CN114551935B - Performance recovery method of zinc-bromine single flow battery - Google Patents

Performance recovery method of zinc-bromine single flow battery Download PDF

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CN114551935B
CN114551935B CN202011340256.9A CN202011340256A CN114551935B CN 114551935 B CN114551935 B CN 114551935B CN 202011340256 A CN202011340256 A CN 202011340256A CN 114551935 B CN114551935 B CN 114551935B
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electrolyte
battery
zinc
storage tank
positive electrode
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CN114551935A (en
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宋杨
李先锋
张华民
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Dalian Institute of Chemical Physics of CAS
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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
    • 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
    • H01M8/008—Disposal or recycling of fuel cells
    • 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
    • H01M8/04—Auxiliary arrangements, e.g. for control of pressure or for circulation of fluids
    • H01M8/04223—Auxiliary arrangements, e.g. for control of pressure or for circulation of fluids during start-up or shut-down; Depolarisation or activation, e.g. purging; Means for short-circuiting defective fuel cells
    • 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
    • H01M8/04—Auxiliary arrangements, e.g. for control of pressure or for circulation of fluids
    • H01M8/04276—Arrangements for managing the electrolyte stream, e.g. heat exchange
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30—Hydrogen technology
    • Y02E60/50—Fuel cells

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  • Life Sciences & Earth Sciences (AREA)
  • Sustainable Development (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Sustainable Energy (AREA)
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  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Hybrid Cells (AREA)

Abstract

The invention relates to an application of an additive which is stable in electrolyte of a zinc-bromine flow battery and has reducibility in the zinc-bromine flow battery, and belongs to the field of flow batteries. The additive consists of one or more than two hydrazine compounds such as hydrazine hydrate, hydrazine hydrochloride and the like. The additive has stable properties in the electrolyte of the zinc-bromine battery, does not participate in charge-discharge reaction in the charge-discharge process of the battery, has reducibility and can reduce bromine simple substance, and the reduction product has oxidizability and can oxidize zinc simple substance accumulated by the negative electrode. After the battery runs for a long time, the positive and negative electrolyte is mixed with each other, and the additive is added into the electrolyte storage tank, so that the performance of the negative electrode of the battery can be greatly recovered, and the service life of the battery is prolonged. The recovery agent has rapid reaction, and can instantaneously react with the residual active substances in the electrolyte when being placed in the electrolyte, thereby greatly improving the recovery efficiency. Compared with the traditional zinc-bromine battery electrolyte restorative, the circulating pump is not needed to circulate the electrolyte, so that the energy consumption and the time are saved.

