WO2017065575A1 - Procédé permettant d'empêcher l'endommagement d'un empilement de batterie à flux redox - Google Patents

Procédé permettant d'empêcher l'endommagement d'un empilement de batterie à flux redox Download PDF

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Publication number
WO2017065575A1
WO2017065575A1 PCT/KR2016/011590 KR2016011590W WO2017065575A1 WO 2017065575 A1 WO2017065575 A1 WO 2017065575A1 KR 2016011590 W KR2016011590 W KR 2016011590W WO 2017065575 A1 WO2017065575 A1 WO 2017065575A1
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WO
WIPO (PCT)
Prior art keywords
electrolyte
stack
cathode
anode
redox flow
Prior art date
Application number
PCT/KR2016/011590
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English (en)
Korean (ko)
Inventor
이남진
김수환
김병철
김태윤
박상은
함성식
Original Assignee
오씨아이 주식회사
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Application filed by 오씨아이 주식회사 filed Critical 오씨아이 주식회사
Publication of WO2017065575A1 publication Critical patent/WO2017065575A1/fr

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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
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/70—Arrangements for stirring or circulating the electrolyte
    • H01M50/77—Arrangements for stirring or circulating the electrolyte with external circulating path
    • 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
    • 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
    • H01M8/04298—Processes for controlling fuel cells or fuel cell systems
    • H01M8/04313—Processes for controlling fuel cells or fuel cell systems characterised by the detection or assessment of variables; characterised by the detection or assessment of failure or abnormal function
    • H01M8/04664—Failure or abnormal function
    • 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
    • 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
    • Y02E60/10—Energy storage using batteries
    • 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

