WO2020021611A1 - Procédé de fonctionnement de pile rédox, et pile rédox - Google Patents

Procédé de fonctionnement de pile rédox, et pile rédox Download PDF

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Publication number
WO2020021611A1
WO2020021611A1 PCT/JP2018/027573 JP2018027573W WO2020021611A1 WO 2020021611 A1 WO2020021611 A1 WO 2020021611A1 JP 2018027573 W JP2018027573 W JP 2018027573W WO 2020021611 A1 WO2020021611 A1 WO 2020021611A1
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Prior art keywords
positive electrode
electrolyte
electrode
battery
negative electrode
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PCT/JP2018/027573
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English (en)
Japanese (ja)
Inventor
康充 筒井
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住友電気工業株式会社
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Application filed by 住友電気工業株式会社 filed Critical 住友電気工業株式会社
Priority to PCT/JP2018/027573 priority Critical patent/WO2020021611A1/fr
Priority to TW108120224A priority patent/TW202011634A/zh
Publication of WO2020021611A1 publication Critical patent/WO2020021611A1/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
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/04—Auxiliary arrangements, e.g. for control of pressure or for circulation of fluids
    • 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
    • Y02E60/30—Hydrogen technology
    • Y02E60/50—Fuel cells

Definitions

  • the present disclosure relates to a method for operating a redox flow battery and a redox flow battery.
  • An RF battery typically includes a battery cell and a liquid flow path for flowing an electrolyte through the battery cell as described in Patent Document 1.
  • the battery cell includes a positive electrode to which a positive electrode electrolyte is supplied, a negative electrode to which a negative electrode electrolyte is supplied, and a diaphragm interposed between the two electrodes.
  • the liquid flow path includes a tank that stores the electrolytic solution, and a pipe that connects between the battery cell and the tank.
  • an RF battery includes a liquid flow path through which a positive electrode electrolyte flows and a liquid flow path through which a negative electrode electrolyte flows.
  • the method of operating the redox flow battery of the present disclosure includes: A battery cell including an electrode used for a positive electrode and an electrode used for a negative electrode, and a method for operating a redox flow battery that operates a redox flow battery including a liquid flow path that circulates an electrolyte for each electrode, In a state where the negative electrode electrolyte is not supplied to the electrode used for the negative electrode, a positive electrode electrolyte is supplied, and a substance attached to the electrode used for the negative electrode is dissolved in the positive electrode electrolyte, Removing ions generated by dissolving the substance by a filter provided in the liquid flow path.
  • the redox flow battery of the present disclosure A battery cell including an electrode used for a positive electrode and an electrode used for a negative electrode, A liquid flow path through which the electrolyte containing the element ions functioning as the positive electrode active material and the element ions functioning as the negative electrode active material flows through each electrode, A switching unit for mutually switching the polarities of both electrodes, A filter provided in the liquid flow path, The filter unit includes: When the positive electrode electrolyte is supplied to the electrode switched from the negative electrode to the positive electrode by the switching unit, ions generated by dissolving a substance attached to the electrode in the positive electrode electrolyte are removed.
  • a battery cell including a positive electrode and a negative electrode, A liquid flow path on the positive electrode side through which a positive electrode electrolyte flows with respect to the positive electrode, A liquid flow path on the negative electrode side through which a negative electrode electrolyte flows with respect to the negative electrode, The liquid flow path on the positive electrode side, A main passage for flowing the positive electrode electrolyte to the positive electrode, A branch for shunting the positive electrode electrolyte to the negative electrode, A switching valve unit for switching between the main road and the branch road, A filter for removing ions generated by dissolving a substance attached to the negative electrode in the positive electrode electrolyte;
  • FIG. 2 is a schematic configuration diagram illustrating a state in which switching is not performed by a switching unit in the redox flow battery of Embodiment 1.
  • FIG. 2 is a schematic configuration diagram illustrating a state in which switching is performed by a switching unit in the redox flow battery of Embodiment 1.
  • FIG. 9 is a schematic configuration diagram illustrating a state during normal operation in the redox flow battery of Embodiment 2.
  • FIG. 9 is a schematic configuration diagram showing a state at the time of dissolving and removing a substance attached to an electrode in the redox flow battery of Embodiment 2. It is a schematic structure figure showing the cell stack used for a redox flow battery.
  • a substance that inhibits a battery reaction or a substance that causes a side reaction may adhere to an electrode over time.
  • the substance includes, for example, a solid substance such as a precipitate containing element ions contained in the electrolytic solution.
  • the substance such as the precipitate adheres to the electrode, the battery performance is reduced or hydrogen gas or the like is generated due to the inhibition of the battery reaction or the occurrence of a side reaction.
  • the above-mentioned substance easily adheres to the electrode surface of the negative electrode compared to the positive electrode. Therefore, in the negative electrode, it is easy to cause inhibition of the battery reaction and generation of hydrogen gas. Therefore, it is desired to remove the substance from the electrode.
  • Patent Document 1 discloses an RF battery including a filter cell for removing impurities in an electrolytic solution.
  • the filter cell has the same structure as the battery cell.
  • the filter cell includes a felt having a high filtering function instead of the positive electrode and the negative electrode of the battery cell.
  • a pipe connecting the battery cell and the tank is provided separately from the above-described liquid flow path.
  • the above-mentioned filter cell is provided in this pipe, and the electrolytic solution flows.
  • the filter cell cannot remove the deposits and the like attached to the electrodes.
  • the redox flow battery operating method of the present disclosure and the redox flow battery of the present disclosure can easily remove a substance attached to an electrode.
  • a method for operating a redox flow battery includes: A battery cell including an electrode used for a positive electrode and an electrode used for a negative electrode, and a method for operating a redox flow battery that operates a redox flow battery including a liquid flow path that circulates an electrolyte for each electrode, In a state where the negative electrode electrolyte is not supplied to the electrode used for the negative electrode, a positive electrode electrolyte is supplied, and a substance attached to the electrode used for the negative electrode is dissolved in the positive electrode electrolyte, Removing ions generated by dissolving the substance by a filter provided in the liquid flow path.
  • an RF battery even if a substance such as a precipitate adheres to the surface of an electrode used as a negative electrode (hereinafter, sometimes referred to as an electrode before regeneration), the substance can be easily removed. Can be removed.