Description

Performance recovery method of zinc-bromine single flow battery
Technical Field
The invention relates to a performance restorative of a zinc-bromine single flow battery.
Technical Field
The zinc-bromine single-flow energy storage battery is a novel low-cost, high-efficiency and environment-friendly flow energy storage battery, has the advantages of high energy density and current efficiency, simple and easy operation of the device, long service life, low cost and the like, and is mainly applied to the fields of renewable energy power generation such as power grid peak shaving, wind energy and solar energy, electric automobiles and the like.
For zinc system flow batteries, the poor stability of zinc cathodes always restricts the important factors for the development of such batteries. In the battery charging process, dendrite growth of the zinc cathode is difficult to control, so that problems of falling off, accumulation and the like of zinc simple substance in the cathode occur in the discharging process, and the stability of the battery is poor. In the discharging process of the battery, the active substances generated by charging cannot be completely consumed after the battery is charged and discharged each time due to the factors such as battery polarization, uneven zinc deposition and the like, so that the active substances are accumulated, and the battery performance is affected.
The performance restorative agent of the zinc-bromine single flow battery utilizes the principle that only nitrogen and water are generated when a hydrazine compound is subjected to oxidation-reduction reaction, one or more than two hydrazine compounds such as hydrazine hydrate, hydrazine hydrochloride and the like are added into electrolyte when the zinc-bromine single flow battery is discharged, the bromine simple substance remained in the electrolyte is reduced into bromide ions by utilizing the strong reducibility of the hydrazine compound, and the generated product hydrobromic acid can be pumped into the cathode of the battery along with an electrolyte circulating pump, and can react with zinc accumulated on the cathode to remove redundant zinc on the cathode. Thereby restoring the battery to an initial state and restoring the battery performance.
Disclosure of Invention
According to the invention, by combining the structural characteristics of the zinc-bromine single flow battery, when the battery is restored by mutual mixing electrolysis, one or more than two hydrazine compounds such as hydrazine hydrate, hydrazine hydrochloride and the like are added into the electrolyte, so that the battery is restored to an initial state, and the performance of the battery is restored.
In order to achieve the above purpose, the technical scheme adopted by the invention is as follows:
when the battery is operated for a period of time until the performance of the battery is greatly reduced (the energy efficiency is reduced by more than 5 percent), stopping charging and discharging after the battery is completely discharged, opening a positive electrolyte inlet valve, mixing the positive electrolyte and the negative electrolyte of the battery, and adding one or more than two hydrazine compounds such as hydrazine hydrate, hydrazine hydrochloride and the like into an electrolyte storage tank; the solution which is dripped into the electrolyte storage tank is hydrazine hydrate liquid or hydrazine hydrate aqueous solution with the molar concentration of 0.5mol/L to 1mol/L, and the saturated hydrazine hydrochloride aqueous solution is 0.8mol/L to 1.2mol/L. The dropping speed of the solution is 5ml/min to 10ml/min, preferably 5ml/min, of electrolyte per liter in the electrolyte storage tank. Introducing the electrolyte in the electrolyte storage tank into a cavity where the anode and the cathode are positioned through a pump to flow while dripping until the electrolyte in the electrolyte storage tank becomes colorless; the additive is reacted with the active material accumulated on the anode and cathode. The final concentration of the catalyst is 0.1mol/L to 0.5mol/L, preferably 0.02mol/L to 0.03mol/L; introducing the electrolyte into a cavity where the positive electrode and the negative electrode are positioned through a pump to flow for more than 1 minute; the additive is reacted with the active material accumulated on the anode and cathode. And the bromine residual in the electrolyte is reduced into bromide ions by utilizing the strong reducibility of the hydrazine compound, the generated product hydrobromic acid can be pumped into the negative electrode of the battery along with the electrolyte circulating pump, and the hydrobromic acid can react with zinc accumulated on the negative electrode to remove redundant zinc on the negative electrode. Thereby restoring the battery to an initial state and restoring the battery performance. The positive liquid inlet of the battery is connected with the electrolyte storage tank through a pipeline by a pump, the liquid outlet of the positive electrode of the battery is connected with the electrolyte storage tank through a pipeline, pipeline valves are arranged at the positive liquid inlet and the liquid outlet of the battery, when the battery operates, the valves at the positive electrolyte liquid inlet and outlet are closed, and when the battery is recovered, the positive electrolyte liquid inlet valves are opened.