Definitions

  • the present invention relates to a stack damage prevention method of a redox flow battery, and more particularly, to a method for storing the stack without damaging the electrolyte solution.
  • a redox flow battery is a device that converts chemical energy of an electrolyte into electrical energy through a battery cell.
  • FIG. 1 is a schematic diagram showing the configuration of a redox flow battery.
  • the redox flow battery stores the positive electrolyte in the positive electrolyte storage tank 110 and the negative electrolyte in the negative electrolyte tank 112.
  • the anode electrolyte storage tank 110 and the cathode electrolyte tank 112 are stored in the anode cell 102A and the cathode cell 102B of the cell 102 through the anode electrolyte and the cathode electrolyte pump 114 and 116, respectively.
  • the movement of electrons through the electrode 106 occurs according to the operation of the power supply / load 118, and thus an oxidation / reduction reaction occurs.
  • the cathode cell 102B the movement of electrons through the electrode 108 occurs according to the operation of the power source / load 118, and thus an oxidation / reduction reaction occurs.
  • the anode electrolyte and the cathode electrolyte are circulated to the cathode electrolyte storage tank 110 and the cathode electrolyte storage tank 112.
  • the anode cell 102A and the cathode cell 102B are separated by an ion exchange membrane 104 through which ions can pass.
  • a movement of ions that is, crossover, may occur between the anode cell 102A and the cathode cell 102B. That is, during the charge / discharge process of the redox flow battery, the anolyte ions of the anode cell 102A may move to the cathode cell 102B, and the catholyte ions of the cathode cell 102B may move to the cathode cell 102A.
  • the operating voltage of the battery cell has a relatively low voltage, such as 1.0 ⁇ 1.7V. Therefore, the stack is formed by stacking cells in series to increase the operating voltage.
  • the stack has a structure in which a plurality of battery cells are electrically connected in series and share electrolytes in parallel.
  • Redox flow batteries are often used as high-capacity power supplies and are installed by manufacturing individual components and then assembling the individual components at the installation site.
  • the most important configuration of the components of a redox flow battery is a stack formed by stacking battery cells.
  • the stack is manufactured by the manufacturer and then subjected to performance tests and then transported and installed to the installation site.
  • the performance test of the stack includes an electrolyte leak test and a charge / discharge performance test.
  • the performance test of the stack is performed by filling the positive and negative electrolytes in the stack.
  • the present invention is to provide a method capable of preventing damage to the stack filled with the positive and negative electrolyte.
  • An object of the present invention is to provide a method for preventing stack damage of a redox flow battery, in which the filled electrolyte is not leaked or exposed to the atmosphere in storing the stack filled with the electrolyte.
  • Another object of the present invention is to provide a method for preventing stack damage of a redox flow battery, which allows an uneven pressure generated through diffusion of an electrolyte through an ion exchange membrane during storage of a stack to be eliminated.
  • Still another object of the present invention is to provide a method for preventing stack damage of a redox flow battery, which can be stored for a long time in a state where an electrolyte is filled and prevents the stack from being damaged during storage.
  • the present invention relates to a stack damage prevention method of a redox flow battery including a cathode electrolyte inlet, an anode electrolyte outlet, an anode electrolyte inlet, and an anode electrolyte outlet, in which a cathode electrolyte and an anode electrolyte are filled in the stack. And a cathode selected from the anode electrolyte inlet or the anode electrolyte outlet and one selected from the cathode electrolyte inlet or the anode electrolyte outlet through an equalizing tube so that the anode cell and the cathode cell in the stack can communicate with the equalizing tube.
  • a method of preventing stack damage of a redox flow battery is provided.
  • the inlet or outlet that is not connected to the equalizing tube is closed.
  • the inlet or outlet that is not connected to the equalizing pipe may be connected to the secondary equalizing pipe.
  • the equalizing tube is preferably made of a transparent or translucent material so as to check the liquid level inside.
  • the on / off valves are provided at the anode electrolyte inlet, the anode electrolyte outlet, the cathode electrolyte inlet, and the cathode electrolyte outlet, respectively, and the open / close valve connected to the equalizing pipe is opened, and the open / close valve is not connected to the equalizing pipe. It is desirable to close.
  • the stack damage prevention method of the redox flow battery according to the present invention has an effect of solving the problem of precipitation of the electrolyte solution by preventing the electrolyte solution from being exposed to the atmosphere while the electrolyte is filled.
  • the stack damage prevention method of the redox flow battery according to the present invention has the effect of preventing the electrolyte filled inside the stack from flowing out during storage or transport.
