CN106558722B - Device and method for realizing black start of zinc-bromine flow system battery - Google Patents

Device and method for realizing black start of zinc-bromine flow system battery Download PDF

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CN106558722B
CN106558722B CN201510616779.4A CN201510616779A CN106558722B CN 106558722 B CN106558722 B CN 106558722B CN 201510616779 A CN201510616779 A CN 201510616779A CN 106558722 B CN106558722 B CN 106558722B
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zinc
bromine
cathode
battery
tank
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CN106558722A (en
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赵乾乾
李如春
徐进亮
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TBEA Shenyang Transformer Group Co Ltd
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    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00Fuel cells; Manufacture thereof
    • H01M8/18Regenerative fuel cells, e.g. redox flow batteries or secondary fuel cells
    • H01M8/184Regeneration by electrochemical means
    • H01M8/188Regeneration by electrochemical means by recharging of redox couples containing fluids; Redox flow type batteries
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00Fuel cells; Manufacture thereof
    • H01M8/04Auxiliary arrangements, e.g. for control of pressure or for circulation of fluids
    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02EREDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30Hydrogen technology
    • Y02E60/50Fuel cells

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  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Sustainable Development (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 belongs to the technical field of zinc-bromine flow batteries, and particularly relates to a device and a method for realizing black start of a zinc-bromine flow system battery. The device comprises a zinc-bromine battery pile, an anode starting tank and a cathode starting tank, wherein the anode starting tank and the cathode starting tank are arranged above the zinc-bromine battery pile, the bottom of the anode starting tank is communicated with an S4 interface of the zinc-bromine battery pile through an electromagnetic valve a, and the bottom of the cathode starting tank is communicated with an S1 interface of the zinc-bromine battery pile through a mixing valve and an electromagnetic valve b in sequence; the active complex in the cathode starting tank flows out from the bottom under the action of gravity and enters into the zinc-bromine battery pile, and reacts with electrolyte from the anode starting tank to discharge in the zinc-bromine battery pile, so that the black start of the zinc-bromine flow system battery is realized. The self-starting method of the zinc-bromine flow battery system is realized under the condition of no external power supply.

Description

Device and method for realizing black start of zinc-bromine flow system battery
Technical Field
The invention belongs to the technical field of zinc-bromine flow batteries, and particularly relates to a device and a method for realizing black start of a zinc-bromine flow system battery.
Background
In the prior art, the zinc-bromine flow battery can overcome the influence of the lead-acid battery on the environment, meanwhile, the possibility of explosion of the battery body is radically eradicated due to the separation of an active material reaction place and a reaction place, and the zinc-bromine flow battery has the advantages of long cycle life, high electric energy density, small volume, low cost, environmental friendliness and the like, is promoted by energy storage requirements in recent years, and is increasingly valued. However, the current zinc-bromine flow battery technology is not mature enough and has a plurality of problems.
The zinc-bromine flow battery system and other non-flow battery systems are most remarkable in that the zinc-bromine battery needs to circularly power a liquid path system by a magnetic pump. Once the system is powered off and stopped, the magnetic pump cannot work and the liquid circuit circulation cannot be recovered, so that the zinc-bromine battery system cannot be started (namely cannot be started in black). Black start is an important indicator for measuring the reliability of a battery system
Disclosure of Invention
In order to overcome the defects in the prior art, the invention aims to provide a device and a method for realizing black start of a zinc-bromine flow system battery.
