium redox flow battery electrolyte reduction system and capacity recovery method - Google Patents
All-vanadium redox flow battery electrolyte reduction system and capacity recovery method Download PDFInfo
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- CN115692808A CN115692808A CN202211332184.2A CN202211332184A CN115692808A CN 115692808 A CN115692808 A CN 115692808A CN 202211332184 A CN202211332184 A CN 202211332184A CN 115692808 A CN115692808 A CN 115692808A
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Abstract
The invention discloses an electrolyte reduction system and a capacity recovery method for an all-vanadium redox flow battery, aiming at solving the technical problems that impurities are introduced and the electrode resistance is increased in the existing electrolyte capacity recovery method, and the technical scheme is as follows: reacting zinc salt and imidazole ligand with 2 times of the mass of the zinc salt for 12 hours in a reaction kettle to obtain carbon-based coated transition metal material catalyst Co 2 NiC, the catalyst is put into the positive pole liquid storage tank for reaction, inert gas and hydrogen are introduced, so that the valence state of the electrolyte after the reaction is 3.503The amount and the efficiency are influenced, the reaction process is controllable, the valence state of the electrolyte after the reaction is 3.503, and the capacity recovery effect reaches 99.9 percent.
Description
Technical Field
The invention belongs to the technical field of all-vanadium redox flow batteries, and particularly relates to an all-vanadium redox flow battery electrolyte reduction system and a capacity recovery method.
Background
The most important problem of the all-vanadium redox flow battery in long-term circulation is the problem of performance attenuation, which mainly comprises two parts, namely, efficiency and capacity attenuation, and the main reasons for the performance attenuation are as follows: (1) The cathode electrolyte is not fully protected, so that vanadium ions are oxidized in the charging and discharging processes, and the integral valence state is further higher than 3.5; (2) In the circulating process, the volume of the electrolyte solution of the anode and the overall concentration of vanadium ions are higher due to proton migration, so that the capacity is attenuated; the performance attenuation not only can greatly increase the maintenance frequency and cost of a later system, but also can directly reduce the service life of the battery; (3) The current technology is expensive to recover the unbalanced electrolyte.
At present, two technical routes are mainly adopted: (1) On the basis of unbalanced electrolyte, firstly charging the electrolyte to ensure that the vanadium ion of the cathode is in a valence state of 3, and because the electrolyte is in an unbalanced state, the valence state of the vanadium ion of the anode electrolyte is higher than a valence state of 4; (2) Under the condition of obtaining the anode electrolyte, the mass of the ferrous ammonium sulfate which needs to be added as a reducing agent is accurately calculated through valence state change, the anode electrolyte is recovered to 4 valence through oxidation-reduction chemical reaction, and finally the finally recovered electrolyte is obtained through liquid mixing. Although the above method restores the valence state by adding a reducing agent, there are the following problems: (1) Ferrous ammonium sulfate is used as a reducing agent, so that 3-valent iron ions and ammonium ions can be introduced in the reaction process, the newly introduced iron ions are variable-valent metal ions, and valence state change can be generated in the charging and discharging processes, so that the capacity and the efficiency are influenced; (2) Iron ions with valence 3 may be adsorbed onto the electrode, increasing the electrode resistance and reducing the electrode reactivity.
Disclosure of Invention
The invention aims to provide an electrolyte reduction system and a capacity recovery method of an all-vanadium redox flow battery, so as to solve the technical problems.
In order to solve the technical problems, the invention adopts the following technical scheme:
an inert gas inlet valve and a hydrogen inlet valve are arranged on one side of the top surface of a positive liquid storage tank, an adsorption device is movably arranged on the other side of the top surface, the inert gas inlet valve is externally connected with an inert gas cylinder, and the hydrogen inlet valve is externally connected with a hydrogen cylinder.
Furthermore, the adsorption device adopts a magnetic bar covered by polyethylene material.
Furthermore, a pressure sensor is arranged in the middle of the top surface of the positive liquid storage tank, and the pressure sensor is externally connected with a display.
A method for recovering electrolyte capacity of an all-vanadium redox flow battery comprises the following steps:
s1, synthesizing a catalyst, and specifically comprising the following steps:
s1.1, weighing 0.1-0.3mol of any one transition metal salt of cobalt chloride, ferric chloride or nickel chloride, dissolving in 100-200mL of methanol solution, and stirring until the transition metal salt is completely dissolved;
s1.2, weighing 0.1-0.3mol of zinc nitrate and 2-methylimidazole of which the mass is 2 times that of the zinc nitrate into the solution obtained in the step S1.1, and stirring until the zinc nitrate and the 2-methylimidazole are completely dissolved;
s1.3, transferring the solution obtained in the step S1.2 into a reaction kettle, reacting for 12 hours at 50-110 ℃, cooling to room temperature, washing for 3 times by using deionized water, drying, transferring into a tubular furnace, reacting for 3 hours at 700 ℃ under the inert gas condition, cooling to room temperature to obtain the carbon-based coated transition metal material catalyst, wherein the catalyst component is Co 2 NiC；
S2, reducing the electrolyte, and specifically comprising the following steps:
s2.1, opening an inert gas inlet valve and a pressure sensor, filling inert gas into the positive liquid storage tank, and discharging air in the tank;
s2.2, mixing the Co obtained in the step S1.3 2 Putting NiC catalyst into used positive liquid storage tube;
s2.3, opening a hydrogen gas inlet valve, filling hydrogen gas into the tank, and storing the hydrogen gas on the positive electrode under the action of a catalystThe electrolyte in the liquid tank is subjected to reduction reaction, and the reaction process is VO 2 + +2H + →VO 2+ +H 2 O；
And S2.4, after the reaction is finished, inserting an adsorption device into the top of the tank, and recovering the catalyst.
