CN114551935A - Performance recovery method of zinc-bromine single flow battery - Google Patents

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

Info

Publication number
CN114551935A
CN114551935A CN202011340256.9A CN202011340256A CN114551935A CN 114551935 A CN114551935 A CN 114551935A CN 202011340256 A CN202011340256 A CN 202011340256A CN 114551935 A CN114551935 A CN 114551935A
Authority
CN
China
Prior art keywords
electrolyte
battery
zinc
positive
storage tank
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
CN202011340256.9A
Other languages
Chinese (zh)
Other versions
CN114551935B (en
Inventor
宋杨
李先锋
张华民
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Dalian Institute of Chemical Physics of CAS
Original Assignee
Dalian Institute of Chemical Physics of CAS
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Dalian Institute of Chemical Physics of CAS filed Critical Dalian Institute of Chemical Physics of CAS
Priority to CN202011340256.9A priority Critical patent/CN114551935B/en
Publication of CN114551935A publication Critical patent/CN114551935A/en
Application granted granted Critical
Publication of CN114551935B publication Critical patent/CN114551935B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Classifications

    • 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

Landscapes

  • Life Sciences & Earth Sciences (AREA)
  • Sustainable Development (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Sustainable Energy (AREA)
  • Chemical & Material Sciences (AREA)
  • 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 zinc-bromine flow battery electrolyte and has reducibility in a zinc-bromine single flow battery, belonging to the field of flow batteries. The additive consists of hydrazine hydrate, hydrazine hydrochloride and other hydrazine compounds or more than two kinds of hydrazine compounds. The additive has stable quality 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 to reduce bromine simple substance, and the reduction product has oxidability to oxidize the zinc simple substance accumulated by a negative electrode. After the battery runs for a long time, the positive electrolyte and the negative electrolyte are mixed, 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 restoring agent is rapid in reaction, can be instantly reacted with active substances remained in the electrolyte when being placed in the electrolyte, and greatly improves restoring efficiency. Compared with the traditional zinc-bromine battery electrolyte recovery agent, the electrolyte is not required to be circulated by using a circulating pump, so that the energy consumption is saved, and the time is saved.

