WO2018134927A1 - Plaque bipolaire, châssis de cellule, empilement de cellules et batterie à flux rédox - Google Patents

Plaque bipolaire, châssis de cellule, empilement de cellules et batterie à flux rédox Download PDF

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Publication number
WO2018134927A1
WO2018134927A1 PCT/JP2017/001614 JP2017001614W WO2018134927A1 WO 2018134927 A1 WO2018134927 A1 WO 2018134927A1 JP 2017001614 W JP2017001614 W JP 2017001614W WO 2018134927 A1 WO2018134927 A1 WO 2018134927A1
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WO
WIPO (PCT)
Prior art keywords
bipolar plate
cell
frame
redox flow
electrolyte
Prior art date
Application number
PCT/JP2017/001614
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English (en)
Japanese (ja)
Inventor
山口　英之
本井　見二
Original Assignee
住友電気工業株式会社
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Publication date
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Priority to PCT/JP2017/001614 priority Critical patent/WO2018134927A1/fr
Publication of WO2018134927A1 publication Critical patent/WO2018134927A1/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
    • H01M8/02—Details
    • 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
    • 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 invention relates to a bipolar plate, a cell frame, a cell stack, and a redox flow battery.
  • Patent Documents 1 and 2 describe a cell stack formed by laminating a plurality of cell frames, positive electrodes, diaphragms, and negative electrodes, and a redox flow battery using the cell stack.
  • the cell frame includes a bipolar plate disposed between the positive electrode and the negative electrode, and a frame provided on the outer periphery of the bipolar plate.
  • positive and negative electrodes are arranged between bipolar plates of adjacent cell frames with a diaphragm interposed therebetween, thereby forming one cell.
  • a redox flow battery performs charge and discharge by circulating and circulating an electrolytic solution in a cell in which electrodes are arranged.
  • the bipolar plate of the present disclosure is A bipolar plate on which electrodes of a redox flow battery are arranged,
  • the radius of curvature of the corner when the bipolar plate is viewed in plan is 5 mm or more and 100 mm or less.
  • the cell frame of the present disclosure includes the bipolar plate of the present disclosure and a frame body provided on the outer periphery of the bipolar plate.
  • the cell stack of the present disclosure includes the cell frame of the present disclosure.
  • the redox flow battery of the present disclosure includes the cell stack of the present disclosure.
  • FIG. 5 is a schematic partial cross-sectional view of a cell frame taken along line VI-VI in FIG. 4.
  • redox flow batteries have attracted attention as one of storage batteries that stabilize the output of renewable energy such as sunlight and wind power, and further improvements in productivity and reliability of redox flow batteries are required. .
  • a rectangular bipolar plate is used, and when the bipolar plate is viewed in plan in the thickness direction, each corner is substantially perpendicular and the radius of curvature of each corner is small. For this reason, when the bipolar plate is handled, such as during cell frame assembly work, cracks may occur in the corners, which has been one factor in reducing productivity.
  • the present inventors have studied to round the corners in plan view of the bipolar plate and increase the curvature radius of the corners. However, it has been found that if the radius of curvature of the corner is too large, the following problem may occur.
  • the cell frame has a recess formed inside the frame on which the bipolar plate is provided, and the shape of the recess is usually a shape corresponding to the planar shape of the bipolar plate.
  • An electrode having substantially the same size is accommodated in the recess, and a cell is constituted by a space surrounded by the recess and the diaphragm formed by the bipolar plate and the frame.
  • the distance between the edges between the one edge and the other edge of the bipolar plate is the width direction (the direction along one edge and the other edge). )
  • the edge-to-edge distance at the center in the width direction is longer than at both ends where the corners are provided. That is, the flow path length of the electrolytic solution is longer at the central portion in the width direction than at both ends. If the radius of curvature of the corner is too large, the difference in flow path length between the central portion and both end portions in the width direction becomes large, and the flow length of the electrolytic solution becomes longer at the central portion. Easily overcharged.
  • an object of the present disclosure is to provide a bipolar plate, a cell frame, and a cell stack that can improve the productivity and reliability of a redox flow battery.
  • Another object of the present disclosure is to provide a redox flow battery that has excellent productivity and high reliability.
  • the bipolar plate according to the embodiment is A bipolar plate on which electrodes of a redox flow battery are arranged,
  • the radius of curvature of the corner when the bipolar plate is viewed in plan is 5 mm or more and 100 mm or less.
  • the curvature radius (corner R) of the corner when the bipolar plate is viewed in plan in the thickness direction is 5 mm or more, so that the corner is cracked when the bipolar plate is handled. hard. Therefore, it is possible to suppress the occurrence of cracks at the corners of the bipolar plate at the time of assembling the cell frame, and to improve the productivity of the redox flow battery.