The beneficial effects of the invention are:
1. the invention reduces 5-valent vanadium ions by introducing hydrogen to generate VO in the reaction process 2 + +2H + →VO 2+ +H 2 The reaction of O, because the reducing metal is coated in the carbon-based material, not only can effectively limit the reduction process of the carbon-based material and realize selective reduction, but also can prevent the 5-valent vanadium ions from being over-reduced into low-valent vanadium ions;
2. due to the special structural property of the catalyst, the metal reducing agent only plays a role of catalysis and does not participate in the actual reduction process, so that the metal reducing agent does not overflow into the electrolyte, 5-valent vanadium ions are effectively reduced, new impurity ions are not introduced, and the electrolyte is ensured not to influence the capacity and the efficiency due to the impurity ions;
3. the reducing metal selected by the invention is the transition metal, the mineral deposit content is rich, the price is low, and the cost generated in the reducing process can be greatly reduced;
4. the invention selects clean energy hydrogen as reducing gas, and harmful gas to the environment can not be generated;
5. the reduction system is arranged in the liquid storage tank, so that the space of the whole energy storage system cannot be additionally increased;
6. the reaction process is controllable, the valence state of the electrolyte after the reaction is 3.503, and the capacity recovery effect reaches 99.9 percent;
drawings
FIG. 1 is a schematic diagram of an electrolyte reduction system according to the present invention;
FIG. 2 is a schematic diagram of the formation of a catalyst according to the present invention;
reference numerals are as follows: 1. an inert gas inlet valve; 2. a hydrogen gas inlet valve; 3. an adsorption device; 4. a pressure sensing device; 5. and a positive liquid storage tank.
Detailed Description
In order to make the technical means, the original characteristics, the achieved purposes and the effects of the invention easily understood, the invention is further described below with reference to the specific embodiments and the attached drawings, but the following embodiments are only the preferred embodiments of the invention, and not all embodiments. Based on the embodiments in the implementation, other embodiments obtained by those skilled in the art without any creative efforts belong to the protection scope of the present invention.
Specific embodiments of the present invention are described below with reference to the accompanying drawings.
The utility model provides an all vanadium redox flow battery electrolyte reduction system, is equipped with inert gas admission valve 1 and hydrogen admission valve 2 in the top surface one side of anodal liquid storage pot 5, and the activity of top surface opposite side is equipped with the magnetic force stick 3 that the polyethylene material covered, the external inert gas cylinder of inert gas admission valve 1, the external hydrogen gas cylinder of hydrogen admission valve 2, the top surface middle part of anodal liquid storage pot 5 is equipped with pressure sensor 4 to external display.