In order to achieve the above purpose, the present invention adopts the following technical scheme:
the device for realizing black start of the zinc-bromine flow system battery comprises a zinc-bromine battery pile, an anode starting tank and a cathode starting tank, wherein the upper part of the zinc-bromine battery pile is provided with an S1 interface and an S3 interface, the lower part of the zinc-bromine battery pile is provided with an S2 interface and an S4 interface, the S1 interface and the S2 interface are connected with a cathode circulating system, the S3 interface and the S4 interface are connected with the anode circulating system, the anode starting tank and the cathode starting tank are arranged above the zinc-bromine battery pile, the bottom of the anode starting tank is communicated with the S4 interface of the zinc-bromine battery pile through an electromagnetic valve a, the bottom of the cathode starting tank is communicated with the S1 interface of the zinc-bromine battery pile through a mixing valve and an electromagnetic valve b in sequence, and the mixing valve is simultaneously communicated with the upper part of the cathode starting tank; and in the power-off state of the zinc-bromine liquid flow system, opening an electromagnetic valve a and an electromagnetic valve b, wherein an active complex in the cathode starting tank flows out from the bottom under the action of gravity, is mixed with upper electrolyte in a mixing valve, enters a zinc-bromine battery pile through the electromagnetic valve b, and reacts with the electrolyte from the anode starting tank in the zinc-bromine battery pile for discharging, so that the black start of the zinc-bromine liquid flow system battery is realized.
And a one-way valve d is further arranged on a pipeline between the electromagnetic valve b and the S1 interface of the zinc-bromine battery pile.
The bottoms of the cathode starting tank and the anode starting tank are more than or equal to 2.8m from the center of the zinc-bromine battery pile so as to ensure that enough circulation pressure difference exists in the zinc-bromine battery pile.
The cathode circulation system comprises a first magnetic pump and a cathode liquid storage tank, wherein a suction inlet of the first magnetic pump is respectively communicated with the upper part and the bottom of the cathode liquid storage tank through a first ball valve and a second ball valve, an outlet of the first magnetic pump is communicated with an S2 interface of a zinc-bromine battery pile, and an S1 interface of the zinc-bromine battery pile is communicated with the cathode liquid storage tank; the anode circulation system comprises a second magnetic pump and an anode liquid storage tank, wherein a suction inlet of the second magnetic pump is communicated with the bottom of the anode liquid storage tank through a third ball valve, and an outlet of the second magnetic pump is communicated with an S4 interface of the zinc-bromine battery pile.
The cathode circulation system further comprises a one-way valve a and a four-way valve, an outlet of the first magnetic pump is connected with an L interface of the four-way valve through the one-way valve a, U, D interfaces of the four-way valve are respectively communicated with an S1 interface and an S2 interface of the zinc-bromine battery pile, an R interface of the four-way valve is communicated with the cathode liquid storage tank, and flow direction switching is achieved through the four-way valve.
The cathode starting tank is further communicated with the outlet of the first magnetic pump through a one-way valve c, and the anode starting tank is further communicated with the outlet of the second magnetic pump through a one-way valve b.
The outlet of the first magnetic pump is further connected with a three-way valve, and the three-way valve is respectively connected with the one-way valve c and the one-way valve a.
The upper part of the cathode starting tank is provided with a vent K1, and the vent K1 is communicated with the top of the cathode liquid storage tank; and the upper part of the anode starting tank is provided with a vent K2, and the vent K2 is communicated with the top of the anode liquid storage tank.
A method for realizing black start of a zinc-bromine flow system battery by using the device comprises the steps that when a circulating system of the zinc-bromine flow system battery is powered off, an electromagnetic valve a and an electromagnetic valve b are automatically opened, active complex in a cathode starting tank flows out from the bottom under the action of gravity and is mixed with upper electrolyte in a mixing valve, then enters a zinc-bromine battery stack through the electromagnetic valve b and a one-way valve d, reacts with electrolyte from an anode starting tank in the zinc-bromine battery stack for discharging, and then supplies power for the circulating system of the zinc-bromine flow system battery after conversion; after the circulating system of the zinc bromine flow system battery works stably, the electromagnetic valve a and the electromagnetic valve b are closed.
The active complex in the cathode starting tank is provided by a cathode circulation system of the zinc-bromine flow system battery, and the electrolyte in the anode starting tank is provided by an anode circulation system of the zinc-bromine flow system battery.
The invention has the advantages and beneficial effects that:
according to the invention, under the condition of no external power supply, active substances are sent into the electric pile under the action of electrolyte gravity, the reaction is discharged, and the magnetic pump is started, so that the self-starting of the zinc-bromine flow battery system is realized. The invention is safe, stable and simple, and does not need a standby power supply.