The positive and negative electrolytes of the zinc-bromine single flow battery are neutral aqueous solutions containing zinc ions, the raw materials of zinc and bromine are zinc bromide, the concentration of the zinc ions in the positive and negative electrolytes of the battery is the same, the concentration of the supporting electrolyte KCl is the same, and the concentration of the zinc ions in the electrolytes is as follows: 2-4mol/L and KCl concentration of 2-5mol/L. Negative electrolyte in an electrolyte storage tank of the zinc-bromine single-flow battery flows at one end of a negative electrode through a pump, and an ion exchange membrane is arranged between the positive electrode and the negative electrode; the liquid inlet of the battery cathode is connected with the electrolyte storage tank through a pipeline by a pump, and the liquid outlet of the battery cathode is connected with the electrolyte storage tank through a pipeline.
The dropping speed of the solution is 5ml/min to 10ml/min, preferably 5ml/min, of electrolyte per liter in the electrolyte storage tank.
The invention has the beneficial effects that:
aiming at the problem of performance attenuation of a zinc-bromine single flow battery in the running process of the battery, the invention removes bromine simple substance remained in the electrolyte by mixing the battery and adding one or more than two substances of hydrazine compounds such as hydrazine hydrate, hydrazine hydrochloride and the like into the electrolyte in the mixing process, and simultaneously, hydrobromic acid which is an oxidation product after reaction can be pumped into the cathode of the battery along with an electrolyte circulating pump, the hydrobromic acid can react with zinc accumulated on the cathode, and the redundant zinc on the cathode is removed. Thereby restoring the battery to an initial state and restoring the battery performance.
The hydrazine substance has strong reducibility, the oxidation product after the hydrazine is oxidized only contains nitrogen and water, the oxidation product does not cause any pollution to electrolyte, (after the reaction of the hydrazine hydrochloride and bromine, the generated product contains nitrogen, water and chloride ions, KCl is used as supporting electrolyte in the electrolysis of the zinc-bromine single flow battery, and the chloride ions in the oxidation product of the additive can not influence the composition of electrolyte substances). The reaction rate of hydrazine and bromine simple substance is extremely high, after hydrazine substances are added into the electrolyte, bromine in the electrolyte can be reduced by the hydrazine substances in extremely short time, and the electrolyte and the additive are not required to be fully mixed by using an electrolyte circulating pump for a long time, so that the electrolyte can be recovered by using a method of slowly dripping the hydrazine and the bromine into the electrolyte, and the additive amount is controlled by the color change (from red to colorless) of the electrolyte, so that the excessive additive is avoided. This reduces pump consumption and saves electrical energy. The method has low cost, quick action, and simple operation. The problem of poor cycling stability of the zinc-bromine single flow battery is solved in a short-time and efficient way, and the development of the zinc-bromine single flow battery is boosted.
Drawings
Fig. 1 is a zinc bromine single flow cell stack (comparative example 1) using electrolyte without any additives, cell stack charge-discharge cycle performance. Charging 60 mins@40 mA/cm current density 2 Discharge @ Current Density 40mA/cm 2
Fig. 2 is a graph showing the charge-discharge cycle performance of a zinc-bromine single-fluid cell stack operated using the operating strategy and recovery method of example 1. Charging 60 mins@40 mA/cm current density 2 Discharge @ Current Density 40mA/cm 2
Table 1 is a change in performance of a zinc bromine single flow cell stack after a first recovery operation using the formic acid recovery agent of comparative example 2. Charging 60 mins@40 mA/cm current density 2 Discharge @ Current Density 40mA/cm 2
Table 2 is a change in performance of a zinc bromine single flow cell stack after a first recovery operation using the hydrazine hydrate solution recovery agent of example 2. Charging 60 mins@40 mA/cm current density 2 Discharge @ Current Density 40mA/cm 2
Comparative example 1
The electrolyte of the battery is 2mol/LZnBr 2 +3mol/LKCl+0.8M MEP, single cell positive electrode end plate, positive electrode 6x6cm in sequence 2 Graphite plate, positive electrode frame and carbon feltDiaphragm, carbon felt, negative electrode frame, negative electrode 6x6cm 2 Graphite plate, negative end plate. The positive electrode electrolyte is sealed in a closed cavity surrounded by the positive electrode frame, the positive electrode current collector (graphite plate) and the battery diaphragm, and does not flow. Charge-discharge current density 40mA/cm 2 . The charging capacity is 40mAh/cm 2 . The battery was subjected to constant current (@ current density 40 mA/cm) 2 ) Charging is carried out in a mode of charging for one hour, and constant current (40 mA/cm of current density is adopted in discharging) 2 ) The discharge was performed by the method of cutting off the voltage to 0.8V.