  • the operation method of the RF battery according to the present disclosure is to supply a positive electrode electrolyte to the pre-regeneration electrode, dissolve and ionize the above-described substance, and use a filter provided in a liquid flow path through which the positive electrode electrolyte flows. It removes ions.
  • Such an operation method of the RF battery can easily remove the above substances and is excellent in workability as compared with a case where the battery cell is disassembled and the electrode is washed.
  • a positive electrode electrolyte is used as a liquid for dissolving the above substance. That is, an electrolytic solution in which the positive electrode active material causes a battery reaction is used.
  • the method for operating an RF battery according to the present disclosure does not require a special cleaning solution or the like for dissolving the above-described substance, and thus is excellent in workability and easy to implement.
  • the positive electrode electrolyte has a higher oxidizing power than the negative electrode electrolyte. Therefore, the positive electrode electrolyte can be suitably used for dissolving the substance such as the above-mentioned precipitate.
  • the above-described substances are removed in an ion state. Therefore, re-precipitation of the substance can be prevented. Further, the positive electrode electrolyte that has passed through the filter part can be reused as the electrolyte for the RF battery. Therefore, according to the operation method of the RF battery of the present disclosure, the cost required for dissolving and removing the above-described substances can be reduced.
  • the redox flow battery includes: A battery cell including an electrode used for a positive electrode and an electrode used for a negative electrode, A liquid flow path through which the electrolyte containing the element ions functioning as the positive electrode active material and the element ions functioning as the negative electrode active material flows through each electrode, A switching unit for mutually switching the polarities of both electrodes, A filter provided in the liquid flow path, The filter unit includes: When the positive electrode electrolyte is supplied to the electrode switched from the negative electrode to the positive electrode by the switching unit, ions generated by dissolving a substance attached to the electrode in the positive electrode electrolyte are removed.
  • the RF battery according to the present disclosure can easily remove the above-mentioned substance even if a substance such as a deposit adheres to the surface of the electrode (electrode before regeneration) used as the negative electrode.
  • the electrolytic solution used for the RF battery of the present disclosure includes both element ions functioning as a positive electrode active material and element ions functioning as a negative electrode active material.
  • Such an electrolyte can be used as a positive electrode electrolyte in which the positive electrode active material performs a battery reaction and a negative electrode electrolyte in which the negative electrode active material performs a battery reaction during a charging operation or a discharging operation. If the charging operation is performed by switching the polarity by the switching unit, the electrolyte used as the negative electrode electrolyte during the normal operation before the switching can be used as the positive electrode electrolyte during the charging operation after the switching.
  • this positive electrode electrolyte can be supplied to the pre-regeneration electrode that has become the positive electrode after the switching.
  • the positive electrode electrolyte has a higher oxidizing power than the negative electrode electrolyte. Therefore, by supplying the positive electrode electrolyte to the pre-regeneration electrode, the substance adhering to the pre-regeneration electrode can be dissolved and ionized. In addition, ions generated by dissolving the substance can be removed by the filter provided in the liquid flow path of the positive electrode electrolyte.
  • Such an RF battery according to the present disclosure can easily remove the above substances and improve workability as compared with a conventional RF battery which requires disassembly and reconstruction of a battery cell to remove the above substances. Excellent.
  • the RF battery according to the present disclosure can easily remove the substance as compared with an RF battery that does not include the switching unit and the filter unit that removes the ions. Further, a positive electrode electrolyte is used as a liquid for dissolving the above substances.
  • the RF battery according to the present disclosure is excellent in workability because a special cleaning liquid or the like is not required for dissolving the above-described substance. Therefore, the RF battery of the present disclosure can easily perform the operation of dissolving / removing the above substance.
  • the above-described substances are removed in an ion state. Therefore, re-precipitation of the substance can be prevented. Further, the positive electrode electrolyte that has passed through the filter part can be reused as the electrolyte for the RF battery. Therefore, the RF battery of the present disclosure can also reduce the cost required for dissolving and removing the above-described substances.
  • the RF battery of the present disclosure can be constructed by assembling the above-described conventional RF battery mainly with a switching unit and the above-described filter unit that removes ions. Further, the RF battery of the present disclosure does not require replacement of the electrolytic solution to dissolve and remove the above-described substances. Therefore, it is not necessary to make a significant design change or the like, and it is easy to construct.
  • the redox flow battery includes: A battery cell including a positive electrode and a negative electrode, A liquid flow path on the positive electrode side through which a positive electrode electrolyte flows with respect to the positive electrode, A liquid flow path on the negative electrode side through which a negative electrode electrolyte flows with respect to the negative electrode, The liquid flow path on the positive electrode side, A main passage for flowing the positive electrode electrolyte to the positive electrode, A branch for shunting the positive electrode electrolyte to the negative electrode, A switching valve unit for switching between the main road and the branch road, A filter for removing ions generated by dissolving a substance attached to the negative electrode in the positive electrode electrolyte;
  • the RF battery according to the present disclosure can easily remove the above substances even if substances such as deposits adhere to the surface of the negative electrode.
  • the switching valve unit switches between the main path and the branch path, so that the positive electrode electrolyte can be supplied to the negative electrode.
  • the positive electrode electrolyte has a higher oxidizing power than the negative electrode electrolyte. Therefore, by supplying the positive electrode electrolyte to the negative electrode, the substance adhering to the negative electrode can be dissolved and ionized. In addition, ions generated by dissolving the substance can be removed by the filter provided in the liquid flow path on the positive electrode side.
  • Such an RF battery according to the present disclosure can easily remove the substance and is excellent in workability, as compared with a conventional RF battery that requires disassembly and reconstruction of a battery cell to remove the substance. .
  • the RF battery according to the present disclosure can easily remove the substance as compared with an RF battery that does not have the switching valve unit, the branch path, and the filter unit that removes the ions. Further, a positive electrode electrolyte is used as a liquid for dissolving the above substances.
  • the RF battery according to the present disclosure is excellent in workability because a special cleaning solution or the like is not required for dissolving the above-described substance. Therefore, the RF battery of the present disclosure can easily perform the operation of dissolving / removing the above substance.
  • the above-described substances are removed in an ion state. Therefore, re-precipitation of the substance can be prevented. Further, the positive electrode electrolyte that has passed through the filter unit can be reused. Therefore, the RF battery of the present disclosure can also reduce the cost required for dissolving and removing the above-described substances.