Drawings
Fig. 1 is a schematic structural view of the present invention.
Wherein: 1 is a first magnetic pump, 2 is a three-way valve, 3 is a one-way valve a,4 is a four-way valve, 5 is a zinc bromine battery stack, 6 is a cathode liquid storage tank, 7 is a first ball valve, 8 is a second ball valve, 9 is a third ball valve, 10 is a second magnetic pump, 11 is a one-way valve b,12 is an anode liquid storage tank, 13 is a solenoid valve a,14 is an anode starting tank, 15 is a cathode starting tank, 16 is a mixing valve, 17 is a solenoid valve b,18 is a one-way valve c, and 19 is a one-way valve d.
Detailed Description
The present invention will be described in further detail with reference to the accompanying drawings.
As shown in FIG. 1, the device for realizing black start of a zinc-bromine flow system battery provided by the invention comprises a zinc-bromine battery stack 5, an anode start tank 14 and a cathode start tank 15, wherein the upper part of the zinc-bromine battery stack 5 is provided with S1 and S3 interfaces, the lower part is provided with S2 and S4 interfaces, the S1 and S2 interfaces are connected with a cathode circulation system, and the S3 and S4 interfaces are connected with the anode circulation system. The anode starting tank 14 and the cathode starting tank 15 are arranged above the zinc-bromine battery pile 5, and the bottom of the anode starting tank 14 is communicated with an S4 interface of the zinc-bromine battery pile 5 through an electromagnetic valve a 13. The bottom of the cathode starting tank 15 is communicated with an S1 interface of the zinc-bromine battery stack 5 sequentially through a mixing valve 16 and an electromagnetic valve b17, and the mixing valve 16 is simultaneously communicated with the upper part of the cathode starting tank 15; in the power-off state of the zinc-bromine liquid flow system, the electromagnetic valve a13 and the electromagnetic valve b17 are opened, the active complex in the cathode starting tank 15 flows out from the bottom under the action of gravity and is mixed with the upper electrolyte in the mixing valve 16, then enters the zinc-bromine battery stack 5 through the electromagnetic valve b17, and reacts with the electrolyte from the anode starting tank 14 in the zinc-bromine battery stack 5 to discharge, so that the black start of the zinc-bromine liquid flow system battery is realized.
And a one-way valve d19 is further arranged on a pipeline between the electromagnetic valve b17 and the S1 interface of the zinc-bromine battery stack 5. The height H of the bottoms of the cathode start-up tank 15 and the anode start-up tank 14 from the center of the zinc-bromine battery cell stack 5 is not less than (i.e., not less than) 2.8m to ensure a sufficient circulation pressure difference in the zinc-bromine battery cell stack 5.
The cathode circulation system comprises a first magnetic pump 1 and a cathode liquid storage tank 6, wherein the suction inlet of the first magnetic pump 1 is respectively communicated with the upper part and the bottom of the cathode liquid storage tank 6 through a first ball valve 7 and a second ball valve 8, the outlet of the first magnetic pump 1 is communicated with the S2 interface of the zinc-bromine battery stack 5, and the S1 interface of the zinc-bromine battery stack 5 is communicated with the cathode liquid storage tank 6; the anode circulation system comprises a second magnetic pump 10 and an anode liquid storage tank 12, wherein a suction inlet of the second magnetic pump 10 is communicated with the bottom of the anode liquid storage tank 12 through a third ball valve 9, and an outlet of the second magnetic pump 10 is communicated with an S4 interface of the zinc-bromine battery pile 5.
The cathode circulation system further comprises a one-way valve a3 and a four-way valve 4, an outlet of the first magnetic pump 1 is connected with an L interface of the four-way valve 4 through the one-way valve a3, U, D interfaces of the four-way valve 4 are respectively communicated with an S1 interface and an S2 interface of the zinc-bromine battery pile 5, an R interface of the four-way valve 4 is communicated with the cathode liquid storage tank 6, and flow direction switching is achieved through the four-way valve 4.