Description

Performance recovery method of zinc-bromine single flow battery
Technical Field
The invention relates to a performance recovery agent 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 power grid peak shaving, power generation of renewable energy sources such as wind energy and solar energy, electric automobiles and the like.
For zinc system flow batteries, poor stability of zinc negative electrodes always restricts important factors of the development of the batteries. In the charging process of the battery, dendritic crystal growth of the zinc cathode is difficult to control, so that the problems of falling, accumulation and the like of a zinc simple substance of the cathode in the discharging process are caused, and the stability of the battery is poor. In the discharging process of the battery, due to factors such as polarization of the battery, uneven zinc deposition and the like, active substances generated by charging cannot be completely consumed after the battery is charged and discharged every time, so that the active substances are accumulated, and the performance of the battery is influenced.
A performance recovery agent for a zinc-bromine single flow battery utilizes the principle that hydrazine compounds only generate nitrogen and water when redox reaction is carried out, when the zinc-bromine single flow battery is discharged, one or more hydrazine compounds such as hydrazine hydrate and hydrazine hydrochloride are added into electrolyte, the strong reducibility of the hydrazine compounds is utilized to reduce bromine elementary substances remained in the electrolyte into bromine ions, generated product hydrobromic acid can be pumped into a battery cathode along with an electrolyte circulating pump, and the hydrobromic acid can react with zinc accumulated by the cathode to remove redundant zinc on the cathode. Thereby restoring the battery to the initial state and restoring the battery performance.
Disclosure of Invention
The invention combines the structural characteristics of the zinc-bromine single flow battery, and when the battery is restored by mutual mixing electrolysis, one or more hydrazine compounds such as hydrazine hydrate, hydrazine hydrochloride and the like are added into the electrolyte to restore the battery to the initial state, thereby restoring the battery performance.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
when the battery runs for a period of time until the performance of the battery is greatly reduced (the energy efficiency is reduced by more than 5%), stopping charging and discharging after the battery is completely discharged, opening a liquid inlet valve of the positive electrolyte, mixing the positive electrolyte and the negative electrolyte of the battery, and adding one or more hydrazine compounds such as hydrazine hydrate, hydrazine hydrochloride and the like into an electrolyte storage tank; the solution dripped into the electrolyte storage tank is hydrazine hydrate liquid or hydrazine hydrate aqueous solution with the molar concentration of 0.5-1 mol/L, and the saturated hydrazine hydrochloride aqueous solution is 0.8-1.2 mol/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. Leading the electrolyte in the electrolyte storage tank into the chamber where the positive electrode and the negative electrode are positioned by a pump to flow while dropwise adding until the electrolyte in the electrolyte storage tank is colorless; the additive is made to react with the active material accumulated on the positive and negative electrodes. The final concentration of the additive is 0.1-0.5 mol/L, preferably 0.02-0.03 mol/L; leading the electrolyte into the chamber with the positive electrode and the negative electrode through a pump to flow for more than 1 minute; the additive is made to react with the active material accumulated on the positive and negative electrodes. The strong reducibility of hydrazine compounds is utilized to reduce bromine elementary substances remained in the electrolyte into bromide ions, the generated product hydrobromic acid can be pumped into the battery cathode along with an electrolyte circulating pump, and the hydrobromic acid can react with zinc accumulated in the cathode to remove redundant zinc on the cathode. Thereby recovering the battery to the initial state and recovering the battery performance. The positive electrode liquid inlet of the battery is connected with the electrolyte storage tank through a pipeline through a pump, the positive electrode liquid outlet of the battery is connected with the electrolyte storage tank through a pipeline, pipeline valves are arranged at the positive electrode liquid inlet and the liquid outlet of the battery, when the battery runs, the valves at the positive electrode electrolyte inlet and outlet are closed, and when the batteries are mutually mixed and recovered, the positive electrode electrolyte liquid inlet valve is opened.
The positive and negative electrolytes of the zinc-bromine single flow battery are neutral aqueous solutions containing zinc ions, zinc and bromine raw materials are zinc bromide, the concentrations of the zinc ions in the positive and negative electrolytes of the battery are the same, the concentrations of KCl supporting electrolytes are the same, and the concentrations of the zinc ions in the electrolytes are as follows: 2-4mol/L and KCl concentration of 2-5 mol/L. 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 battery negative electrode liquid inlet is connected with the electrolyte storage tank through a pump through a pipeline, and the battery negative electrode liquid outlet 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 operation process of the battery, the residual bromine in the electrolyte is removed by mixing the battery and adding one or more of hydrazine compounds such as hydrazine hydrate, hydrazine hydrochloride and the like into the electrolyte in the mixing process, and meanwhile, an oxidation product hydrobromic acid after reaction is pumped into the negative electrode of the battery along with an electrolyte circulating pump, and the hydrobromic acid can react with zinc accumulated in the negative electrode to remove redundant zinc on the negative electrode. Thereby restoring the battery to the initial state and restoring the battery performance.