  • the RF battery of the present disclosure does not require a charging operation or the like for dissolving and removing the above-described substances.
  • the electrical connection structure can be simplified.
  • the filter section is provided downstream of the battery cell in a liquid flow path through which the positive electrode electrolyte flows.
  • the above-mentioned ions dissolved in the positive electrode electrolyte can be efficiently removed for the following reasons.
  • the positive electrode electrolyte that has passed through the pre-regeneration electrode or the negative electrode flows downstream of the battery cell. This is because the positive electrode electrolyte passed through the pre-regeneration electrode or the negative electrode easily contains a large amount of ions generated by dissolving the above-mentioned substance.
  • the RF battery 1 includes an electrode 13 used as a positive electrode (hereinafter, sometimes referred to as a positive electrode 14) and an electrode 13 used as a negative electrode (hereinafter, sometimes referred to as a negative electrode 15). And a liquid flow path 3 through which an electrolytic solution flows through each electrode 13.
  • one liquid flow path 3 is used as a liquid flow path 4 on the positive electrode side through which a positive electrode electrolyte flows through the positive electrode 14.
  • the other liquid flow path 3 is used as the liquid flow path 5 on the negative electrode side that allows the negative electrode electrolyte to flow through the negative electrode 15.
  • the battery cell 10 includes a positive electrode 14 to which a positive electrode electrolyte is supplied, a negative electrode 15 to which a negative electrode electrolyte is supplied, and a diaphragm 11 interposed between the positive electrode 14 and the negative electrode 15.
  • the battery cell 10 is constructed using the cell frame 12 illustrated in FIG.
  • the RF battery 1 is used as a single cell battery including a single battery cell 10 as shown in FIG. 1 and FIG. 3 described below.
  • the RF battery 1 is used as a multi-cell battery including a cell stack 100 in which a plurality of battery cells 10 are stacked as shown in FIG.
  • the cell frame 12 includes, for example, a structure including a bipolar plate 120 and a frame 121 as shown in FIG.
  • the positive electrode 14 is disposed on one surface of the bipolar plate 120.
  • the negative electrode 15 is arranged on the other surface of the bipolar plate 120.
  • the frame body 121 is provided on the periphery of the bipolar plate 120.
  • One surface of the frame body 121 has a supply path and a discharge path for the positive electrode electrolyte.
  • the positive electrode supply path includes a liquid supply hole 4i and a slit extending from the liquid supply hole 4i to the inner peripheral edge of the frame 121.
  • the positive electrode discharge path includes a drain hole 4o and a slit extending from the inner peripheral edge to the drain hole 4o.
  • the other surface of the frame 121 has a supply path and a discharge path for the negative electrode electrolyte.
  • the negative electrode supply path includes a liquid supply hole 5i and a slit extending from the liquid supply hole 5i to the inner peripheral edge.
  • the negative electrode discharge path includes a drain hole 5o and a slit extending from the inner peripheral edge to the drain hole 5o.
  • the cell stack 100 includes the following stacked body, a pair of end plates 101 sandwiching the stacked body, and a plurality of fastening members 102 for fastening between both end plates 101.
  • the laminate is repeatedly laminated in the order of the cell frame 12, the positive electrode 14, the diaphragm 11, and the negative electrode 15.
  • the tightening members 102 such as long bolts and nuts
  • the stacked state of the stacked body is maintained. Further, by this tightening, the space between the adjacent cell frames 12 is kept liquid-tight.
  • a predetermined number of battery cells 10 may be a sub-cell stack 110, and the cell stack 100 may include a plurality of sub-cell stacks 110.
  • the liquid flow path 3 includes a tank, a pipe, and a pump as illustrated in FIG.
  • the piping connects between the battery cell 10 and the tank.
  • the liquid flow path 3 is constructed so as to circulate and supply the electrolytic solution to the battery cells 10 by a pump.
  • the liquid flow path 4 on the positive electrode side includes a tank 46 for storing the positive electrode electrolyte, pipes 42 and 44 connecting the battery cell 10 or the cell stack 100 and the tank 46, and a pump 40.
  • the pump 40 is provided on an upstream pipe 42 for flowing the positive electrode electrolyte toward the battery cell 10.
  • the liquid flow path 5 on the negative electrode side includes a tank 56 for storing the negative electrode electrolyte, pipes 52 and 54 connecting the tank 56 with the battery cell 10 or the cell stack 100, and a pump provided on the pipe 52 on the upstream side. 50.
  • the pipe by the above-mentioned liquid supply hole 4i is connected to the pipe.
  • the pipe 44 is connected to the pipe by the drain hole 4o.
  • the pipe 52 is connected to the pipe by the liquid supply hole 5i.
  • the pipe by the above-mentioned drain hole 5o is connected to the pipe 54.
  • the electrode 13 may be a porous body such as a fiber aggregate of a carbon material.
  • the diaphragm 11 includes an ion exchange membrane and the like.
  • the bipolar plate 120 includes a conductive plastic plate containing a conductive material such as graphite and an organic material such as a resin.
  • the constituent material of the frame 121 includes a resin such as vinyl chloride, polyethylene, and polypropylene.
  • the constituent materials of the pipes 42, 44, 52, 54 include resins such as vinyl chloride.
  • the pumps 40 and 50 include an electric pump and the like.
  • Elemental ions that function as an active material include metal ions whose valence changes due to redox.
  • metal element ions that function as a positive electrode active material include vanadium ions, manganese ions, and iron ions.
  • metal element ions that function as a negative electrode active material include vanadium ions, titanium ions, chromium ions, and the like.
  • As the positive electrode electrolyte a solution containing an element ion functioning as a positive electrode active material can be used.
  • As the negative electrode electrolyte a solution containing an element ion functioning as a negative electrode active material can be used.
  • an electrolyte in which the positive electrode electrolyte and the negative electrode electrolyte do not contain ions of a common element type that is, a so-called two-pack type electrolyte
  • an electrolyte solution containing ions of element types common to the positive electrode electrolyte solution and the negative electrode electrolyte solution (the valencies may be different) can be used.
  • an electrolyte containing both an element ion functioning as a positive electrode active material and an element ion functioning as a negative electrode active material is given.