As can be seen from fig. 1, the pile stability is poor, the pile performance attenuation is serious, the pile uniformity is poor, the pile cycle stability is relatively poor, and the pile life is low.
Example 1
The electrolyte of the battery is 2mol/LZnBr 2 +3mol/LKCl+0.8M MEP, single cell positive electrode end plate, positive electrode 6x6cm in sequence 2 Graphite plate, positive electrode frame, carbon felt, diaphragm, carbon felt, negative electrode frame, negative electrode 6x6cm 2 Graphite plate, negative end plate. The positive electrode electrolyte is sealed in a closed cavity surrounded by the positive electrode frame, the positive electrode current collector (graphite plate) and the battery diaphragm, and does not flow. Charge-discharge current density 40mA/cm 2 . The charging capacity is 40mAh/cm 2 。
The liquid inlet of the battery cathode is connected with the electrolyte storage tank through a pipeline by a cathode electrolyte circulating pump, and the liquid outlet of the battery cathode is connected with the electrolyte storage tank through a pipeline.
The positive electrolyte inlet of the battery is connected with the electrolyte storage tank through a positive electrolyte circulating pump by a pipeline, the positive electrolyte outlet of the battery is connected with the electrolyte storage tank by a pipeline, pipeline valves are arranged at the positive electrolyte inlet and the electrolyte outlet of the battery, when the battery operates, the valves at the positive electrolyte inlet and outlet are closed, and when the battery is recovered, the positive electrolyte inlet valves are opened.
When the performance is obviously reduced (coulomb efficiency is reduced by more than 5%) in the running process of the electric pile, the electric pile is restored by using the method disclosed by the invention, namely the battery is completely discharged, the hydrazine hydrate solution with the concentration of 0.5mol/L is used for dropwise adding the hydrazine hydrate solution into the electrolyte at the speed of 5ml/min, meanwhile, the positive and negative electrode liquid inlet valves of the battery are opened, and the positive electrode electrolyte circulating pump is opened. When the electrolyte became colorless, the dropwise addition was stopped. By using the method to recover the electrolyte, the pile performance can be kept stable.
As can be seen from fig. 2, the stack cycle performance is stable, and the stack life is also prolonged, as compared with a stack without additives. The additive has excellent performance and remarkable effect.
Comparative example 2
The electrolyte of the battery is 2mol/LZnBr 2 +3mol/LKCl+0.8M MEP, single cell positive electrode end plate, positive electrode 6x6cm in sequence 2 Graphite plate, positive electrode frame, carbon felt, diaphragm, carbon felt, negative electrode frame, negative electrode 6x6cm 2 Graphite plate, negative end plate. The positive electrode electrolyte is sealed in a closed cavity surrounded by the positive electrode frame, the positive electrode current collector (graphite plate) and the battery diaphragm, and does not flow. Charge-discharge current density 40mA/cm 2 . The charging capacity is 40mAh/cm 2 . The battery was subjected to constant current (@ current density 40 mA/cm) 2 ) Charging is carried out in a mode of charging for one hour, and constant current (40 mA/cm of current density is adopted in discharging) 2 ) The discharge was performed by the method of cutting off the voltage to 0.8V.
The liquid inlet of the battery cathode is connected with the electrolyte storage tank through a pipeline by a cathode electrolyte circulating pump, and the liquid outlet of the battery cathode is connected with the electrolyte storage tank through a pipeline.
The positive electrolyte inlet of the battery is connected with the electrolyte storage tank through a positive electrolyte circulating pump by a pipeline, the positive electrolyte outlet of the battery is connected with the electrolyte storage tank by a pipeline, pipeline valves are arranged at the positive electrolyte inlet and the electrolyte outlet of the battery, when the battery operates, the valves at the positive electrolyte inlet and outlet are closed, and when the battery is recovered, the positive electrolyte inlet valves are opened.
When the electric pile runs to the 29 th circulation, the electric pile is restored, after the electric pile is completely discharged, a positive electrolyte circulation valve is opened, positive electrolyte in the positive electrode of the zinc-bromine single-flow battery is led into an electrolyte storage tank, the positive electrolyte and the negative electrolyte of the battery are mixed with each other, 50ml of formic acid solution with the mass fraction of 99% is added into the electrolyte, and the electrolyte is led into a positive cavity and a negative cavity by using an electrolyte circulation pump, so that the electrolyte circularly flows in the positive and the negative and the liquid storage tank for more than 4 hours. And after the operation is finished, closing the positive electrolyte inlet valve, and continuing to operate the galvanic pile.