  • the stack damage prevention method of the redox flow battery according to the present invention has the effect of preventing damage to the ion exchange membrane or gasket in the stack during storage by solving the problem of pressure imbalance caused by the electrolyte diffused through the ion exchange membrane. Bring it.
  • FIG. 1 is a schematic diagram showing the configuration of a redox flow battery.
  • FIG. 2 illustrates a stack of redox flow cells.
  • FIG 3 is a view showing a state in which the on-off valve of the stack of the redox flow battery is attached.
  • FIG. 4 is a view showing a stack damage prevention method of a redox flow battery according to a first embodiment of the present invention.
  • FIG. 5 is a view showing a stack damage prevention method of a redox flow battery according to a second embodiment of the present invention.
  • FIG. 6 is a view showing a stack damage prevention method of a redox flow battery according to a third embodiment of the present invention.
  • FIG. 7 is a view showing a stack damage prevention method of a redox flow battery according to a fourth embodiment of the present invention.
  • FIG 8 and 9 are photographs showing the storage state of the stack using the stack damage prevention method of the redox flow battery according to the present invention.
  • anode electrolyte storage tank 112 cathode electrolyte storage tank
  • anode electrolyte inlet 212 anode electrolyte outlet
  • cathode electrolyte inlet 222 cathode electrolyte outlet
  • auxiliary equalizing tube 270 stopper
  • Redox flow battery system is a system for storing electricity by flowing the electrolyte stored in the electrolyte tank to flow into / out of the stack capable of electrically charging / discharging.
  • the stack that is charged and discharged is assembled to the system after assembling the stack, performing basic performance evaluation and screening tests.
  • Screening tests to assess the basic performance of the stack and to identify initial failures are carried out by installing the stack in the evaluation equipment and then introducing and discharging electrolyte into the stack.
  • the stack After evaluation, the stack is stored after disassembly from the evaluation equipment and before installation in a redox flow cell system.
  • it is difficult to completely discharge the electrolyte filled in the stack from the stack, and the electrolyte must be injected again at the time of installation, so it is advantageous to store the electrolyte without discharging the electrolyte.
  • the electrolyte has a strong acidity, and if it is leaked to the outside, it may harm the worker's body and cause a safety accident.When the electrolyte is exposed to the air due to the reactivity of the electrolyte, it may cause problems such as oxidation or precipitation of the electrolyte. do.
  • the electrolyte oil inlet / outlet of the stack was simply sealed.
  • some ions move through the ion exchange membrane, causing a difference in the pressure between the anode and cathode cells in the stack. If a pressure difference occurs between the anode cell and the cathode cell, the ion exchange membrane or the bipolar plate in between may be damaged, and if the pressure is excessively greater than the operating pressure, the stack structure may be affected by affecting the stack structure. It can also cause permanent damage.
  • the present invention proposes a method for preventing damage to the stack by storing the stack so that the electrolyte solution inside the stack does not leak out, but does not generate a pressure difference due to the movement of ions between the anode and cathode cells.
  • FIG. 2 illustrates a stack of redox flow cells.
  • the stack 200 of the redox flow battery has a positive electrolyte inlet 210 to allow the positive electrolyte to flow into the stack, and a positive electrolyte outlet 212 to discharge the positive electrolyte from the stack, into the stack.
  • the anode electrolyte and the cathode electrolyte are not mixed with each other and flow into the anode cell and the cathode cell, respectively, and flow to both sides of the ion exchange membrane.
  • the stack 200 is formed by stacking a plurality of cells with a bipolar plate interposed therebetween, whereby a positive electrode cell and a negative electrode cell are formed on both sides of the bipolar plate.
  • FIG 3 is a view showing a state in which the on-off valve of the stack of the redox flow battery is attached.
  • the electrolyte inlet and the outlet of the stack are connected to the electrolyte tank through a pipe.
  • the electrolyte inlets 210, 212, 220 and 222 of the stack are preferably provided with opening and closing valves 211, 213, 221 and 223, respectively. .
  • the on-off valves 211, 213, 221, 223 are not provided, the electrolyte inside the pipe is leaked to the outside when separated from the pipe in the stack 200, so that the on / off valve is provided to prevent this.
  • the assembled stack is connected to the evaluation apparatus, and electrolyte is injected to perform the performance evaluation of the stack.
  • electrolyte is injected to perform the performance evaluation of the stack.
  • all the closing valves are closed and separated.
  • the stack is sealed while the electrolyte is filled inside the stack.
  • the pressure of the anode cell is lowered and the pressure of the cathode cell is increased.
  • This pressure inequality may cause damage to the ion exchange membrane located between the anode cell and the cathode cell, and may cause damage to the airtight structure that prevents the outflow of the electrolyte when an excessive pressure difference occurs.
  • FIG. 4 is a view showing a stack damage prevention method of a redox flow battery according to a first embodiment of the present invention.