  • a typical example is a so-called one-pack type electrolytic solution.
  • the RF battery 1 using the one-component electrolyte has the following effects (1) and (2) as compared with the case of using the two-component electrolyte. (1) It is excellent in productivity of an electrolytic solution. (2) It is easy to correct when a liquid transfer or a valence balance shift occurs.
  • Examples of the one-component electrolyte include the following (a) to (c).
  • the RF battery 1 is typically connected to a power generation unit 92 and a load 93 via an AC / DC converter 90, a substation facility 91, and the like.
  • the RF battery 1 performs charging using the power generation unit 92 as a power supply source. Further, the RF battery 1 performs discharge with the load 93 as a power supply target.
  • the terminal portion 62 is connected to one electrode 13. Further, the positive electrode terminal 63 of the AC / DC converter 90 is electrically connected to the one terminal 62 so that the one electrode 13 functions as the positive electrode 14.
  • a terminal 66 is connected to the other electrode 13.
  • the other electrode 13 functions as the negative electrode 15 by electrically connecting the negative terminal 67 of the AC / DC converter 90 to the other terminal 66.
  • an electrolyte is supplied to each electrode 13.
  • the battery cell 10 or the cell stack 100 and the AC / DC converter 90 are electrically connected as described above.
  • the positive electrode electrolyte stored in the tank 46 is supplied to the positive electrode 14.
  • the negative electrode electrolyte stored in the tank 56 is supplied to the negative electrode 15.
  • the power generation unit 92 includes, for example, a solar power generator, a wind power generator, and other general power plants.
  • the load 93 is, for example, a power system, a customer, or the like.
  • the RF battery 1 can be used as a storage battery for power generation of natural energy such as solar power generation and wind power generation, for the purpose of stabilizing fluctuations in power generation output, storing power when excess power is generated, leveling the load, and the like.
  • the RF battery 1 is provided in a general power plant, and can be used as a storage battery for the purpose of measures for instantaneous voltage drop, power outage, and load leveling.
  • the RF battery 1A of the first embodiment includes a switching unit 6 and a filter unit 7 in addition to the battery cell 10 and the liquid channel 3 described in the above basic configuration.
  • the electrolytic solution supplied to each electrode 13 contains an element ion functioning as a positive electrode active material and an element ion functioning as a negative electrode active material.
  • the switching unit 6 switches the polarity of each electrode 13 mutually.
  • the filter section 7 is provided in the liquid flow path 3.
  • the filter unit 7 is provided with the positive electrode electrolyte supplied to the electrode 13 that has been switched from the negative electrode to the positive electrode by the switching unit 6, so that ions 81 generated by dissolving the substance 80 attached to the electrode 13 (FIG. 2) Is removed.
  • the substance 80 is schematically shown by a solid circle. 2 and 4, the ions 81 are schematically indicated by broken circles.
  • the electrode 13 (pre-reproduction electrode) used as the negative electrode 15 before switching is made to function as the positive electrode 14 after switching (FIG. 2).
  • the electrolytic solution in the tank 56 used as the negative electrode tank before the switching is replaced with the positive electrode electrolyte in which the element ions functioning as the positive electrode active material perform the battery reaction after the switching. Let it function as a liquid. Therefore, after the switching, the positive electrode electrolyte can be supplied to the pre-regeneration electrode. Further, the substance 80 attached to the pre-regeneration electrode can be dissolved and ionized by the positive electrode electrolyte. Further, the ions 81 generated by the dissolution can be removed by the filter unit 7.
  • each component will be described in detail.
  • the switching unit 6 includes, for example, a unit including the following conductive connection units 61 and 65.
  • One conductive connection portion 61 electrically connects between a terminal portion 62 connected to one electrode 13 and a positive terminal portion 63 or a negative terminal portion 67 of the AC / DC converter 90.
  • the other conductive connection portion 65 electrically connects the terminal portion 66 connected to the other electrode 13 and the terminal portion 63 on the positive electrode side or the terminal portion 67 on the negative electrode side.
  • the switching operation of the connection state of the conductive connection portions 61 and 65 may be performed manually, or a configuration may be employed in which a control device (not shown) is provided and the control device automatically performs the switching according to the set conditions.
  • the switching unit 6 includes an operation unit such as a knob or a button.
  • an operation unit such as a knob or a button.
  • Specific examples include a mode including a toggle switch and a mode including a switch and a relay.
  • the conductive connection portions 61 and 65 may be formed of a conductor wire or the like. In this case, the connection between the conductive connection portion 61 and the terminal portion 62 and the terminal portions 63 and 67, and the connection between the conductive connection portion 65 and the terminal portion 66 and the terminal portions 63 and 67 may be manually connected.
  • a control device it is preferable that the timing of the normal operation and the timing of the dissolving / removing operation of the substance 80 are set in advance and stored in the control device.
  • FIG. 1 illustrates a case where the terminal portion 62 on the left side of the drawing is connected to the above-described terminal portion 63 on the positive side by the conductive connecting portion 61, and the electrode 13 on the left side of the drawing functions as the positive electrode 14.
  • FIG. 1 exemplifies a case in which the terminal portion 66 on the right side of the drawing and the above-described negative terminal portion 67 are connected by the conductive connection portion 65, and the electrode 13 on the right side of the drawing functions as the negative electrode 15.
  • FIG. 2 illustrates a case where the terminal portion 62 on the left side of the drawing and the terminal portion 67 on the negative side are connected by the conductive connecting portion 61, and the electrode 13 on the left side of the drawing functions as the negative electrode 15.
  • 2 exemplifies a case where the terminal portion 66 on the right side of the drawing and the terminal portion 63 on the positive side are connected by the conductive connection portion 65, and the electrode 13 on the right side of the drawing functions as the positive electrode 14.
  • a filter unit that can remove ions 81 generated by dissolving the substance 80 can be used. It may be appropriately selected according to the type of the ion 81.
  • the filter unit 7 may be a filter unit having a functional group that adsorbs ions 81 to a base material made of resin or the like.
  • a commercially available ion removal filter can be used for the filter unit 7.
  • the filter section 7 is provided at an arbitrary position with respect to the liquid flow path 3 through which the positive electrode electrolyte for dissolving and ionizing the substance 80 flows.