The cathode starting tank 15 is further communicated with the outlet of the first magnetic pump 1 through a one-way valve c18, the outlet of the first magnetic pump 1 is further communicated with an A interface of the three-way valve 2, a B, C interface of the three-way valve 2 is respectively connected with the one-way valve c18 and the one-way valve a3, and the operation of a cathode circulation system and the feeding operation of the cathode starting tank 15 are switched through the three-way valve 2. The anode starting tank 14 is further communicated with the outlet of the second magnetic pump 10 through a one-way valve b11, namely, the outlet electrolyte of the second magnetic pump 10 is divided into two paths after passing through the one-way valve b11, one path directly enters an S4 interface of the zinc-bromine battery stack 5, and the other path enters the anode starting tank 14 through an electromagnetic valve a 13.
The upper part of the cathode starting tank 15 is provided with a vent K1, and the vent K1 is communicated with the top of the cathode liquid storage tank 6; the upper part of the anode starting tank 14 is provided with a vent K2, and the vent K2 is communicated with the top of the anode liquid storage tank 12. The air vents K1 and K2 at the upper parts of the cathode starting tank 15 and the anode starting tank 14 can recycle excessive electrolyte in the starting tank (the cathode starting tank 15 or the anode starting tank 14) into the liquid storage tank (the cathode liquid storage tank 6 or the anode liquid storage tank 12) in addition to the air vents, so as to maintain the liquid level balance in the starting tank.
The method for realizing black start of the zinc-bromine flow system battery by the device comprises the following steps:
when the circulation system of the zinc-bromine flow system battery is powered off and stops working, the electromagnetic valve a13 and the electromagnetic valve b17 are automatically opened, active complex in the cathode starting tank 15 flows out from the bottom under the action of gravity, is mixed with upper electrolyte in the mixing valve 16, enters the zinc-bromine battery stack 5 through the electromagnetic valve b17 and the one-way valve d19, reacts with electrolyte from the anode starting tank 14 in the zinc-bromine battery stack 5 for discharging, and is converted by the converter to supply power for the circulation system of the zinc-bromine flow system battery; after the circulating system of the zinc-bromine flow system battery stably works, the electromagnetic valve a13 and the electromagnetic valve b17 are closed.
The active complex in the cathode start-up tank 15 is provided by the cathode circulation system of the zinc-bromine flow system battery, and the electrolyte in the anode start-up tank 14 is provided by the anode circulation system of the zinc-bromine flow system battery.
According to the invention, under the condition of no external power supply, active substances are sent into the electric pile under the action of electrolyte gravity, the reaction is discharged, and the magnetic pump is started, so that the self-starting of the zinc-bromine flow battery system is realized. The invention is safe, stable and simple, and does not need a standby power supply.
The working principle of the invention is as follows:
during charge-discharge circulation, the first magnetic pump 1 and the second magnetic pump 10 are started under the action of an external power supply, the electromagnetic valve a13 and the electromagnetic valve b17 are electrified to be normally closed, and the AC flow direction of the three-way valve 2 is conducted. Electrolyte in the cathode liquid storage tank 6 enters the zinc-bromine battery pile 5 through the first magnetic pump 1 and the four-way valve 4; meanwhile, electrolyte in the anode liquid storage tank 12 enters the zinc-bromine battery pile 5 through the second magnetic pump 10 and the one-way valve b11, the two electrolytes perform charge and discharge reactions in the zinc-bromine battery pile 5, and after the reactions, catholyte flows back into the cathode liquid storage tank 6, and anolyte flows back into the anode liquid storage tank 12.
After the battery is charged, the three-way valve 2 is switched, the AB flow direction of the three-way valve 2 is conducted, the electromagnetic valve a13 and the electromagnetic valve b17 are opened, part of active complex in the cathode liquid storage tank 6 is respectively conveyed into the cathode starting tank 15, and anolyte in the anode liquid storage tank 12 is conveyed into the anode starting tank 14. After the operation is completed, the three-way valve 2, the electromagnetic valve a13 and the electromagnetic valve b17 are reset, and the system enters a black start preparation state.