Because hydrazine substances have strong reducibility, and oxidation products of hydrazine after oxidation only comprise nitrogen and water, the oxidation products do not cause any pollution to electrolyte (after the hydrazine hydrochloride reacts with bromine, the generated products comprise nitrogen, water and chloride ions, and KCl is used as supporting electrolyte in the zinc-bromine single flow battery electrolysis, and the chloride ions in the oxidation products of the additive do not influence the composition of the electrolyte). Hydrazine and bromine simple substance reaction rate is very fast, after adding hydrazine class material into electrolyte, bromine in the electrolyte just can be reduced by hydrazine class material in the time of the utmost point short, need not to use the electrolyte circulating pump to fully mix electrolyte and additive for a long time, consequently, can use the method of slowly dropwise add to electrolyte to resume electrolyte, control the additive amount through electrolyte color change (from red to colorless), avoid the additive excessive. This reduces pump consumption and saves electric energy. The method has low cost, rapid action, and simple operation. The problem of poor circulation stability of the zinc bromine single flow battery is solved in a short time and high efficiency mode, and the development of the zinc bromine flow battery is promoted.
Drawings
Fig. 1 shows the performance of a zinc-bromine single flow cell stack (comparative example 1) using electrolyte without any additive, and the cell stack charge-discharge cycle. Charging 60mins @ Current Density 40mA/cm2Discharge @ Current Density 40mA/cm2
Figure 2 shows the stack charge-discharge cycle performance for a zinc-bromine single flow galvanic stack operated using the operating strategy and recovery method of example 1. Charging 60mins @ Current Density 40mA/cm2Discharge @ Current Density 40mA/cm2
Table 1 shows the performance of the zinc-bromine single-flow thermopile recovered using the formic acid recovering agent of comparative example 2, after the first recovery operation, the performance of the thermopile was changed. Charging 60mins @ Current Density 40mA/cm2Discharge @ Current Density 40mA/cm2
Table 2 shows the performance of the zinc-bromine single-flow thermopile recovered using the hydrazine hydrate solution recovering agent of example 2, after the first recovery operation, the performance of the thermopile was changed. Charging 60mins @ Current Density 40mA/cm2Discharge @ Current Density 40mA/cm2
Comparative example 1
The electrolyte of the battery is 2mol/LZnBr2+3mol/LKCl +0.8M MEP, positive end plate of single cell, positive 6x6cm2Graphite plate, positive electrode frame, carbon felt, diaphragm, carbon felt, negative electrode frame, negative electrode 6x6cm2Graphite plate, negative pole end plate. The positive electrolyte is sealed in a closed cavity surrounded by the positive electrode frame, the positive current collector (graphite plate) and the battery diaphragm, and does not flow. Charging and discharging current density of 40mA/cm2. The charging capacity is 40mAh/cm2. The battery is 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 (@ current density 40 mA/cm) is adopted for discharging2) The discharge was carried out by cutting off the voltage to 0.8V.
As can be seen from fig. 1, the stability of the stack is poor, the performance degradation of the stack is severe, the uniformity of the stack is poor, the cycle stability of the stack is relatively poor, and the life of the stack is short.
Example 1
The electrolyte of the battery is 2mol/LZnBr2+3mol/LKCl +0.8M MEP, positive end plate of single cell in sequence, positive 6x6cm2Graphite plate, positive electrode frame, carbon felt, diaphragm, carbon felt, negative electrode frame, negative electrode 6x6cm2Graphite plate, negative pole end plate. The anode electrolyte is sealed in the anode frame and anode current collectorThe body (graphite plate) and the battery diaphragm enclose a closed cavity, and the positive electrolyte does not flow. The charging and discharging current density is 40mA/cm2. The charging capacity is 40mAh/cm2。
The battery negative pole inlet passes through the negative pole electrolyte circulating pump and links to each other with the electrolyte storage tank through the pipeline, and the battery negative pole liquid outlet passes through the pipeline and links to each other with the electrolyte storage tank.
The positive electrode liquid inlet of the battery is connected with the electrolyte storage tank through a positive electrode electrolyte circulating pump through a pipeline, the positive electrode liquid outlet of the battery is connected with the electrolyte storage tank through a pipeline, pipeline valves are arranged at the positive electrode liquid inlet and the liquid outlet of the battery, when the battery runs, the valves at the positive electrode electrolyte inlet and outlet are closed, and when the batteries are mutually mixed and recovered, the positive electrode electrolyte liquid inlet valve is opened.
When the performance of the galvanic pile is obviously reduced (the coulombic efficiency is attenuated by more than 5%) in the running process of the galvanic pile, the galvanic pile is recovered by using the method disclosed by the invention, namely, the battery is completely discharged, 0.5mol/L hydrazine hydrate solution is used for dropwise adding 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 performance of the galvanic pile can be kept stable.
As can be seen from fig. 2, the cycle performance of the stack is stable, and compared with the stack without the additive, the cycle performance of the stack is greatly improved, and the life of the stack is also prolonged. The additive has excellent performance and obvious effect.
Comparative example 2
The electrolyte of the battery is 2mol/LZnBr2+3mol/LKCl +0.8M MEP, positive end plate of single cell, positive 6x6cm2Graphite plate, positive electrode frame, carbon felt, diaphragm, carbon felt, negative electrode frame, negative electrode 6x6cm2Graphite plate, negative pole end plate. The positive electrolyte is sealed in a closed cavity surrounded by the positive electrode frame, the positive current collector (graphite plate) and the battery diaphragm, and does not flow. Charging and discharging current density of 40mA/cm2. The charging capacity is 40mAh/cm2. The battery is 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 (@ current density 40 mA/cm) is adopted for discharging2) The discharge was carried out by a method of cutting off the voltage to 0.8V.