  • the positive electrode electrolyte flowing on the downstream side of the battery cell 10 has more ions 81 due to passing through the electrode 13 to which the substance 80 is attached than the liquid flowing on the upstream side of the battery cell 10. Easy to include. Therefore, if the filter 7 is provided downstream of the battery cell 10 in the liquid flow path 3, the filter 7 can efficiently remove the ions 81.
  • the filter part 7 can also be provided in the said liquid flow path 3 in the upstream of the battery cell 10.
  • the number of filter units 7 in one liquid flow path 3 may be one as in this example, or may be plural.
  • Can be The arrangement position of each filter unit 7 can be appropriately selected.
  • all of the plurality of filter units 7 may be provided downstream of the battery cells 10 in the liquid flow path 3.
  • a part of the plurality of filter units 7 may be provided on the downstream side of the battery cell 10 in the liquid flow path 3, and the other part may be provided on the upstream side of the battery cell 10 in the liquid flow path 3.
  • the RF battery 1A of this example includes filter portions 74 and 75 in the pipes 44 and 54 of the liquid flow paths 3 on the downstream side of the battery cell 10, respectively. Therefore, even when any of the two liquid flow paths 3 is used as a flow path for flowing the positive electrode electrolyte for dissolving the substance 80, the ions 81 can be reliably removed by the filter unit 74 or the filter unit 75.
  • the filter section 7 may be provided in only one of the two liquid flow paths 3. In this case, only the liquid flow path 3 including the filter unit 7 is used as a flow path for flowing the positive electrode electrolyte for dissolving the substance 80.
  • an electrolyte supplied to the electrode 13 functioning as the negative electrode 15 during normal operation and functioning as the positive electrode 14 after the switching of the polarity by the switching unit 6 (hereinafter, referred to as a regeneration electrolyte)
  • the regenerating electrolyte functions as a negative electrode electrolyte during normal operation, and may be capable of dissolving the substance 80 when dissolving or removing the substance 80 after switching the polarity.
  • Examples of the electrolytic solution that can dissolve the substance 80 include those containing element ions having high oxidizing power. Element ions having high oxidizing power include element ions that function as positive electrode active materials.
  • the regeneration electrolyte containing an element ion functioning as a positive electrode active material and an element ion functioning as a negative electrode active material can be suitably used.
  • the electrolyte that is supplied to the electrode 13 that functions as the positive electrode 14 during normal operation can function as a positive electrode electrolyte during normal operation, and can function as a negative electrode electrolyte after the above-described polarity switching.
  • Examples of such an electrolytic solution include those containing an element ion functioning as a positive electrode active material and an element ion functioning as a negative electrode active material.
  • the electrolyte used for the RF battery 1A of the first embodiment the above-mentioned one-pack type electrolyte can be suitably used.
  • the RF battery 1A of the first embodiment performs a normal operation, that is, a charging operation or a discharging operation, for example, as follows.
  • a terminal 62 connected to one electrode 13 (the left side in FIG. 1) and a terminal 63 on the positive electrode side of the AC / DC converter 90 are electrically connected by a conductive connection 61.
  • This electrode 13 is used as a positive electrode 14.
  • the liquid flow path 3 on one side (the left side in FIG. 1 on the paper) is a liquid flow path 4 on the positive electrode side.
  • a terminal 66 connected to the electrode 13 on the other side (the right side in FIG.
  • each of the tanks 46 and 56 provided in each of the liquid flow paths 4 and 5 stores, for example, an electrolytic solution containing an element ion functioning as a positive electrode active material and an element ion functioning as a negative electrode active material.
  • the RF battery 1A performs a normal operation by supplying the electrolytic solution to the positive electrode 14 from the tank 46 and supplying the electrolytic solution to the negative electrode 15 from the tank 56.
  • element ions as the positive electrode active material in the above-mentioned electrolytic solution perform a battery reaction.
  • element ions as the negative electrode active material in the electrolytic solution perform a battery reaction.
  • dissolving process A step of supplying a positive electrode electrolyte in a state in which the negative electrode electrolyte is not supplied to the electrode 13 (pre-regeneration electrode) used for the negative electrode, and dissolving the substance 80 attached to the pre-regeneration electrode in the positive electrode electrolyte.
  • Removal process A step of removing ions 81 generated by dissolving the substance 80 by the filter unit 7 provided in the liquid flow path 3.
  • the following operation is performed when the normal operation is not performed.
  • the time when the normal operation is not performed includes a time of standby, a time of repair, and the like.
  • (1) The driving of the pumps 40 and 50 of both the liquid flow paths 4 and 5 is stopped, so that the electrolyte is not supplied to both the electrodes 13.
  • the switching unit 6 switches the polarity.
  • the electrode 13 on the right side of the drawing (electrode before regeneration) is connected to the negative terminal 67 of the AC / DC converter 90 as shown in FIG. Is connected to the terminal portion 63.
  • At least charging operation is performed by supplying an electrolytic solution to each electrode 13 from tanks 46 and 56 provided in each liquid flow path 3.
  • the electrolyte flowing through the liquid flow path 3 (the liquid flow path 3 on the right side of the paper in FIG. 2) corresponding to the above-mentioned electrode before regeneration is a negative electrode electrolyte in which the negative electrode active material performs a battery reaction.
  • the electrolyte flowing through the liquid flow path 3 on the right side of the drawing is the negative electrode electrolyte.
  • the electrolyte flowing through the liquid flow path 3 on the right side of the drawing functions as a positive electrode electrolyte in which the positive electrode active material performs a battery reaction. Furthermore, the element operation as the positive electrode active material is charged by the charging operation, and functions as a positive electrode electrolyte having high oxidizing power. Therefore, during the charging operation, the positive electrode electrolyte having high oxidizing power is supplied to the pre-regeneration electrode, and the substance 80 attached to the pre-regeneration electrode can be dissolved and ionized in the positive electrode electrolyte.
  • the positive electrode electrolyte passed through the pre-regeneration electrode may include ions 81 generated by dissolving the substance 80.
  • the positive electrode electrolyte which may include the ions 81, flows through the liquid flow path 3 including the filter section 75, so that the ions 81 can be removed by the filter section 75. By removing the ions 81 with the filter unit 75, re-precipitation of the substance 80 can be prevented.
  • the electrolyte that flows through the liquid flow path 3 on the left side of the paper and functions as a positive electrode electrolyte before the polarity is switched functions as a negative electrode electrolyte by the charging operation after the polarity is switched.
  • the negative electrode electrolyte before the switching is performed by the charging operation after the switching.
  • the oxidizing power can be gradually increased by the charging operation.
  • a typical example of such an electrolyte is an all-vanadium-based electrolyte.
  • Charging conditions for dissolving / removing the substance 80 can be appropriately set within a range in which the substance 80 can be dissolved.
  • SOC state of charge
  • charging operation may be performed until the SOC of the positive electrode electrolyte becomes 50% or more.
  • the charging operation may be performed until the SOC of the positive electrode electrolyte becomes 60% or more, and further 70% or more.
  • the SOC may be appropriately measured using a known method or device.
  • the RF battery 1A is used for normal operation.
  • the normal operation may be performed, for example, without changing the connection state of the terminal portions 62 and 66 while the dissolving and removing operation of the substance 80 is performed.
  • the electrode 13 on the left side of the drawing is used as a negative electrode 15, and the electrolyte flowing through the liquid flow path 3 on the left side of the drawing is made to function as a negative electrode electrolyte.
  • the electrode 13 on the right side of the drawing is used as the positive electrode 14, and the electrolyte flowing through the liquid flow path 3 on the right side of the drawing is made to function as the positive electrode electrolyte.
  • the substance 80 may adhere to the electrode 13 (the electrode before regeneration) on the left side of the drawing as the negative electrode 15 with time.
  • the polarity is switched by the switching unit 6 and the connection state of the terminal units 62 and 66 is changed to the state shown in FIG. It is preferable to perform a charging operation or the like.
  • the positive electrode electrolyte passing through the pre-regeneration electrode on the left side of the drawing may include ions 81 generated by dissolving the substance 80.
  • the positive electrode electrolyte which may include the ions 81, flows through the liquid flow path 3 on the left side of the drawing including the filter part 74, so that the ions 81 can be removed by the filter part 74. By removing the ions 81 by the filter unit 74, re-precipitation of the substance 80 can be prevented.
  • the RF battery 1 of this example includes the filter portions 74 and 75 in the two liquid flow paths 3 respectively. Therefore, regardless of which of the two electrodes 13 is used as the negative electrode 15 for normal operation, the substance 80 attached to the electrode 13 used as the negative electrode can be removed as ions 81 by the filter unit 7. This is because if the charging operation is performed while the polarity is changed as described above, the substance 80 attached to the electrode 13 used for the negative electrode can be dissolved and ionized in the positive electrode electrolyte.
  • the normal operation may be performed, for example, after the polarity is switched by the switching unit 6 from the state at the time of the work of dissolving and removing the substance 80 and the connection state of the terminal units 62 and 66 is returned to the original state.
  • the connection state shown in FIG. 2 is returned to the connection state shown in FIG. That is, the electrode 13 on the left side of the drawing is the positive electrode 14, and the electrode 13 on the right side of the drawing is the negative electrode 15.
  • the substance 80 can adhere to the electrode 13 on the right side of the paper used for the negative electrode over time. Therefore, it is preferable to provide the filter unit 75 only in the liquid flow path 3 on the right side of the drawing corresponding to the electrode 13 on the right side of the drawing.
  • the filter section 7 may be omitted from the liquid flow path 3 on the left side of the drawing.
  • the RF battery 1A according to the first embodiment includes a switching unit 6 and a filter unit 7. Therefore, even if the substance 80 such as a precipitate adheres to the surface of the electrode 13 (electrode before regeneration) used as the negative electrode 15, the substance 80 is dissolved by switching the polarity by the switching unit 6 and performing a charging operation or the like. Then, the ions 81 can be removed by the filter unit 7.
  • the RF battery 1A of the first embodiment can easily remove the substance 80 from the following points. (1) Disassembly / reconstruction of the battery cell 10 is not required to remove the substance 80. (2) No special liquid is required for dissolving the substance 80. (3) No need to replace the electrolyte.
  • the substance 80 is removed not in a solid state such as the substance 80 but in the state of the ions 81, so that re-precipitation of the substance 80 can be prevented.
  • the electrolyte used to dissolve the substance 80 can be reused. Therefore, the RF battery 1A can also reduce the cost required for dissolving and removing the substance 80.
  • the RF battery 1A of the first embodiment can be constructed by mainly attaching the switching unit 6 and the filter unit 7 to the above-described basic configuration. Therefore, a significant design change is not required, and construction is easy.
  • the method of operating the RF battery according to the embodiment is performed on the RF battery 1A according to the first embodiment, so that the substance 80 can be ionized and easily removed as described above.
  • the RF battery 1B of the second embodiment includes the battery cell 10 described in the above basic configuration, the liquid flow path 4 on the positive electrode side, and the liquid flow path 5 on the negative electrode side.
  • the RF battery 1B includes a filter section 7 while the liquid flow path 4 on the positive electrode side is branched.
  • the liquid flow path 4 on the positive electrode side includes a main trunk path 4T, a branch path 4B, and switching valve parts 47 and 48.
  • the main trunk path 4 ⁇ / b> T circulates a positive electrode electrolyte with respect to the positive electrode 14.
  • the branch path 4B shunts the positive electrode electrolyte to the negative electrode 15.
  • the switching valve portions 47 and 48 switch between the main road 4T and the branch road 4B.
  • the liquid flow path 4 on the positive electrode side includes a filter unit 7.
  • the filter unit 7 removes ions 81 (FIG. 4) generated by dissolving the substance 80 attached to the negative electrode 15 in the positive electrode electrolyte.
  • the switching valve portions 47 and 48 are switched so that the main trunk 4T can be used, and the positive electrode electrolyte is supplied to the positive electrode 14.
  • the positive electrode electrolyte can be supplied to the negative electrode 15.
  • the substance 80 attached to the negative electrode 15 can be dissolved and ionized by the positive electrode electrolyte.
  • the ions 81 generated by the dissolution can be removed by the filter unit 7.
  • the main path 4T of this example is substantially the same as the liquid flow path 3 having the above-described basic configuration.
  • the main road 4T includes an upstream pipe 42 and a downstream pipe 44.
  • the upstream pipe 42 allows the cathode electrolyte to flow from the tank 46 toward the battery cell 10.
  • the downstream pipe 44 returns the positive electrode electrolyte from the battery cell 10 to the tank 46.
  • the branch path 4B of the present example includes an upstream pipe 43 and a downstream pipe 45.
  • the upstream pipe 43 is connected to the upstream pipe 42 and the battery cell 10.
  • the downstream pipe 45 is connected to the battery cell 10 and the downstream pipe 44.
  • the switching valve portion 47 is provided so as to be able to switch between the upstream pipes 42 and 43.
  • the switching valve portion 47 is disposed downstream of the pump 40 provided in the upstream pipe 42. That is, in this example, one pump 40 is shared by the main trunk path 4T and the branch path 4B. In addition, a pump may be provided in each of the main trunk path 4T and the branch path 4B. This point is the same for a main road 5T and a branch road 5B to be described later.
  • the switching valve portion 48 is provided so as to be able to switch between the downstream pipes 44 and 45.
  • a resin such as vinyl chloride is used as in the pipes 42 and 44.
  • the switching valve portions 47 and 48 include, for example, a three-way valve and the like.
  • a filter unit that can remove ions 81 generated by dissolving the substance 80 can be appropriately used as the filter unit 7.
  • the details of the filter unit 7 may be referred to in the first embodiment.
  • the filter unit 7 is provided at an arbitrary position with respect to the liquid flow path 4 on the positive electrode side. As in this example, it is preferable to provide the filter section 7 on the downstream side of the battery cell 10 in the liquid flow path 4 on the positive electrode side. As described in the first embodiment, the positive electrode electrolyte flowing downstream of the battery cell 10 in the liquid flow path 4 contains a large amount of ions 81 generated by dissolving the substance 80. Therefore, the filter unit 7 provided on the downstream side of the battery cell 10 can efficiently remove the ions 81.
  • the filter section 7 of the present example is provided downstream of the switching valve section 48 in the downstream pipe 44 forming the main trunk path 4T.
  • the filter section 7 may be provided in the downstream pipe 45 forming the branch path 4B.
  • the filter unit 7 may be provided on the liquid flow path 4 on the positive electrode side on the upstream side of the battery cell 10.
  • the filter section 7 may be provided on the upstream pipe 42 forming the main trunk path 4T on the upstream side of the switching valve section 47 or on the upstream pipe 43 forming the branch path 4B.
  • the liquid flow path 5 on the negative electrode side similarly to the liquid flow path 4 on the positive electrode side, the liquid flow path 5 on the negative electrode side also includes a main trunk path 5T, a branch path 5B, and switching valve portions 57 and 58. Therefore, the negative electrode electrolyte can be supplied to the positive electrode 14. However, the liquid flow path 5 on the negative electrode side does not include the filter unit 7.
  • the main trunk path 5T of this example is substantially the same as the liquid flow path 3 having the above-described basic configuration.
  • the main road 5T includes an upstream pipe 52 and a downstream pipe 54.
  • the upstream pipe 52 allows the negative electrode electrolyte to flow from the tank 56 toward the battery cell 10.
  • the downstream pipe 54 returns the negative electrode electrolyte from the battery cell 10 to the tank 56.
  • the branch path 5B of this example includes an upstream pipe 53 and a downstream pipe 55.
  • the upstream pipe 53 is connected to the upstream pipe 52 and the battery cell 10.
  • the downstream pipe 55 is connected to the battery cell 10 and the downstream pipe 54.
  • the switching valve portion 57 is provided so as to be able to switch between the upstream pipes 52 and 53. Further, the switching valve portion 57 is disposed downstream of the pump 50 provided in the upstream pipe 52.
  • the switching valve section 58 is provided so as to be able to switch between the downstream pipes 54 and 55.
  • examples of the cathode electrolyte include those containing element ions functioning as a cathode active material.
  • examples of the negative electrode electrolyte include those containing an element functioning as a negative electrode active material.
  • the above-described two-component electrolyte can be used.
  • the branch passages 4B and 5B are used, the negative electrode electrolyte is supplied to the positive electrode 14 and the positive electrode electrolyte is supplied to the negative electrode 15.
  • the electrolyte of each electrode remaining in the battery cell 10 and the electrolyte of each electrode newly supplied are mixed to function as an active material of each electrode. It is allowed to contain element ions.
  • examples of the electrolytic solution used for the RF battery 1B of Embodiment 2 include those containing an element ion functioning as a positive electrode active material and an element ion functioning as a negative electrode active material.
  • the above-mentioned one-component electrolyte can be used.
  • problems caused by the above-described mixing such as a decrease in the active material of each electrode, do not substantially occur.
  • the RF battery 1B of the second embodiment performs a normal operation, for example, a charging operation or a discharging operation as follows.
  • the switching valve portions 47, 48, 57, 58 are switched so that the main trunk roads 4T, 5T can be used.
  • the positive electrode electrolyte is supplied to the positive electrode 14 (the electrode on the left side in FIG. 3) using the main trunk path 4T of the liquid flow path 4 on the positive electrode side (see black arrows).
  • a negative electrode electrolyte is supplied to the negative electrode 15 (the right electrode in FIG. 3) using the main trunk path 5T of the liquid flow path 5 on the negative electrode side (see black arrows).
  • the method of operating the RF battery according to the above-described embodiment is performed to remove the substance 80. More specifically, the following operation is performed when normal operation such as standby or repair is not performed.
  • the positive electrode electrolyte is supplied to the negative electrode 15 from the tank 46 provided in the liquid flow path 4 on the positive electrode side.
  • a negative electrode electrolyte is supplied to the positive electrode 14 from a tank 56 provided in the liquid flow path 5 on the negative electrode side.
  • the positive electrode electrolyte is supplied from the tank 46 to the negative electrode 15 through the pipe 42 of the main trunk path 4T and the pipe 43 of the branch path 4B (see a black broken arrow).
  • the positive electrode electrolyte passed through the negative electrode 15 returns to the tank 46 via the pipe 45 of the branch path 4B and the pipe 44 of the main trunk path 4T.
  • the negative electrode electrolyte is supplied to the positive electrode 14 via the pipes 52 and 53, and returns to the tank 56 via the pipes 55 and 54 (see white broken arrows).
  • the positive electrode electrolyte has a high oxidizing power. Therefore, when the positive electrode electrolyte is supplied to the negative electrode 15, the substance 80 attached to the negative electrode 15 can be dissolved in the positive electrode electrolyte.
  • the positive electrode electrolyte passed through the negative electrode 15 may include ions 81 generated by dissolving the substance 80.
  • the positive electrode electrolyte which may include the ions 81 flows through the liquid flow path 4 on the positive electrode side including the filter unit 7, whereby the ions 81 can be removed by the filter unit 7. By removing the ions 81 by the filter unit 7, re-precipitation of the substance 80 can be prevented.
  • the conditions such as the time for supplying the positive electrode electrolyte to the negative electrode 15 for dissolving and removing the substance 80 can be appropriately set within a range where the substance 80 can be dissolved.
  • the SOC of the positive electrode electrolyte is 60% or more, and more preferably 70% or more, the liquid supply time can be further shortened.
  • the positive electrode electrolyte after the charging operation usually has a high SOC (for example, 50% or more). Therefore, the positive electrode electrolyte after the charging operation can be suitably used as a solution for dissolving and removing the substance 80.
  • the RF battery 1B is used for normal operation. Specifically, the driving of the pumps 40 and 50 is stopped. Then, in a state where the electrolyte is not supplied to the positive electrode 14 and the negative electrode 15, the switching valve portions 47, 48, 57, 58 are switched so that the main trunks 4T, 5T can be used. That is, the state shown in FIG. 4 is returned to the state where the positive electrode electrolyte is supplied to the positive electrode 14 and the negative electrode electrolyte is supplied to the negative electrode 15 as shown in FIG.
  • the valence balance may be appropriately adjusted after the substance 80 is dissolved and removed.
  • the RF battery 1B of the second embodiment includes the branch passage 4B, the switching valves 47 and 48, and the filter 7 in the liquid flow path 4 on the positive electrode side. Therefore, even if the substance 80 such as a deposit adheres to the surface of the negative electrode 15, the positive electrode electrolyte can be supplied to the negative electrode 15 by switching from the main trunk path 4 ⁇ / b> T to the branch path 4 ⁇ / b> B by the switching valve parts 47 and 48.
  • the substance 80 can be dissolved in the positive electrode electrolyte and removed as ions 81 by the filter unit 7.
  • the RF battery 1B of the second embodiment can easily remove the substance 80 from the following points. (1) Disassembly / reconstruction of the battery cell 10 is not required to remove the substance 80. (2) No special liquid is required for dissolving the substance 80.
  • the substance 80 is removed in the state of the ions 81, re-precipitation of the substance 80 can be prevented.
  • the electrolyte used for dissolving the substance 80 can be reused. Therefore, the cost required for dissolving and removing the substance 80 can be reduced in the RF battery 1B.
  • the RF battery 1B of the second embodiment does not require a charging operation or the like for dissolving and removing the substance 80. Therefore, the electrical connection structure can be simplified.
  • the method of operating the RF battery according to the embodiment is performed on the RF battery 1B according to the second embodiment, so that the substance 80 can be ionized and easily removed as described above.
  • the branch channel 4B can be used in the liquid channel 4 on the positive electrode side
  • the branch channel 5B can be used in the liquid channel 5 on the negative electrode side.
  • the polarity is switched by the switching unit 6 to perform the charging operation and the like.
  • Such an RF battery can quickly supply a positive electrode electrolyte to the electrode 13 used as the negative electrode 15. Further, since the electrode 13 functions as the positive electrode 14, the SOC of the positive electrode electrolyte is not easily reduced due to the dissolution of the substance 80.
  • this RF battery can supply the positive electrode electrolyte having a high oxidizing power to the electrode 13 to which the substance 80 can adhere, from the beginning to the end of the dissolving and removing operation of the substance 80.
  • Such an RF battery can more reliably dissolve the substance 80. Further, it is expected that the work time required for dissolving and removing the substance 80 can be reduced.
  • the liquid flow path 5 on the negative electrode side is only the main trunk path 5T, and the branch path 5B and the switching valve portions 57 and 58 are omitted.
  • the stored amount of the electrolyte in the tanks 46 and 56 may be shifted. Therefore, after the dissolution / removal operation of the substance 80 is completed, it is preferable to correct the deviation of the stored amount.
  • a pipe (not shown) for communicating the two tanks 46 and 56 is provided. By opening this pipe, the deviation of the stored amount can be easily corrected.

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Abstract

La présente invention concerne un procédé de fonctionnement d'une pile rédox qui a un élément de pile comprenant une électrode utilisée en tant qu'électrode positive et une électrode utilisée en tant qu'électrode négative et un trajet d'écoulement de liquide qui permet à un électrolyte de circuler autour de chaque électrode, le procédé comprenant : une étape consistant à fournir à l'électrode utilisée en tant qu'électrode négative un électrolyte d'électrode positive dans un état dans lequel aucun électrolyte d'électrode négative n'est fourni à celle-ci de manière à permettre à une substance adhérant à l'électrode utilisée en tant qu'électrode négative de se dissoudre dans l'électrolyte d'électrode positive ; et une étape consistant à éliminer les ions générés en raison de la dissolution de la substance avec une section de filtration disposée dans le trajet d'écoulement de liquide.
PCT/JP2018/027573 2018-07-23 2018-07-23 Procédé de fonctionnement de pile rédox, et pile rédox WO2020021611A1 (fr)

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TW108120224A TW202011634A (zh) 2018-07-23 2019-06-12 氧化還原液流電池之運轉方法及氧化還原液流電池

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CN113451629A (zh) * 2021-07-14 2021-09-28 大连海事大学 一种低成本铁钛液流电池
WO2022216783A1 (fr) * 2021-04-06 2022-10-13 Vizn Energy Systems, Inc. Décontamination de cuve de circulation

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TWI728857B (zh) * 2020-07-07 2021-05-21 行政院原子能委員會核能研究所 液流電池電量量測方法與量測系統裝置

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JP2016119258A (ja) * 2014-12-22 2016-06-30 住友電気工業株式会社 レドックスフロー電池の運転方法、及びレドックスフロー電池システム
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WO2022216783A1 (fr) * 2021-04-06 2022-10-13 Vizn Energy Systems, Inc. Décontamination de cuve de circulation
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