After the zinc-bromine flow battery system is in power-off shutdown, the first magnetic pump 1 and the second magnetic pump 10 are in power-off shutdown, the electromagnetic valve a13 and the electromagnetic valve b17 are automatically opened, active complex in the cathode starting tank 15 flows out from the bottom under the action of gravity, and enters the zinc-bromine battery stack 5 through the electromagnetic valve b17 and the one-way valve d19 after being mixed with upper electrolyte in the mixing valve 16, and is in reaction discharge with electrolyte from the anode starting tank 14 in the zinc-bromine battery stack 5, and after being converted by the converter, the first magnetic pump 1 and the second magnetic pump 10 are powered, the started first magnetic pump 1 and the started second magnetic pump 10 start the circulation of a cathode circulation system and an anode circulation system of the battery system, and the zinc-bromine battery stack 5 starts to discharge steadily to the outside. After the zinc bromine flow battery system is circularly stable, the electromagnetic valve a13 and the electromagnetic valve b17 are closed.
In the zinc-bromine flow battery system, the height H from the bottoms of a cathode starting tank 15 and an anode starting tank 14 to the center of the zinc-bromine battery pile 5 is not less than 2.8m so as to ensure that enough circulation pressure difference exists in the zinc-bromine battery pile 5. The one-way valve a3 in the zinc-bromine flow battery system is used for preventing electrolyte in the cathode starting tank 15 from flowing back into the first magnetic pump 1. The check valve b11 in the system is used for preventing the electrolyte in the anode starting tank 14 from flowing back into the second magnetic pump 10. The function of the mixing valve 16 in the system is to mix the active complex at the bottom of the cathode start-up tank 15 with the electrolyte at the upper part to form a low concentration mixture to enhance the fluidity of the active substance and to enhance the uniform distribution of the active complex in the zinc-bromine battery stack 5.
In summary, the invention can send active substances into the zinc-bromine battery stack under the action of electrolyte gravity without external power supply, and perform reaction discharge, and start the magnetic pump to realize self-starting of the zinc-bromine flow battery system.

Claims (8)

1. The device for realizing black start of the zinc-bromine flow system battery is characterized by comprising a zinc-bromine battery pile (5), an anode starting tank (14) and a cathode starting tank (15), wherein the upper part of the zinc-bromine battery pile (5) is provided with S1 and S3 interfaces, the lower part of the zinc-bromine battery pile is provided with S2 and S4 interfaces, the S1 and S2 interfaces are connected with a cathode circulation system, the S3 and S4 interfaces are connected with the anode circulation system, the anode starting tank (14) and the cathode starting tank (15) are arranged above the zinc-bromine battery pile (5), the bottom of the anode starting tank (14) is communicated with the S4 interface of the zinc-bromine battery pile (5) through an electromagnetic valve a (13), the bottom of the cathode starting tank (15) is communicated with the S1 interface of the zinc-bromine battery pile (5) through a mixing valve (16) and an electromagnetic valve b (17), and the mixing valve (16) is simultaneously communicated with the upper part of the cathode starting tank (15); under the power-off state of the zinc-bromine liquid flow system, opening an electromagnetic valve a (13) and an electromagnetic valve b (17), wherein an active complex in the cathode starting tank (15) flows out from the bottom under the action of gravity, is mixed with an upper electrolyte in a mixing valve (16), enters a zinc-bromine battery stack (5) through the electromagnetic valve b (17), and reacts with the electrolyte from the anode starting tank (14) in the zinc-bromine battery stack (5) for discharging, so that the black start of the zinc-bromine liquid flow system battery is realized;
a one-way valve d (19) is further arranged on a pipeline between the electromagnetic valve b (17) and the S1 interface of the zinc-bromine battery stack (5);
the cathode circulation system comprises a first magnetic pump (1) and a cathode liquid storage tank (6), wherein a suction inlet of the first magnetic pump (1) is respectively communicated with the upper part and the bottom of the cathode liquid storage tank (6) through a first ball valve (7) and a second ball valve (8), an outlet of the first magnetic pump (1) is communicated with an S2 interface of a zinc-bromine battery electric pile (5), and an S1 interface of the zinc-bromine battery electric pile (5) is communicated with the cathode liquid storage tank (6);
the anode circulation system comprises a second magnetic pump (10) and an anode liquid storage tank (12), wherein a suction inlet of the second magnetic pump (10) is communicated with the bottom of the anode liquid storage tank (12) through a third ball valve (9), and an outlet of the second magnetic pump (10) is communicated with an S4 interface of the zinc-bromine battery pile (5).
2. The device for realizing black start of a zinc-bromine flow system battery according to claim 1, wherein the bottoms of the cathode start-up tank (15) and the anode start-up tank (14) are at least 2.8m from the center of the zinc-bromine battery stack (5) to ensure a sufficient circulation pressure difference in the zinc-bromine battery stack (5).
3. The device for realizing black start of a zinc-bromine flow system battery according to claim 1, wherein the cathode circulation system further comprises a one-way valve a (3) and a four-way valve (4), an outlet of the first magnetic pump (1) is connected with an L interface of the four-way valve (4) through the one-way valve a (3), U, D interfaces of the four-way valve (4) are respectively communicated with an S1 interface and an S2 interface of a zinc-bromine battery electric pile (5), an R interface of the four-way valve (4) is communicated with the cathode liquid storage tank (6), and flow direction switching is realized through the four-way valve (4).
4. A device for realizing black start of a zinc bromine flow system battery according to claim 3, wherein the cathode start-up tank (15) is further communicated with the outlet of the first magnetic pump (1) through a one-way valve c (18), and the anode start-up tank (14) is further communicated with the outlet of the second magnetic pump (10) through a one-way valve b (11).
5. The device for realizing black start of a zinc bromine flow system battery according to claim 4, wherein the outlet of the first magnetic pump (1) is further connected with a three-way valve (2), and the three-way valve (2) is respectively connected with the one-way valve c (18) and the one-way valve a (3).
6. The device for realizing the black start of the zinc-bromine flow system battery according to claim 1, wherein a vent K1 is arranged at the upper part of the cathode starting tank (15), and the vent K1 is communicated with the top of the cathode liquid storage tank (6); the upper part of the anode starting tank (14) is provided with a vent K2, and the vent K2 is communicated with the top of the anode liquid storage tank (12).
7. A method for realizing black start of a zinc-bromine flow system battery by using the device of any one of claims 1-6, characterized in that when a circulation system of the zinc-bromine flow system battery is powered off, the electromagnetic valve a (13) and the electromagnetic valve b (17) are automatically opened, active complex in a cathode starting tank (15) flows out from the bottom under the action of gravity and is mixed with upper electrolyte in a mixing valve (16), enters a zinc-bromine battery stack (5) through the electromagnetic valve b (17) and a one-way valve d (19), reacts with electrolyte from an anode starting tank (14) in the zinc-bromine battery stack (5), and then supplies power to the circulation system of the zinc-bromine flow system battery after conversion; after the circulating system of the zinc bromine flow system battery works stably, the electromagnetic valve a (13) and the electromagnetic valve b (17) are closed.
8. The method of claim 7, wherein the active complex in said cathode start-up tank (15) is provided by a cathode circulation system of said zinc-bromine flow system battery and the electrolyte in said anode start-up tank (14) is provided by an anode circulation system of said zinc-bromine flow system battery.
CN201510616779.4A 2015-09-23 2015-09-23 Device and method for realizing black start of zinc-bromine flow system battery Active CN106558722B (en)

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CN116885237A (en) * 2023-01-31 2023-10-13 安徽海螺融华储能科技有限公司 Operation method of gravity potential energy and heat energy integrated recovery device of all-vanadium redox flow battery

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