The battery negative pole inlet passes through the negative pole electrolyte circulating pump and links to each other with the electrolyte storage tank through the pipeline, and the battery negative pole liquid outlet passes through the pipeline and links to each other with the electrolyte storage tank.
The positive electrode liquid inlet of the battery is connected with the electrolyte storage tank through a positive electrode electrolyte circulating pump through a pipeline, the positive electrode liquid outlet of the battery is connected with the electrolyte storage tank through a pipeline, pipeline valves are arranged at the positive electrode liquid inlet and the liquid outlet of the battery, when the battery runs, the valves at the positive electrode electrolyte inlet and outlet are closed, and when the batteries are mutually mixed and recovered, the positive electrode electrolyte liquid inlet valve is opened.
When the electric pile runs to the 29 th cycle, the electric pile is recovered, after the electric pile is completely discharged, a positive electrolyte circulation valve is opened, the positive electrolyte in the positive electrode of the zinc-bromine single flow battery is led into an electrolyte storage tank, the electrolytes of the positive electrode and the negative electrode of the battery are mixed with each other, 50ml of formic acid solution with the mass fraction of 99% is added into the electrolyte, an electrolyte circulation pump is used for leading the electrolyte into a positive electrode cavity and a negative electrode cavity, and the electrolyte circularly flows in the positive electrode, the negative electrode and a liquid storage tank for more than 4 hours. And after the operation is finished, closing the anode electrolyte inlet valve and continuing to operate the galvanic pile.
Because of can't confirm the additive amount of formic acid, in this experiment, adopt excessive formic acid to resume electrolyte, this leads to electrolyte to resume the back that finishes, has partial formic acid to remain in the electrolyte, and in the charging process afterwards, formic acid in the electrolyte can react with the zinc simple substance that the negative pole generated, influences the pile performance (coulomb efficiency and descends), and the pile just resumes normally at the 4 th cycle performance after finishing resuming for the recovery process is too troublesome and the time is longer.
Example 2
The electrolyte of the battery is 2mol/LZnBr2+3mol/LKCl +0.8M MEP, positive end plate of single cell, positive 6x6cm2Graphite plate, positive electrode frame, carbon felt, diaphragm, carbon felt, negative electrode frame, negative electrode 6x6cm2Graphite plate, negative pole end plate. The positive electrolyte is sealed at the positive electrodeThe electrode frame, the positive electrode current collector (graphite plate) and the battery diaphragm are enclosed to form a closed cavity, and the positive electrolyte does not flow. Charging and discharging current density of 40mA/cm2. The charging capacity is 40mAh/cm2. The battery is 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 (@ current density 40 mA/cm) is adopted for discharging2) The discharge was carried out by a method of cutting off the voltage to 0.8V.
The battery negative pole inlet passes through the negative pole electrolyte circulating pump and links to each other with the electrolyte storage tank through the pipeline, and the battery negative pole liquid outlet passes through the pipeline and links to each other with the electrolyte storage tank.
The positive electrode liquid inlet of the battery is connected with the electrolyte storage tank through a positive electrode electrolyte circulating pump through a pipeline, the positive electrode liquid outlet of the battery is connected with the electrolyte storage tank through a pipeline, pipeline valves are arranged at the positive electrode liquid inlet and the liquid outlet of the battery, when the battery runs, the valves at the positive electrode electrolyte inlet and outlet are closed, and when the batteries are mutually mixed and recovered, the positive electrode electrolyte liquid inlet valve is opened.
When the electric pile runs to the 29 th cycle, the electric pile is recovered, after the electric pile is completely discharged, a positive electrolyte circulation valve is opened, the 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, hydrazine hydrate aqueous solution with the concentration of 0.5mol/L is dripped into the electrolyte, the electrolyte in the electrolyte storage tank is led into a chamber where the positive electrode and the negative electrode are positioned by a pump to flow while dripping, and the electrolyte in the electrolyte storage tank is stopped until the electrolyte in the electrolyte storage tank is colorless, so that the additive reacts with active substances accumulated on the positive electrode and the negative electrode. And after the operation is finished, closing the anode electrolyte inlet valve and continuing to operate the galvanic pile.
As can be seen from table 2, the stack was restored using the method in example 2, and the performance of the stack was rapidly restored during the charging process after the restoration (compared to comparative example 1). And the hydrazine compound has strong reducibility, reduces the residual bromine in the electrolyte by using a dripping mode, has short reaction time, can determine the dripping dosage according to the color of the electrolyte (from red to colorless), and avoids excessive dripping. Therefore, when the galvanic pile operates again, no redundant reducing additive exists in the electrolyte, the zinc elementary substance of the negative electrode of the galvanic pile cannot be consumed, and the performance of the galvanic pile can be recovered quickly (as can be seen from table 2, after the galvanic pile is recovered, the initial performance can be recovered by only two cycles). Compared with other additives, the additive used in the patent has higher recovery efficiency, more excellent performance and obvious effect. And the additive amount can be accurately controlled.
TABLE 1
Number of cycles of stack operation 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 cycles of stack operation CE/％ VE/％ EE/％
29 92 81 75
30 82 77 63
31 88 79 70
32 92 80 74
33 92 80 74