  • the stack damage prevention method of the redox flow battery according to the first embodiment of the present invention is to alleviate the pressure difference generated between the anode cell and the cathode cell in a state where the cathode electrolyte and the cathode electrolyte are filled in the stack. Each electrolyte is allowed to move or the pressure is evenly distributed.
  • one selected from the positive electrolyte inlet or the positive electrolyte outlet and one selected from the negative electrolyte inlet or the negative electrolyte outlet are connected to the equalizing tube, so that the negative cell and the positive electrode in the stack communicate with the equalizing tube 250. By doing so, the pressures of the anode and cathode cells are made uniform.
  • the equalizing tube 250 is preferably formed of a material having acid resistance to the electrolyte, and more preferably formed of a transparent or translucent material so as to check the level of the electrolyte in the equalizing tube 250.
  • the equalizing pipe 250 may be configured in the form of a rigid pipe or may be configured in the form of a soft hose.
  • the equalizing tube 250 shows the form of connecting the positive electrolyte inlet 210 and the negative electrolyte outlet 222. It is only necessary to connect the equalizing tube 250 so that the anode cell and the cathode cell communicate with each other, and may connect the anode electrolyte outlet 212 and the cathode electrolyte inlet 220, and the anode electrolyte outlet 212 and the cathode electrolyte outlet ( 222 may be connected, or the anode electrolyte inlet 210 and the cathode electrolyte inlet 220 may be connected.
  • the inlet or the outlet connected to the equalizing tube should connect different electrolytes, and if the same electrolytes are connected, the pressure difference generated between the ion exchange membranes cannot be alleviated.
  • the inlets or outlets 212 and 220 which are not connected close the on / off valves 213 and 221 so that the internal electrolyte of the stack does not flow out.
  • FIG. 5 is a view showing a stack damage prevention method of a redox flow battery according to a second embodiment of the present invention.
  • the remaining inlet or It is characterized in that the outlet connected to the secondary equalizing pipe (260).
  • the equalizing pipe 250 and the auxiliary equalizing pipe 260 perform the same function and have the same configuration.
  • the damage prevention method as in the second embodiment is characterized in that the anode cell and the cathode cell are connected by two equalizing tubes, so that the pressure of the anode cell and the cathode cell can be maintained more evenly.
  • FIG. 6 is a view showing a stack damage prevention method of a redox flow battery according to a third embodiment of the present invention
  • Figure 7 is a view showing a stack damage prevention method of a redox flow battery according to a fourth embodiment of the present invention. to be.
  • FIG. 6 and 7 illustrate a state in which the stack damage prevention method according to the present invention is applied to a type in which an on / off valve is not provided in the stack 200 of the fuel cell.
  • FIG. 6 illustrates a method using an equalizing tube 250 and a stopper
  • FIG. 7 illustrates a method using an equalizing tube 250 and an auxiliary equalizing tube 260.
  • an equalizing tube 250 connects an anode electrolyte inlet 210 and an anode electrolyte cathode electrolyte outlet 222, and a cathode electrolyte outlet 212 and an anode electrolyte inlet 220 are separate.
  • the stopper 270 is combined to prevent damage to the stack.
  • the stopper 270 may be in the form of being covered with the electrolyte inlet or outlet as shown in the embodiment, but when the electrolyte inlet or outlet is a flap tube may be in the form of a plate is fastened to the flange tube.
  • the shape of the plug can be variously modified depending on the type of the electrolyte inlet outlet.
  • one of the electrolyte inlets or outlets connected to the positive electrode using one equalizing tube 250 and the electrolyte inlet or outlet connected to the negative electrode may be used. After connecting one, the remaining inlet or outlet is connected to the secondary equalizing pipe 260 to prevent damage to the stack.
  • FIG 8 and 9 are photographs showing the storage state using the stack damage prevention method of the redox flow battery according to the present invention.
  • FIG. 8 shows a state immediately after connecting one side of the anode cell and the cathode cell with an equalizing tube
  • FIG. 9 shows the state after storage for three weeks.
  • the electrolyte on one side has risen into the equalizing tube.
  • the amount of the equalized electrolyte is considered to be a leaking part if all the outlets are closed without the equalizing tube. Since the electrolyte is not leaked and the damage is prevented in the equalizing tube, the electrolyte flows from the side into which the electrolyte is introduced. It can be seen that the pressure difference is resolved.
  • the anode cell and the cathode cell communicate with each other through an equalizing tube, so that the pressure difference between the anode cell and the cathode cell caused by the diffusion of the electrolyte through the ion exchange membrane is eliminated.
  • This storage form can prevent leakage of the electrolyte filled inside the stack to the outside during transport and storage, and also to prevent foreign matter from entering the inside of the stack, and to prevent the electrolyte from being oxidized or precipitated. Bring it.