A method for recovering electrolyte capacity of an all-vanadium redox flow battery comprises the following steps:
s1, synthesizing a catalyst, and specifically comprising the following steps:
s1.1, weighing 0.2mol of cobalt chloride, dissolving in 150mL of methanol solution, and stirring until the cobalt chloride is completely dissolved;
s1.2, weighing 0.2mol of zinc nitrate and 0.4mol of 2-methylimidazole, and stirring the zinc nitrate and the 2-methylimidazole into the solution obtained in the step S1.1 until the zinc nitrate and the 2-methylimidazole are completely dissolved;
s1.3, transferring the solution obtained in the step S1.2 into a reaction kettle, reacting for 12 hours at 70 ℃, cooling to room temperature, washing for 3 times by using deionized water, drying, transferring into a tubular furnace, reacting for 3 hours at 700 ℃ under the inert gas condition, cooling to room temperature to obtain the carbon-based coated transition metal material catalyst, wherein the catalyst component is Co 2 NiC；
S2, reducing the electrolyte, and specifically comprising the following steps:
s2.1, opening an inert gas inlet valve 1 and a pressure sensor 4, filling inert gas into an anode liquid storage tank 5, and discharging air in the tank;
s2.2, taking the Co obtained in the step S1.3 2 1g of NiC catalyst is put into a used anode liquid storage pipe 5;
s2.3, opening the hydrogen inlet valve 2, filling 300kpa of hydrogen into the tank, stirring and reacting to obtain reduced electrolyte, and carrying out reduction reaction on the electrolyte in the anode liquid storage tank 5 by the hydrogen under the action of a catalyst, wherein the reaction process is VO 2 + +2H + →VO 2+ +H 2 O；
S2.4, after the reaction is finished, inserting an adsorption device 3 into the top of the tank, recovering the catalyst, and weighing the catalyst to obtain 1g after washing and drying, which indicates that the catalyst has no loss after the reaction. Experiments prove that 1g of catalyst can enable 10L of electrolyte to recover the initial valence, the valence of the electrolyte after reaction is 3.503, and the capacity recovery effect reaches 99.9%;
the transition metal salt in the step S1.1 can also be ferric chloride or nickel chloride in the amount of 0.1-0.3mol, and the methanol solution can also be any value between 100-200 mL;
the zinc nitrate in the step S1.2 can be any value of 0.1-0.3 mol;
the first reaction temperature in step S1.3 may also be any value from 50 to 110 ℃;
in the present invention, unless otherwise expressly stated or limited, "above" or "below" a first feature means that the first and second features are in direct contact, or that the first and second features are not in direct contact but are in contact with each other via another feature therebetween. Also, the first feature "on," "above" and "over" the second feature may include the first feature being directly above and obliquely above the second feature, or simply indicating that the first feature is at a higher level than the second feature. "beneath," "under" and "beneath" a first feature includes the first feature being directly beneath and obliquely beneath the second feature, or simply indicating that the first feature is at a lesser elevation than the second feature.
The foregoing shows and describes the general principles, essential features, and advantages of the invention. It should be understood by those skilled in the art that the present invention is not limited to the above embodiments, and the above embodiments and descriptions are only preferred examples of the present invention and are not intended to limit the present invention, and that various changes and modifications may be made without departing from the spirit and scope of the present invention, which fall within the scope of the claimed invention. The scope of the invention is defined by the appended claims and equivalents thereof.
Claims (4)
1. The utility model provides an all vanadium redox flow battery electrolyte reduction system, its characterized in that is equipped with inert gas admission valve (1) and hydrogen admission valve (2) in the top surface one side of anodal liquid storage pot (5), and the activity of top surface opposite side is equipped with adsorption equipment (3), the external inert gas cylinder of inert gas admission valve (1), the external hydrogen gas cylinder of hydrogen admission valve (2).
2. The all-vanadium redox flow battery electrolyte reduction system according to claim 1, wherein the adsorption device (3) adopts a magnetic bar covered by a polyethylene material.
3. The electrolyte reduction system of the all-vanadium redox flow battery, according to claim 1, wherein a pressure sensor (4) is disposed in a middle portion of a top surface of the positive liquid storage tank (5), and the pressure sensor (4) is externally connected with a display.
4. An all-vanadium flow battery electrolyte capacity recovery method using the all-vanadium flow battery electrolyte reduction system of any one of claims 1 to 3, characterized by comprising the following steps:
s1, synthesizing a catalyst, comprising the following specific steps:
s1.1, weighing 0.1-0.3mol of any one transition metal salt of cobalt chloride, ferric chloride or nickel chloride, dissolving in 100-200mL of methanol solution, and stirring until the transition metal salt is completely dissolved;
s1.2, weighing 0.1-0.3mol of zinc nitrate and 2-methylimidazole with the mass of 2 times of that of the zinc nitrate into the solution obtained in the step S1.1, and stirring until the zinc nitrate and the 2-methylimidazole are completely dissolved;
s1.3, transferring the solution obtained in the step S1.2 into a reaction kettle, reacting for 12 hours at 50-110 ℃, cooling to room temperature, washing for 3 times by using deionized water, drying, transferring into a tubular furnace, reacting for 3 hours at 700 ℃ under the inert gas condition, cooling to room temperature to obtain the carbon-based coated transition metal material catalyst, wherein the catalyst component is Co 2 NiC；
S2, reducing the electrolyte, and specifically comprising the following steps:
s2.1, opening an inert gas inlet valve (1) and a pressure sensor (4), filling inert gas into a positive pole liquid storage tank (5), and discharging air in the tank;
s2.2, mixing the Co obtained in the step S1.3 2 Putting NiC catalyst into used anode liquid storage tube (5);
s2.3, opening the hydrogen inlet valve (2), filling hydrogen into the tank, and carrying out reduction reaction on the electrolyte in the anode liquid storage tank (5) by the hydrogen under the action of a catalyst, wherein the reaction process is VO 2 + +2H + →VO 2+ +H 2 O；
And S2.4, after the reaction is finished, inserting an adsorption device (3) into the top of the tank, and recovering the catalyst.
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| CN202211332184.2A CN115692808A (en) | 2022-10-28 | 2022-10-28 | All-vanadium redox flow battery electrolyte reduction system and capacity recovery method |
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Cited By (1)
| 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 |
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Cited By (2)
| 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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