Claims (5)

1. A performance recovery method of a zinc bromine single flow battery comprises an electrolyte storage tank, wherein electrolyte in the electrolyte storage tank circularly flows in a chamber where a negative electrode of the zinc bromine single flow battery is located, and the method is characterized in that:
1) when the coulomb efficiency is reduced after the battery runs, the battery is completely discharged;
2) opening a valve of a positive electrolyte inlet and outlet, introducing the positive electrolyte in the positive electrode of the zinc-bromine single flow battery into an electrolyte storage tank, mixing the positive electrolyte and the negative electrolyte of the battery, dropwise adding one or more than two of hydrazine compounds such as hydrazine hydrate and hydrazine hydrochloride into the electrolyte storage tank, and introducing the electrolyte in the electrolyte storage tank into a chamber where the positive electrode and the negative electrode are positioned by a pump to flow while dropwise adding until the electrolyte in the electrolyte storage tank is colorless and stops; reacting the additive with the active material accumulated on the positive and negative electrodes;
3) and closing a valve of the positive electrolyte inlet and outlet to operate the zinc-bromine single flow battery.
2. The method of claim 1, wherein: the positive and negative electrolytes of the zinc-bromine single flow battery are neutral aqueous solutions containing zinc ions, the zinc and bromine raw materials are zinc bromide, the concentrations of the zinc ions in the positive and negative electrolytes of the battery are the same, the concentration of the supporting electrolyte KCl is the same, and the concentrations of the zinc ions in the electrolytes are as follows: 2-4mol/L and KCl concentration of 2-5 mol/L.
3. The method according to claim 1 or 2, wherein the negative electrode electrolyte in the electrolyte storage tank of the zinc-bromine single flow battery flows at one end of the negative electrode through a pump, and an ion exchange membrane is arranged between the positive electrode and the negative electrode; the battery negative electrode liquid inlet is connected with the electrolyte storage tank through a pump through a pipeline, and the battery negative electrode liquid outlet is connected with the electrolyte storage tank through a pipeline.
4. The method of claim 1, wherein: dropwise adding a solution into the electrolyte storage tank, wherein the solution is hydrazine hydrate liquid or hydrazine hydrate aqueous solution with the molar concentration of 0.5-1 mol/L, and the saturated hydrazine hydrochloride aqueous solution is 0.8-1.2 mol/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.
5. The method of claim 1, wherein the positive inlet of the battery is connected to the electrolyte tank via a pump via a pipeline, the positive outlet of the battery is connected to the electrolyte tank via a pipeline, pipeline valves are provided at the positive inlet and outlet of the battery, when the battery is in operation, the valves at the positive electrolyte inlet and outlet are closed, and when the battery is back-mixed, the positive electrolyte inlet valve is opened.
CN202011340256.9A 2020-11-25 2020-11-25 Performance recovery method of zinc-bromine single flow battery Active CN114551935B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202011340256.9A CN114551935B (en) 2020-11-25 2020-11-25 Performance recovery method of zinc-bromine single flow battery