Because the additive amount of formic acid cannot be determined, in the experiment, excessive formic acid is adopted to recover the electrolyte, after the electrolyte is recovered, partial formic acid remains in the electrolyte, in the subsequent charging process, the formic acid in the electrolyte can react with zinc simple substance generated by the negative electrode, the performance of a galvanic pile is influenced (the coulomb efficiency is reduced), and the 4 th cycle performance of the galvanic pile is recovered to be normal after the recovery is completed, so that the recovery process is excessively troublesome and the time is longer.
Example 2
The electrolyte of the battery is 2mol/LZnBr 2 +3mol/LKCl+0.8M MEP, single cell positive electrode end plate, positive electrode 6x6cm in sequence 2 Graphite plate, positive electrode frame, carbon felt, diaphragm, carbon felt, negative electrode frame, negative electrode 6x6cm 2 Graphite plate, negative end plate. The positive electrode electrolyte is sealed in a closed cavity surrounded by the positive electrode frame, the positive electrode current collector (graphite plate) and the battery diaphragm, and does not flow. Charge-discharge current density 40mA/cm 2 . The charging capacity is 40mAh/cm 2 . The battery was subjected to constant current (@ current density 40 mA/cm) 2 ) Charging is carried out in a mode of charging for one hour, and constant current (40 mA/cm of current density is adopted in discharging) 2 ) The discharge was performed by the method of cutting off the voltage to 0.8V.
The liquid inlet of the battery cathode is connected with the electrolyte storage tank through a pipeline by a cathode electrolyte circulating pump, and the liquid outlet of the battery cathode is connected with the electrolyte storage tank through a pipeline.
The positive electrolyte inlet of the battery is connected with the electrolyte storage tank through a positive electrolyte circulating pump by a pipeline, the positive electrolyte outlet of the battery is connected with the electrolyte storage tank by a pipeline, pipeline valves are arranged at the positive electrolyte inlet and the electrolyte outlet of the battery, when the battery operates, the valves at the positive electrolyte inlet and outlet are closed, and when the battery is recovered, the positive electrolyte inlet valves are opened.
When the electric pile runs to the 29 th circulation, the electric pile is restored, after the electric pile is completely discharged, a positive electrolyte circulation valve is opened, positive electrolyte in the positive electrode of the zinc-bromine single-flow battery is led into an electrolyte storage tank, the positive electrolyte and the negative electrolyte of the battery are mixed with each other, meanwhile, hydrazine hydrate aqueous solution with the concentration of 0.5mol/L is dropwise added into the electrolyte, the electrolyte in the electrolyte storage tank is led into a cavity where the positive electrode and the negative electrode are located through a pump to flow while dropwise adding until the electrolyte in the electrolyte storage tank becomes colorless, and the additive reacts with active substances accumulated on the positive electrode and the negative electrode. And after the operation is finished, closing the positive electrolyte inlet valve, and continuing to operate the galvanic pile.
As can be seen from table 2, the pile was restored using the method in example 2, and the performance of the pile was rapidly restored during the charging after the restoration (compared to comparative example 1). The hydrazine compound has strong reducibility, the residual bromine simple substance in the electrolyte is reduced by using a dripping mode, the reaction time is short, the dripping dosage can be determined according to the color of the electrolyte (from red to colorless), and excessive dripping is avoided. Thus, when the galvanic pile runs again, no redundant reducing additive exists in the electrolyte, the zinc simple substance of the cathode of the galvanic pile cannot be consumed, and the performance of the galvanic pile can be quickly recovered (as can be seen from the table 2, the initial performance of the galvanic pile is recovered only by two cycles after the recovery is finished). Compared with other additives, the additive used in the preparation method has the advantages of higher recovery efficiency, more excellent performance and remarkable effect. And the additive amount can be precisely controlled.
TABLE 1
Number of operating cycles of the stack CE/％ VE/％ EE/％
29 92 81 75
30 70 76 53
31 81 77 62
32 86 79 68
33 91 80 73
TABLE 2
Number of operating cycles of the stack CE/％ VE/％ EE/％
29 92 81 75
30 82 77 63
31 88 79 70
32 92 80 74
33 92 80 74