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

Abstract

L'invention concerne un procédé pour empêcher l'endommagement d'un empilement de batterie à flux redox pourvu d'un orifice d'entrée d'électrolyte cathodique, d'un orifice de sortie d'électrolyte cathodique, d'un orifice d'entrée d'électrolyte anodique et d'un orifice de sortie d'électrolyte anodique, le procédé consistant à raccorder, dans un état dans lequel l'électrolyte cathodique et l'électrolyte anodique sont chargés à l'intérieur de l'empilement, un orifice choisi parmi l'orifice d'entrée d'électrolyte cathodique et l'orifice de sortie d'électrolyte cathodique et un autre orifice choisi parmi l'orifice d'entrée d'électrolyte anodique et l'orifice de sortie d'électrolyte anodique avec un tube d'égalisation pour permettre à un compartiment cathodique et un compartiment anodique à l'intérieur de l'empilement de communiquer par le tube d'égalisation.
PCT/KR2016/011590 2015-10-15 2016-10-14 Procédé permettant d'empêcher l'endommagement d'un empilement de batterie à flux redox WO2017065575A1 (fr)

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KR1020150144307A KR101791311B1 (ko) 2015-10-15 2015-10-15 레독스 흐름 전지의 스택 손상 방지 방법
KR10-2015-0144307 2015-10-15

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110071319A (zh) * 2018-01-23 2019-07-30 北京普能世纪科技有限公司 一种液流电池系统及其液流电池电堆

Families Citing this family (4)

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Publication number Priority date Publication date Assignee Title
KR102381015B1 (ko) * 2017-11-28 2022-04-01 스미토모덴키고교가부시키가이샤 레독스 플로우 전지
KR20220061724A (ko) 2020-11-06 2022-05-13 남도금형(주) 레독스 흐름전지 스택 프레스 장치
KR20220090219A (ko) 2020-12-22 2022-06-29 지엔에스티주식회사 작업대 가변이 가능한 레독스 흐름 전지용 프레스장치
KR20230064456A (ko) 2021-11-03 2023-05-10 남도금형(주) 레독스 흐름 전지 스택 밀착 조립용 프레스 장치

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JPH07272738A (ja) * 1994-03-31 1995-10-20 Toyota Motor Corp 燃料電池システム
JP2011119283A (ja) * 2011-03-17 2011-06-16 Kansai Electric Power Co Inc:The レドックスフロー電池およびその運転方法
JP2011170995A (ja) * 2010-02-16 2011-09-01 Toyota Motor Corp 燃料電池システム
US20130157162A1 (en) * 2011-03-25 2013-06-20 Sumitomo Electric Industries, Ltd. Redox flow battery and method of operating the same
US20140272483A1 (en) * 2013-03-15 2014-09-18 Enervault Corporation Systems and Methods for Rebalancing Redox Flow Battery Electrolytes

Patent Citations (5)

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Publication number Priority date Publication date Assignee Title
JPH07272738A (ja) * 1994-03-31 1995-10-20 Toyota Motor Corp 燃料電池システム
JP2011170995A (ja) * 2010-02-16 2011-09-01 Toyota Motor Corp 燃料電池システム
JP2011119283A (ja) * 2011-03-17 2011-06-16 Kansai Electric Power Co Inc:The レドックスフロー電池およびその運転方法
US20130157162A1 (en) * 2011-03-25 2013-06-20 Sumitomo Electric Industries, Ltd. Redox flow battery and method of operating the same
US20140272483A1 (en) * 2013-03-15 2014-09-18 Enervault Corporation Systems and Methods for Rebalancing Redox Flow Battery Electrolytes

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110071319A (zh) * 2018-01-23 2019-07-30 北京普能世纪科技有限公司 一种液流电池系统及其液流电池电堆

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