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202011340256.9A CN114551935B (en) 2020-11-25 2020-11-25 Performance recovery method of zinc-bromine single flow battery

Publications (2)

Publication Number Publication Date
CN114551935A true CN114551935A (en) 2022-05-27
CN114551935B CN114551935B (en) 2023-09-15

Family

ID=81660178

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202011340256.9A Active CN114551935B (en) 2020-11-25 2020-11-25 Performance recovery method of zinc-bromine single flow battery

Country Status (1)

Country Link
CN (1) CN114551935B (en)

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

Also Published As

Publication number Publication date
CN114551935B (en) 2023-09-15

Similar Documents

Publication Publication Date Title
CN101572319B (en) Electrolyte for all-vanadium redox flow battery and preparation method thereof, and all-vanadium redox flow battery including the electrolyte
US20070072067A1 (en) Vanadium redox battery cell stack
CN103326055B (en) Zinc cathode electrolyte applied to redox battery
CN110416586B (en) Iron-based flow battery, positive and negative electrolyte thereof and preparation method
CN112786938B (en) Acid-base mixed high-voltage aqueous zinc battery and zinc flow battery with double dissolution deposition reaction
JP2018537838A (en) Regenerative fuel cell
CN108134120B (en) Zinc-bromine flow battery performance recovery method
CN107565151B (en) Regeneration method of electrode activity of all-vanadium redox flow battery
CN114551935B (en) Performance recovery method of zinc-bromine single flow battery
CN104300169A (en) Alkaline zinc vanadium flow battery
CN111244517B (en) Method for recovering performance of alkaline zinc-nickel flow battery
CN116231021A (en) Recovery method of zinc-bromine flow battery electrolyte
CN111193033B (en) Alkaline zinc-iron single flow battery
CN113067025B (en) Online recovery method for electrolyte of alkaline zinc-iron flow battery
CN114614038A (en) Zinc-bromine flow battery electrolyte and application thereof in zinc-bromine flow battery
CN110071317A (en) A kind of tin bromine flow battery
CN109950599A (en) Positive and negative anodes electrolyte and preparation method thereof and in A8It is applied in model flow battery
CN110010949A (en) Positive and negative anodes electrolyte and preparation method thereof and in A11It is applied in model flow battery
CN110010943A (en) Positive and negative anodes electrolyte and preparation method thereof and in A14It is applied in model flow battery
CN110010944A (en) Positive and negative anodes electrolyte and preparation method thereof and in A13It is applied in model flow battery
CN114551915B (en) Zinc-bromine single flow battery operation strategy
CN219435925U (en) Flow battery pack
CN113013460B (en) Negative electrolyte for alkaline zinc-iron flow battery and zinc-iron flow battery
CN116264309A (en) Alkaline zinc-iron single flow battery
CN118016944A (en) Water system iron-cerium flow battery

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant