WO2018105091A1 - レドックスフロー電池 - Google Patents
レドックスフロー電池 Download PDFInfo
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- WO2018105091A1 WO2018105091A1 PCT/JP2016/086643 JP2016086643W WO2018105091A1 WO 2018105091 A1 WO2018105091 A1 WO 2018105091A1 JP 2016086643 W JP2016086643 W JP 2016086643W WO 2018105091 A1 WO2018105091 A1 WO 2018105091A1
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- Prior art keywords
- bipolar plate
- electrode
- frame
- cell
- redox flow
- Prior art date
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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
- H01M8/02—Details
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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
- H01M8/02—Details
- H01M8/0297—Arrangements for joining electrodes, reservoir layers, heat exchange units or bipolar separators to each other
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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
- H01M8/02—Details
- H01M8/0202—Collectors; Separators, e.g. bipolar separators; Interconnectors
- H01M8/0247—Collectors; Separators, e.g. bipolar separators; Interconnectors characterised by the form
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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
- H01M8/02—Details
- H01M8/0271—Sealing or supporting means around electrodes, matrices or membranes
- H01M8/0273—Sealing or supporting means around electrodes, matrices or membranes with sealing or supporting means in the form of a frame
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/18—Regenerative fuel cells, e.g. redox flow batteries or secondary fuel cells
- H01M8/184—Regeneration by electrochemical means
- H01M8/188—Regeneration by electrochemical means by recharging of redox couples containing fluids; Redox flow type batteries
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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
- H01M8/24—Grouping of fuel cells, e.g. stacking of fuel cells
- H01M8/2455—Grouping of fuel cells, e.g. stacking of fuel cells with liquid, solid or electrolyte-charged reactants
-
- 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
- H01M8/24—Grouping of fuel cells, e.g. stacking of fuel cells
- H01M8/2465—Details of groupings of fuel cells
- H01M8/2484—Details of groupings of fuel cells characterised by external manifolds
- H01M8/2485—Arrangements for sealing external manifolds; Arrangements for mounting external manifolds around a stack
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- 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 redox flow battery.
- Patent Document 1 describes a cell stack in which a plurality of cell frames, positive electrodes, diaphragms, negative electrodes, and cell frames are stacked, and the stacked body is sandwiched between supply and discharge plates, and a redox flow battery using the cell stack.
- the cell frame includes a bipolar plate sandwiched between a positive electrode and a negative electrode, and a frame that supports the bipolar plate from the outer periphery. In this configuration, one cell is formed between the bipolar plates of adjacent cell frames.
- the redox flow battery of the present disclosure is Electrodes, A cell frame comprising a frame and a bipolar plate, and having a fitting recess into which the electrode is fitted; A redox flow battery comprising a diaphragm sandwiching the electrode with the bipolar plate, Among the outer peripheral end surfaces of the electrode, a distance between a side end surface parallel to the flowing direction of the electrolytic solution and an inner wall surface of the fitting recess facing the side end surface is 0.1 mm or more and 12 mm or less.
- FIG. 3 is an operation principle diagram of the redox flow battery according to Embodiment 1.
- FIG. 1 is a schematic configuration diagram of a redox flow battery according to Embodiment 1.
- FIG. 1 is a schematic configuration diagram of a cell stack according to Embodiment 1.
- FIG. It is the top view which looked at the assembly of the cell frame and electrode which concern on Embodiment 1 from the one surface side.
- FIG. 5 is a VV cross-sectional view of FIG. 4. It is the top view which looked at the assembly of the cell frame and electrode which concern on Embodiment 2 from the one surface side.
- FIG. 7 is a sectional view taken along line VII-VII in FIG. 6. It is a cross-sectional view of a cell frame and electrode assembly according to a modification.
- redox flow batteries have attracted attention as a means for storing renewable energy, and development of redox flow batteries having a large discharge capacity is desired.
- the present inventors have focused on the fact that a leak flow path is formed between the outer peripheral end surface of the electrode and the inner wall surface of the fitting portion of the electrode.
- the leak channel is a gap between the electrode and a member facing the outer peripheral end surface of the electrode.
- the electrolyte flowing into the leak channel is discharged from the cell with almost no contact with the electrode. Therefore, since the discharge capacity of the redox flow battery decreases as the amount of electrolyte flowing through the leak channel increases, it is considered important to appropriately manage the size of the leak channel.
- This disclosure is intended to provide a redox flow battery having an excellent discharge capacity by managing the size of the leak channel to an appropriate value.
- the redox flow battery of the present disclosure is excellent in battery performance.
- the redox flow battery according to the embodiment is Electrodes, A cell frame comprising a frame and a bipolar plate, and having a fitting recess into which the electrode is fitted; A redox flow battery comprising a diaphragm sandwiching the electrode with the bipolar plate, Among the outer peripheral end surfaces of the electrode, a distance between a side end surface parallel to the flowing direction of the electrolytic solution and an inner wall surface of the fitting recess facing the side end surface is 0.1 mm or more and 12 mm or less.
- a leak channel is formed between the outer peripheral end surface of the electrode and the inner wall surface of the fitting recess. If the side leakage channel formed between the portion parallel to the flow direction of the electrolyte in the leakage channel, that is, the side end surface of the electrode and the inner wall surface of the fitting recess facing it is narrowed, the side leakage flow The amount of electrolyte flowing through the path can be reduced. As a result, a reduction in discharge capacity of the redox flow battery can be suppressed. Specifically, the reduction in the discharge capacity of the redox flow battery can be effectively suppressed by setting the width of the side leak channel to 12 mm or less.
- the width of the side leak channel is preferably 6 mm or less, and more preferably 3 mm or less.
- the flow direction of the electrolytic solution is a direction in the frame body from the frame piece with the liquid supply manifold to the frame piece with the discharge manifold.
- the width of the side leak channel is set to 0.1 mm or more, that is, an electrode that is slightly smaller than the fitting recess to suppress the electrode from protruding from the fitting recess, and an excessive surface on the diaphragm It can suppress that a pressure acts.
- the width of the side leak channel is preferably 1 mm or more, and more preferably 1.5 mm or more.
- the said insertion recessed part can mention the form comprised by the inner peripheral end surface of the said frame, and one surface of the said bipolar plate which faces the said electrode.
- the contour shape on the inner peripheral side of the frame body forms the contour shape of the opening of the fitting recess. That is, the step portion between the frame body and the bipolar plate originally provided in the cell frame is a fitting recess, and the electrode is easily fitted into the fitting recess.
- the said insertion recessed part can mention the form formed of the dent formed in one surface of the said bipolar plate.
- the frame body is a member to which the stress of the tightening mechanism that tightens the cell constituent members acts, and if the electrode is sandwiched between the adjacent frame bodies, the electrolyte may leak from the cell. According to the above configuration in which the recessed portion is formed in the bipolar plate, the possibility that the electrode is sandwiched between the frames can be extremely reduced.
- interval can mention the form which is 1.5 mm or more and 3 mm or less.
- the interval is 1.5 mm or more and 3 mm or less, it is possible to reduce the amount of the electrolyte flowing through the side leak channel while more effectively suppressing the excessive surface pressure from acting on the diaphragm. As a result, the battery performance of the redox flow battery can be improved.
- a redox flow battery (hereinafter referred to as an RF battery) according to an embodiment will be described with reference to FIGS.
- the RF battery is one of electrolyte circulation type storage batteries, and is used for storing new energy such as solar power generation and wind power generation.
- the RF battery 1 includes a redox potential of active material ions contained in the positive electrode electrolyte and a redox potential of active material ions contained in the negative electrode electrolyte. It is a battery which charges / discharges using the difference with this.
- the RF battery 1 includes a cell 100 separated into a positive electrode cell 102 and a negative electrode cell 103 by a diaphragm 101 that transmits hydrogen ions.
- the positive electrode cell 102 the positive electrode 4 is incorporated, and a positive electrode electrolyte solution tank 106 for storing a positive electrode electrolyte is connected through conduits 108 and 110.
- the conduit 108 is provided with a pump 112, and these members 106, 108, 110, 112 constitute a positive electrode circulation mechanism 100P that circulates the positive electrode electrolyte.
- the negative electrode cell 103 contains a negative electrode 5, and a negative electrode electrolyte solution tank 107 for storing a negative electrode electrolyte solution is connected via conduits 109 and 111.
- the conduit 109 is provided with a pump 113, and these members 107, 109, 111, 113 constitute a negative electrode circulation mechanism 100N for circulating the negative electrode electrolyte.
- the electrolyte stored in the tanks 106 and 107 is circulated in the cells 102 and 103 by the pumps 112 and 113 during charging and discharging. When charging / discharging is not performed, the pumps 112 and 113 are stopped and the electrolytic solution is not circulated.
- the cell 100 is usually formed inside a structure called a cell stack 200 as shown in FIGS.
- the cell stack 200 is configured by sandwiching a laminated structure called a sub stack 200 s (FIG. 3) between two end plates 210 and 220 from both sides and tightening with a tightening mechanism 230 (illustrated in FIG. 3).
- the configuration uses a plurality of sub-stacks 200s).
- a plurality of cell frames 2, positive electrodes 4, diaphragms 101, and negative electrodes 5 are stacked, and the stacked body is a supply / discharge plate 190, 190 (see the lower diagram in FIG. 3, omitted in FIG. 2). ).
- the cell frame 2 includes a frame body 22 having a through window and a bipolar plate 21 that closes the through window. That is, the frame 22 supports the bipolar plate 21 from the outer peripheral side.
- the positive electrode 4 is disposed on one surface side of the bipolar plate 21 and the negative electrode 5 is disposed on the other surface side of the bipolar plate 21.
- one cell 100 is formed between the bipolar plates 21 fitted in the adjacent cell frames 2 (see the upper diagram of FIG. 3).
- the flow of the electrolytic solution to the cell 100 through the supply / discharge plates 190 and 190 shown in the lower part of FIG. 3 is performed by supplying the supply manifolds 123 and 124 formed on the frame 22 of the cell frame 2 and the discharge manifold 125. , 126 (see also FIG. 4).
- the positive electrode electrolyte is supplied from the liquid supply manifold 123 to the positive electrode 4 through an inlet slit 123 s (FIG. 4) formed on one side (the front side of the paper) of the cell frame 2, and is formed on the upper part of the cell frame 2. Is discharged to the drainage manifold 125 via the outlet slit 125s (FIG. 4).
- the negative electrode electrolyte is supplied from the liquid supply manifold 124 to the negative electrode 5 through the inlet slit 124 s (FIG. 4) formed on the other surface side (back side of the paper surface) of the cell frame 2.
- the liquid is discharged to the drainage manifold 126 through an outlet slit 126s (FIG. 4) formed in the upper portion.
- An annular seal member 127 (FIG. 3) such as an O-ring or a flat packing is disposed between the cell frames 2 to suppress leakage of the electrolytic solution from the sub stack 200s. In this example, as shown in FIG.
- a seal groove 127s into which the O-ring is fitted is formed in the cell frame 2 (if a flat packing is used, the seal groove 127s may be omitted).
- a seal member may be provided so as to surround the outer periphery of each manifold 123, 124, 125, 126.
- the entire electrolyte flow direction (flow direction) in the cell frame 2 is a direction from the frame piece with the liquid supply manifolds 123 and 124 to the frame piece with the discharge manifolds 125 and 126 in the frame body 22. That is, it is the upward direction in FIG.
- the frame body 22 of this example has two frame-shaped divided bodies having a cross-sectional shape that is symmetrical in the stacking direction (vertical direction in the drawing). It is formed by bonding 22A and 22B.
- the through-window side (paper surface center side) of the frame-shaped divided bodies 22A, 22B is formed thin, and when the two frame-shaped divided bodies 22A, 22B are bonded together, the thin-walled of both frame-shaped divided bodies 22A, 22B.
- a space for accommodating the outer peripheral edge portion of the bipolar plate 21 is formed between the portions.
- the material of the frame 22 is preferably excellent in insulating properties, and more preferably has acid resistance.
- a material of the frame 22 for example, vinyl chloride, chlorinated polyethylene, chlorinated paraffin, or the like can be used.
- the bipolar plate 21 is a member whose one side is in contact with the positive electrode 4 and whose other side is in contact with the negative electrode 5.
- the bipolar plate 21 of this example is a plate material having a substantially uniform thickness.
- the outer peripheral edge portion of the bipolar plate 21 is sandwiched between two frame-like divided bodies 22A and 22B constituting the frame body 22, as shown in FIG.
- the bipolar plate 21 is integrally fixed to the frame body 22 by this sandwiching.
- a groove is formed in the outer peripheral edge portion of the bipolar plate 21, and an O-ring (seal member) 21 s is disposed in the groove.
- the material of the bipolar plate 21 is preferably excellent in conductivity, and more preferably has acid resistance and flexibility.
- it can be made of a conductive material containing a carbon material, specifically, a conductive plastic made of graphite and a chlorinated organic compound.
- a conductive plastic in which a part of the graphite is replaced with at least one of carbon black and diamond-like carbon may be used.
- the chlorinated organic compound include vinyl chloride, chlorinated polyethylene, and chlorinated paraffin.
- the positive electrode 4 and the negative electrode 5 are disposed on one side (upper side of the paper) and the other side (lower side of the paper) of the bipolar plate 21. More specifically, the positive electrode 4 (negative electrode 5) includes an inner peripheral end face 22i (see an enlarged circle) of the frame 22, and one surface of the bipolar plate 21 facing the positive electrode 4 (negative electrode 5). It is inserted in the insertion recessed part 24 (25) comprised by these. See also FIG. 4 for the insertion recess 24. In FIG. 4, the fitting recess 25 (FIG. 5) is not shown, but has the same configuration as the fitting recess 24.
- the outer peripheral end surfaces 4o and 5o of the electrodes 4 and 5 and the inner wall surfaces 24i and 25i (inner peripheral end surface 22i) of the fitting recesses 24 and 25 are provided.
- a leak channel 3 is formed between the two.
- a portion of the leak flow path 3 that is parallel to the flow direction of the electrolyte (in FIG. 5, the direction from the front to the back in the drawing) is particularly referred to as a side leak flow path 3s.
- the side leak channel 3s is formed between the side end surfaces 4os and 5os of the electrodes 4 and 5 and the inner wall surfaces 24i and 25i of the fitting recesses 24 and 25 facing it.
- the width of the side leak channel 3s affects the discharge capacity of the RF battery 1 (FIGS. 1 and 2). This is because if the width of the side leak channel 3s is increased, the amount of the electrolyte discharged outside the cell 100 (FIGS. 1 and 2) without much contact with the electrodes 4 and 5 increases. From such a viewpoint, if the width of the side leak channel 3s (left and right direction in the drawing) is narrowed, the amount of the electrolyte flowing through the side leak channel 3s can be reduced, and the decrease in the discharge capacity of the RF battery 1 can be suppressed. Conceivable.
- the width of the side leak channel 3s is set to 12 mm or less, and as a result, the reduction of the discharge capacity of the RF battery 1 is effectively suppressed.
- the width of the side leak channel 3s is preferably 6 mm or less, and more preferably 3 mm or less.
- the width of the side leak channel 3s the smaller the electrolyte flowing through the side leak channel 3s.
- the diaphragm 101 that directly faces the electrodes 4 and 5 may be damaged.
- the width of the side leak channel 3s is too narrow, the end portions on the outer peripheral side of the electrodes 4 and 5 protrude from the fitting recesses 24 and 25 when the cell 100 (FIG. 1) is compressed or when the electrolyte solution flows. This is because the protruding portion may ride on the frame body 22 and cause an excessive surface pressure to act on the diaphragm 101.
- the width of the side leak flow path 3s is preferably 1 mm or more, and more preferably 1.5 mm or more.
- the electrodes 4 and 5 are porous bodies, and even when compressed between the adjacent cell frames 2, the size in the plane direction hardly changes. Therefore, if the cell stack 200 (FIG. 3) is disassembled and the width of the side leak channel 3s between the fitting recess 24 (25) and the electrode 4 (5) in FIG. It may be considered that it is equal to the width of the side leak channel 3s in the cell stack 200. That is, before assembling the cell stack 200, the width of the side leak flow path 3 s measured by fitting the uncompressed electrode 4 (5) in the fitting recess 24 (25) is also the side leak flow in the cell stack 200. It can be considered that the width of the path 3s and the width of the side leak flow path 3s measured after disassembling the cell stack 200 are substantially equal.
- the material of the electrodes 4 and 5 is preferably excellent in conductivity, and more preferably has acid resistance.
- the electrodes 4 and 5 can be formed of a woven fabric or a nonwoven fabric made of carbon fiber.
- carbon paper or the like can be used as the electrodes 4 and 5.
- ⁇ Test example ⁇ A plurality of RF batteries 1 (test bodies A to G) having different widths of the side leak flow path 3s are manufactured, and a charge / discharge test is performed on each of the test bodies A to G. The rates were compared. The conditions for the charge / discharge test were: discharge end voltage: 1 V, charge end voltage: 1.6 V, current: 120 mA / cm 2 . For the evaluation of the discharge capacity / current efficiency, a charge / discharge curve was prepared based on the charge / discharge test, and the discharge capacity / current efficiency of the third cycle was evaluated from the charge / discharge curve.
- Specimen A RF battery 1 having a side leak channel 3s having a width of 0.0 mm
- Specimen B RF battery 1 having a side leak channel 3s having a width of 0.1 mm
- C RF battery 1 having a side leak channel 3s having a width of 1.5 mm
- D RF battery 1 having a side leak channel 3s having a width of 3 mm
- Test specimen E RF battery 1 having a side leak flow path 3s having a width of 6 mm
- F RF battery 1 having a side leak channel 3s having a width of 12 mm
- Specimen G RF battery 1 having a side leak channel 3s having a width of 13 mm
- the elongation of the diaphragm 101 of the test body G is due to the expansion of the diaphragm 101 due to the differential pressure generated in the positive electrode 4 and the negative electrode 5 or the repulsive force of the electrodes 4 and 5 in the wide side leak channel 3s. It is thought that occurred. In the other specimens B, C, D, E, and F, no defects such as tearing and elongation were formed in the diaphragm 101 were recognized.
- the charge / discharge test was evaluated, it was not possible to evaluate the specimen A.
- the test bodies B to G can be evaluated, and the discharge capacities of the test bodies C and D are the highest.
- the discharge capacities of the other test bodies B, E, F, and G are larger than the discharge capacities of the test bodies C and D, respectively.
- the results were as low as -3%, -4%, -7%, and -30%.
- the current efficiency was the highest at 98% for the test specimens C, D, and E, and 97%, 97%, and 60% for the other test specimens B, F, and G were observed to be reduced.
- the width of the side leak channel 3s is 0.1 mm or more and 12 mm or less, the diaphragm 101 is not easily broken or stretched, and the discharge capacity of the RF battery 1 is suppressed from decreasing. I understood that. Moreover, from the viewpoint of suppressing a decrease in the discharge capacity of the RF battery 1, it has become clear that the width of the side leak channel 3s is preferably 6 mm or less, and more preferably 3 mm or less.
- Embodiment 2 demonstrates the structure which provided the recessed parts 24 and 25 of the electrodes 4 and 5 in the bipolar plate 21 based on FIG. 6 is a plan view of the cell frame 2 viewed from the positive electrode 4 side, and FIG. 7 is a cross-sectional view taken along the line VII-VII in FIG.
- the outer peripheral edge portion 21c of the bipolar plate 21 formed thinly is formed on the stepped portion 22c formed on the inner peripheral edge portion (the vicinity of the through window) of the frame body 22.
- An engaged fitting structure is adopted.
- the stepped portion 22 c is configured such that the peripheral edge surrounding the through window of the frame body 22 over the entire circumference is thinner than the other portions of the frame body 22.
- the outer peripheral edge portion 21 c of the bipolar plate 21 is locally thin so as to engage with the stepped portion 22 c of the frame body 22.
- the surface of the outer peripheral edge portion 21 c is substantially flush with both surfaces of the frame body 22 other than the stepped portion 22 c when fitted into the stepped portion 22 c of the frame body 22.
- the surface on the negative electrode 5 side of the bipolar plate 21 is disposed at a position recessed from the surface of the frame body 22 when the outer peripheral edge portion 21 c of the bipolar plate 21 is fitted into the stepped portion 22 c of the frame body 22.
- the stepped portion 22c of the frame body 22 and the outer peripheral edge portion 21c of the bipolar plate 21 are engaged in the thickness direction of the frame body 22 over the entire circumference.
- the through window of the frame 22 is closed by the bipolar plate 21.
- the frame body 22 and the bipolar plate 21 are arranged so that the electrolyte does not flow between the one surface side and the other surface side of the bipolar plate 21. It is necessary to seal between.
- an annular groove is formed in a portion of the outer peripheral edge portion 21c of the bipolar plate 21 that faces the step portion 22c, and an O-ring (seal member) 21s is disposed in the groove.
- the O-ring 21s is compressed when a plurality of cell frames 2 are stacked and tightened, and functions as a seal.
- the gap between the stepped portion 22c of the frame body 22 and the outer peripheral edge portion 21c of the bipolar plate 21 may be sealed with a flat packing or an adhesive.
- a fitting recess 24 into which the positive electrode 4 is fitted is formed in a portion of the bipolar plate 21 of the present example facing the positive electrode 4 (see also FIG. 4).
- a side leak channel 3 s is formed between the inner wall surface 24 i of the fitting recess 24 formed in the bipolar plate 21 and the side end surface 4 os of the positive electrode 4.
- the width of the side leak channel 3s is also set to 0.1 mm or more and 12 mm or less, as in the first embodiment, so that damage to the diaphragm 101 (FIG. 3) directly facing the positive electrode 4 is suppressed, and the RF battery The reduction in the discharge capacity of 1 (FIGS. 1 and 2) can be suppressed.
- the upper limit of the width of the side leak channel 3s is preferably 6 mm or less, and more preferably 3 mm or less. Further, the lower limit of the width of the side leak channel 3s is preferably 1 mm or more, and more preferably 1.5 mm or more.
- the fitting recess 25 into which the negative electrode 5 is fitted is configured by an inner peripheral end face 22 i of the frame 22 and one surface of the bipolar plate 21 facing the negative electrode 5, as in the first embodiment. Accordingly, a side leak channel 3 s is formed between the inner peripheral end face 22 i and the side end face 5 os of the negative electrode 5.
- the width of the side leak channel 3s on the negative electrode 5 side may be set in the same manner as in the first embodiment. By doing so, it is possible to suppress a decrease in the discharge capacity of the RF battery 1 (FIGS. 1 and 2) while suppressing damage to the diaphragm 101 (FIG. 3) that directly faces the negative electrode 5.
- the fitting recess 25 may be provided on the surface of the bipolar plate 21 on the negative electrode 5 side. good. According to this configuration, the size of the positive electrode 4 in the planar direction and the size of the negative electrode 5 in the planar direction can be made the same.
- a recess is provided in a portion corresponding to the positive electrode 4 (negative electrode 5) in the bipolar plate 21, and the recess It is good also as a structure which inserts the positive electrode 4 (negative electrode 5).
- the recessed portion 24 (25) is formed by the recess on the positive electrode 4 side (negative electrode 5 side) of the bipolar plate 21 and the inner peripheral end face 22 i of the frame body 22.
- RF battery (redox flow battery) 2 Cell frame 21 Bipolar plate 21c Outer peripheral edge 21s O-ring (seal member) 22 Frame body 22A, 22B Frame-shaped division body 22c Step part 22i Inner peripheral end face 22s O-ring (seal member) 24, 25 Insertion recess 24i, 25i Inner wall surface 123, 124 Liquid supply manifold 125, 126 Drain manifold 123s, 124s Inlet slit 125s, 126s Outlet slit 127 Seal member 127s Seal groove 3 Leakage channel 30 Side leak channel 4 positive electrode 4o outer peripheral end surface 4os side end surface 5 negative electrode 5o outer peripheral end surface 5os side end surface 100 cell 101 diaphragm 102 positive electrode cell 103 negative electrode cell 100P positive electrode circulation mechanism 100N negative electrode circulation mechanism 106 positive electrode electrolyte tank 107 negative electrode electrolyte tank 108, 109, 110, 111 Conduit 112, 113 Pump 190 Supply / discharge plate 200 Cell stack 200s Sub
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Abstract
Description
電極と、
枠体および双極板を備え、前記電極が嵌め込まれる嵌込凹部を有するセルフレームと、
前記電極を前記双極板との間に挟み込む隔膜と、を備えるレドックスフロー電池であって、
前記電極の外周端面のうち、電解液の流通方向に平行な側端面と、前記側端面に対向する前記嵌込凹部の内壁面との間隔が、0.1mm以上12mm以下である。
近年、再生可能エネルギーの蓄電手段としてレドックスフロー電池が注目されており、放電容量の大きなレドックスフロー電池の開発が望まれている。本発明者らは、そのような要請に応えるべく、電極の外周端面とその電極の嵌め込み箇所の内壁面との間にリーク流路が形成されることに着目した。リーク流路は、電極と、電極の外周端面に対向する部材との間の隙間である。このリーク流路に流れ込んだ電解液は電極に殆ど接触しないままセルから排出される。そのため、リーク流路を流れる電解液が多くなるほど、レドックスフロー電池の放電容量が低下するので、リーク流路の大きさを適切に管理することが重要であると考えられる。
本開示のレドックスフロー電池は、電池性能に優れる。
最初に本願発明の実施形態の内容を列記して説明する。
電極と、
枠体および双極板を備え、前記電極が嵌め込まれる嵌込凹部を有するセルフレームと、
前記電極を前記双極板との間に挟み込む隔膜と、を備えるレドックスフロー電池であって、
前記電極の外周端面のうち、電解液の流通方向に平行な側端面と、前記側端面に対向する前記嵌込凹部の内壁面との間隔が、0.1mm以上12mm以下である。
前記嵌込凹部は、前記枠体の内周端面と、前記電極に対面する前記双極板の一面とで構成される形態を挙げることができる。
前記嵌込凹部は、前記双極板の一面に形成される凹みによって形成される形態を挙げることができる。
前記間隔は、1.5mm以上3mm以下である形態を挙げることができる。
以下、本開示のレドックスフロー電池(RF電池)の実施形態を説明する。なお、本発明は実施形態に示される構成に限定されるわけではなく、請求の範囲によって示され、請求の範囲と均等の意味および範囲内の全ての変更が含まれることを意図する。
実施形態に係るレドックスフロー電池(以下、RF電池)を図1~図5に基づいて説明する。
RF電池は、電解液循環型の蓄電池の一つであって、太陽光発電や風力発電といった新エネルギーの蓄電に利用されている。図1のRF電池1の動作原理図に示すように、RF電池1は、正極用電解液に含まれる活物質イオンの酸化還元電位と、負極用電解液に含まれる活物質イオンの酸化還元電位との差を利用して充放電を行う電池である。RF電池1は、水素イオンを透過させる隔膜101で正極セル102と負極セル103とに分離されたセル100を備える。
上記セル100は通常、図2,3に示すような、セルスタック200と呼ばれる構造体の内部に形成される。セルスタック200は、サブスタック200s(図3)と呼ばれる積層構造物をその両側から二枚のエンドプレート210,220で挟み込み、締付機構230で締め付けることで構成されている(図3に例示する構成では、複数のサブスタック200sを用いている)。
セルフレーム2は、貫通窓を有する枠体22と、その貫通窓を塞ぐ双極板21と、を有している。つまり、枠体22は、双極板21をその外周側から支持している。双極板21の一面側には正極電極4が接触するように配置され、双極板21の他面側には負極電極5が接触するように配置される。この構成では、隣接する各セルフレーム2に嵌め込まれた双極板21の間に一つのセル100が形成されることになる(図3の上図を参照)。
正極電極4および負極電極5はそれぞれ、図5に示すように、双極板21の一面側(紙面上側)と他面側(紙面下側)に配置される。より具体的には、正極電極4(負極電極5)は、枠体22の内周端面22i(丸囲み拡大図参照)と、正極電極4(負極電極5)に対面する双極板21の一面とで構成される嵌込凹部24(25)に嵌め込まれている。嵌込凹部24については図4も合わせて参照のこと。図4では、嵌込凹部25(図5)は図示されていないが、嵌込凹部24と同様の構成を備える。
サイドリーク流路3sの幅が異なる複数のRF電池1(試験体A~G)を作製し、各試験体A~Gに対して充放電試験を行なって、各試験体A~Gのセル抵抗率を比較した。充放電試験の条件は、放電終了電圧:1V、充電終了電圧:1.6V、電流:120mA/cm2とした。放電容量・電流効率の評価は、充放電試験に基づいて充放電曲線を作成し、その充放電曲線から3サイクル目の放電容量・電流効率の評価を行った。
・試験体A…サイドリーク流路3sの幅が0.0mmであるRF電池1
・試験体B…サイドリーク流路3sの幅が0.1mmであるRF電池1
・試験体C…サイドリーク流路3sの幅が1.5mmであるRF電池1
・試験体D…サイドリーク流路3sの幅が3mmであるRF電池1
・試験体E…サイドリーク流路3sの幅が6mmであるRF電池1
・試験体F…サイドリーク流路3sの幅が12mmであるRF電池1
・試験体G…サイドリーク流路3sの幅が13mmであるRF電池1
実施形態2では、双極板21に電極4,5の嵌込凹部24,25を設けた構成を図6,7に基づいて説明する。図6は、セルフレーム2を正極電極4側から見た平面図、図7は、図6のVII-VII断面図である。
図8に示すように、双極板21における正極電極4側の面に嵌込凹部24を設けることに加えて、双極板21における負極電極5側の面にも、嵌込凹部25を設けても良い。この構成によれば、正極電極4の平面方向の大きさと負極電極5の平面方向の大きさを同じにすることができる。
実施形態1の図5に示す二つの枠状分割体22A,22Bで双極板21を挟み込む構成において、双極板21における正極電極4(負極電極5)に対応する部分に凹みを設け、その凹みに正極電極4(負極電極5)を嵌め込む構成としても良い。この構成では、双極板21の正極電極4側(負極電極5側)の凹みと、枠体22の内周端面22iとで嵌込凹部24(25)が形成される。
2 セルフレーム
21 双極板
21c 外周縁部分 21s Oリング(シール部材)
22 枠体
22A,22B 枠状分割体
22c 段差部分 22i 内周端面 22s Oリング(シール部材)
24,25 嵌込凹部 24i,25i 内壁面
123,124 給液用マニホールド 125,126 排液用マニホールド
123s,124s 入口スリット 125s,126s 出口スリット
127 シール部材 127s シール溝
3 リーク流路 30 サイドリーク流路
4 正極電極
4o 外周端面 4os 側端面
5 負極電極
5o 外周端面 5os 側端面
100 セル 101 隔膜 102 正極セル 103 負極セル
100P 正極用循環機構 100N 負極用循環機構
106 正極電解液用タンク 107 負極電解液用タンク
108,109,110,111 導管 112,113 ポンプ
190 給排板
200 セルスタック
200s サブスタック
210,220 エンドプレート
230 締付機構
Claims (4)
- 電極と、
枠体および双極板を備え、前記電極が嵌め込まれる嵌込凹部を有するセルフレームと、
前記電極を前記双極板との間に挟み込む隔膜と、を備えるレドックスフロー電池であって、
前記電極の外周端面のうち、電解液の流通方向に平行な側端面と、前記側端面に対向する前記嵌込凹部の内壁面との間隔が、0.1mm以上12mm以下であるレドックスフロー電池。 - 前記嵌込凹部は、前記枠体の内周端面と、前記電極に対面する前記双極板の一面とで構成される請求項1に記載のレドックスフロー電池。
- 前記嵌込凹部は、前記双極板の一面に形成される凹みによって形成される請求項1または請求項2に記載のレドックスフロー電池。
- 前記間隔は、1.5mm以上3mm以下である請求項1から請求項3のいずれか1項に記載のレドックスフロー電池。
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PCT/JP2016/086643 WO2018105091A1 (ja) | 2016-12-08 | 2016-12-08 | レドックスフロー電池 |
EP16923294.9A EP3553863A4 (en) | 2016-12-08 | 2016-12-08 | REDOX BATTERY |
US15/556,408 US10680254B2 (en) | 2016-12-08 | 2016-12-08 | Redox flow battery |
KR1020187017493A KR20190089718A (ko) | 2016-12-08 | 2016-12-08 | 레독스 플로우 전지 |
JP2018520622A JP6751275B2 (ja) | 2016-12-08 | 2016-12-08 | レドックスフロー電池 |
AU2016432004A AU2016432004B2 (en) | 2016-12-08 | 2016-12-08 | Redox flow battery |
CN201711275634.8A CN108183252B (zh) | 2016-12-08 | 2017-12-06 | 氧化还原液流电池 |
CN201721687089.9U CN207542329U (zh) | 2016-12-08 | 2017-12-06 | 氧化还原液流电池 |
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CN112534614B (zh) * | 2018-08-13 | 2023-08-04 | 住友电气工业株式会社 | 氧化还原液流电池单体及氧化还原液流电池 |
EP3920292A4 (en) * | 2019-01-29 | 2022-06-08 | Sumitomo Electric Industries, Ltd. | BATTERY CELL, CELL STACK AND REDOX FLOW BATTERY |
CN112151827A (zh) * | 2019-11-25 | 2020-12-29 | 国家电投集团科学技术研究院有限公司 | 液流电池的电池单元和具有其的液流电池 |
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