Claims (6)

1. The method for recovering the performance of the zinc-bromine single-flow battery comprises an electrolyte storage tank, wherein electrolyte in the electrolyte storage tank circularly flows in a cavity where a negative electrode of the zinc-bromine single-flow battery is located, and the method is characterized in that:
1) Discharging the battery completely when coulomb efficiency decreases after the battery is operated;
2) Opening a valve of an electrolyte inlet and outlet of the positive electrode, introducing the positive electrode electrolyte in the positive electrode of the zinc-bromine single flow battery into an electrolyte storage tank, mixing the positive electrode electrolyte and the negative electrode electrolyte of the battery, dropwise adding one or more than two solutions of hydrazine compounds such as hydrazine hydrate, hydrazine hydrochloride and the like into the electrolyte storage tank, introducing the electrolyte in the electrolyte storage tank into a cavity where the positive electrode and the negative electrode are positioned through a pump while dropwise adding the solution until the electrolyte in the electrolyte storage tank becomes colorless and stops; reacting the additive with the active material accumulated on the anode and cathode;
3) And closing a valve of the positive electrolyte inlet and outlet, and operating the zinc-bromine single flow battery.
2. The method according to claim 1, characterized in that: the positive and negative electrolytes of the zinc-bromine single flow battery are neutral aqueous solutions containing zinc ions, the raw materials of zinc and bromine are zinc bromide, the concentration of the zinc ions in the positive and negative electrolytes of the battery is the same, the concentration of the supporting electrolyte KCl is the same, and the concentration of the zinc ions in the electrolytes is as follows: 2-4mol/L and KCl concentration of 2-5mol/L.
3. The method according to claim 1 or 2, wherein a negative electrode electrolyte in an electrolyte storage tank of the zinc-bromine single flow battery flows at one end of a negative electrode through a pump, and an ion exchange membrane is arranged between the positive electrode and the negative electrode; the liquid inlet of the battery cathode is connected with the electrolyte storage tank through a pipeline by a pump, and the liquid outlet of the battery cathode is connected with the electrolyte storage tank through a pipeline.
4. The method according to claim 1, characterized in that: the solution dropwise added into the electrolyte storage tank is hydrazine hydrate liquid, or hydrazine hydrate aqueous solution with the molar concentration of 0.5 mol/L-1 mol/L, or hydrazine hydrochloride aqueous solution with the molar concentration of 0.8 mol/L-1.2 mol/L;
the dropping speed of the solution is 5 ml/min-10 ml/min of electrolyte per liter in the electrolyte storage tank.
5. The method of claim 4, wherein the dropping rate of the solution is 5ml/min per liter of electrolyte in the electrolyte tank.
6. The method of claim 1, wherein the battery positive electrode liquid inlet is connected with the electrolyte storage tank through a pipeline by a pump, the battery positive electrode liquid outlet is connected with the electrolyte storage tank through a pipeline, pipeline valves are arranged at the battery positive electrode liquid inlet and liquid outlet, the valves at the positive electrode electrolyte liquid inlet and outlet are closed when the battery is operated, and the positive electrode electrolyte liquid inlet valve is opened when the battery is restored after mixing.
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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH06333609A (en) * 1993-05-21 1994-12-02 Meidensha Corp Method for operating zinc-bromine battery
CN106159286A (en) * 2016-09-12 2016-11-23 北京科技大学 A kind of modified electrode being applied to zinc-bromine flow battery and preparation method thereof
CN108134120A (en) * 2016-12-01 2018-06-08 中国科学院大连化学物理研究所 A kind of zinc-bromine flow battery method for restoring performance
CN109860658A (en) * 2017-11-28 2019-06-07 中国科学院大连化学物理研究所 A kind of restoration methods of zinc bromine single flow battery performance
CN111244517A (en) * 2018-11-28 2020-06-05 中国科学院大连化学物理研究所 Method for recovering performance of alkaline zinc-nickel flow battery

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH06333609A (en) * 1993-05-21 1994-12-02 Meidensha Corp Method for operating zinc-bromine battery
CN106159286A (en) * 2016-09-12 2016-11-23 北京科技大学 A kind of modified electrode being applied to zinc-bromine flow battery and preparation method thereof
CN108134120A (en) * 2016-12-01 2018-06-08 中国科学院大连化学物理研究所 A kind of zinc-bromine flow battery method for restoring performance
CN109860658A (en) * 2017-11-28 2019-06-07 中国科学院大连化学物理研究所 A kind of restoration methods of zinc bromine single flow battery performance
CN111244517A (en) * 2018-11-28 2020-06-05 中国科学院大连化学物理研究所 Method for recovering performance of alkaline zinc-nickel flow battery

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