  • the angle R in a plan view of the bipolar plate is 100 mm or less, the difference in the flow path length of the electrolyte can be reduced between the central portion in the width direction of the bipolar plate and the end portion provided with the corner portion. Therefore, the electrolyte is unlikely to be overcharged at the center of the bipolar plate, and damage to the electrodes and the like due to overcharge can be suppressed, so that the reliability of the redox flow battery can be improved.
  • bipolar plate One form of the bipolar plate is that the planar shape of the bipolar plate is rectangular.
  • planar shape of the bipolar plate (the shape when the bipolar plate is viewed in plan in the thickness direction) is a rectangular shape, both edges facing each other have parallel straight sides and the width excluding the corners
  • the flow path length of the electrolyte solution in the central portion in the direction can be made substantially constant over the width direction. Therefore, it is easy to suppress overcharging at the center in the width direction of the bipolar plate.
  • a cell frame according to the embodiment includes the bipolar plate according to the above (1) or (2) and a frame body provided on an outer periphery of the bipolar plate.
  • the productivity and reliability of the redox flow battery can be improved.
  • a cell stack according to the embodiment includes the cell frame described in (3) above.
  • the cell stack includes the cell frame according to the above-described embodiment, the productivity and reliability of the redox flow battery can be improved.
  • a redox flow battery according to the embodiment includes the cell stack described in (4) above.
  • the RF battery 1 shown in FIG. 1 and FIG. 2 uses an electrolytic solution containing, as an active material, a metal ion whose valence changes as a result of oxidation and reduction in the positive electrode electrolyte and the negative electrode electrolyte.
  • the battery performs charging / discharging by utilizing the difference between the redox potential and the redox potential of ions contained in the negative electrode electrolyte.
  • the RF battery 1 as shown in FIG.
  • a case of a vanadium-based RF battery using a vanadium electrolyte solution containing V ions serving as an active material in a positive electrode electrolyte and a negative electrode electrolyte is shown.
  • a solid line arrow in the cell 100 in FIG. 1 indicates a charging reaction, and a broken line arrow indicates a discharging reaction.
  • the RF battery 1 is one of the electrolyte circulation type storage batteries. For example, applications such as load leveling, sag compensation, emergency power supply, etc., and regeneration of solar and wind power, which are being introduced in large quantities. Used for smoothing output of possible energy.
  • 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.
  • a positive electrode 104 is built in the positive electrode cell 102, and a positive electrode electrolyte solution tank 106 for storing the positive electrode electrolyte is connected via conduits 108 and 110.
  • the conduit 108 is provided with a pump 112 that pumps the positive electrode electrolyte to the positive electrode cell 102, and a positive electrode circulation mechanism 100 ⁇ / b> P that circulates the positive electrode electrolyte is constituted by these members 106, 108, 110, and 112. .
  • the negative electrode cell 103 contains a negative electrode 105 and is connected to a negative electrode electrolyte tank 107 for storing a negative electrode electrolyte via conduits 109 and 111.
  • the conduit 109 is provided with a pump 113 for pumping the negative electrode electrolyte to the negative electrode cell 103, and a negative electrode circulation mechanism 100N for circulating the negative electrode electrolyte is constituted by these members 107, 109, 111, 113. .
  • the electrolytes stored in the tanks 106 and 107 are circulated in the cell 100 (the positive electrode cell 102 and the negative electrode cell 103) by the pumps 112 and 113 at the time of charging and discharging, and at the time of standby without charging and discharging. Pumps 112 and 113 are stopped and not circulated.
  • the cell 100 is usually formed inside a structure called a cell stack 2 shown in FIGS.
  • the cell stack 2 is configured by sandwiching a laminate called a sub stack 200 (see FIG. 3) from two sides with two end plates 220 and fastening the end plates 220 on both sides with a fastening mechanism 230 (see FIG. 3 includes a plurality of sub-stacks 200).
  • the sub stack 200 is formed by stacking a plurality of cell frames 3, positive electrodes 104, diaphragms 101, and negative electrodes 105, and supply / discharge plates 210 (see the lower figure in FIG. 3, omitted in FIG. 2) at both ends of the laminated body. It is an arranged configuration.
  • the cell frame 3 includes a bipolar plate 31 disposed between the positive electrode 104 and the negative electrode 105, and a frame body 32 provided on the outer periphery of the bipolar plate 31.
  • the positive electrode 104 is disposed on one surface side of the bipolar plate 31 and the negative electrode 105 is disposed on the other surface side of the bipolar plate 31.
  • the sub stack 200 (cell stack 2), one cell 100 is formed between the bipolar plates 31 of the adjacent cell frames 3 respectively.
  • the bipolar plate 31 is made of, for example, plastic carbon, and the frame body 32 is made of, for example, plastic such as vinyl chloride resin (PVC), polypropylene, polyethylene, fluorine resin, or epoxy resin.
  • PVC vinyl chloride resin
  • the bipolar plate 31 can be formed by a known method such as injection molding, press molding, or vacuum molding.
  • the electrolyte solution flows into the cell 100 through supply / discharge plates 210 (see the lower diagram in FIG. 3), and supply manifolds 33, 34 provided through the frame body 32 of the cell frame 3 shown in FIG. This is performed by the drainage manifolds 35 and 36, the liquid supply slits 33s and 34s formed in the frame 32, and the drainage slits 35s and 36s (see also FIG. 4).
  • the positive electrode electrolyte is supplied from the liquid supply manifold 33 provided at the lower part of the frame body 32 on the one surface side (the paper surface side) of the frame body 32.
  • the negative electrode electrolyte is supplied to the negative electrode 105 from a liquid supply manifold 34 provided in the lower part of the frame 32 through a liquid supply slit 34 s formed on the other surface side (back side of the paper) of the frame 32.
  • the liquid is discharged to the drainage manifold 36 through the drainage slit 36s formed in the upper part of the frame 32.
  • a rectifying portion (not shown) may be formed along the edge at the lower edge and the upper edge inside the frame 32 on which the bipolar plate 31 is provided.
  • the rectifying unit diffuses each electrolytic solution supplied from the liquid supply slits 33 s and 34 s along the lower edge portion of each electrode, or discharges each electrolytic solution discharged from the upper edge portion of each electrode to the drain slits 35 s, It has the function of consolidating to 36s.
  • the electrolytic solution is supplied from the lower side of the bipolar plate 31 and is discharged from the upper side of the bipolar plate 31, and electrolysis is performed from the lower edge portion of the bipolar plate 31 toward the upper edge portion. Liquid flows.
  • a thick line arrow on the left side of the drawing indicates an overall electrolyte flow direction of the electrolyte solution in the bipolar plate 31.
  • a plurality of grooves may be formed on the surface of the bipolar plate 31 in contact with each electrode along the flow direction of the electrolytic solution. Thereby, the distribution
  • the cross-sectional shape of the groove (the cross-sectional shape orthogonal to the flow direction of the electrolyte) is not particularly limited, and examples thereof include a rectangular shape, a triangular shape (V shape), a trapezoidal shape, a semicircular shape, and a semielliptical shape. It is done.
  • annular seal member 37 (see FIGS. 2 and 3) such as an O-ring and a flat packing is disposed between the frame bodies 32 of each cell frame 3 in order to suppress leakage of the electrolyte from the cell 100.
  • a seal groove 38 (see FIG. 4) for arranging the seal member 37 is formed in the frame body 32.
  • the radius of curvature (corner R) of the corner when the bipolar plate 31 is viewed in plan is 5 mm or more and 100 mm or less.
  • the bipolar plate 31 has a shape having a corner 40 when viewed in plan.
  • the planar shape of the bipolar plate 31 is a rectangular shape having four corners 41 to 44, and the lower and upper edges of the bipolar plate 31 that are opposite to each other are straight side portions 45 and 46 that are parallel to each other.
  • Have The bipolar plate 31 has round corners 40 in plan view, and the radius of curvature (corner R) of each of the corners 41 to 44 is not less than 5 mm and not more than 100 mm.
  • the size of the bipolar plate 31 for example, the length in the vertical direction (up and down direction in FIG.
  • the length in the width direction (left and right direction in FIG. 5) is 200 mm or more and 2000 mm or less
  • the thickness is It is 3.0 mm or more and 10.0 mm or less.
  • the cell frame 3 is configured by providing a frame 32 on the outer periphery of the bipolar plate 31.
  • the frame 32 has an opening 50 formed therein, and the bipolar plate 31 is disposed in the opening 50.
  • the frame body 32 has a rectangular frame shape, and the opening 50 is formed in a shape corresponding to the outer shape of the bipolar plate 31. That is, the shape of the opening 50 is substantially the same shape (similar shape) as the planar shape of the bipolar plate 31, and the corner of the inner peripheral edge of the frame 32 where the opening 50 is formed is Like the corner 40, it is rounded and has substantially the same corner R as the bipolar plate 31.
  • a stepped portion 51 in contact with the outer peripheral edge of the bipolar plate 31 is formed at the inner peripheral edge of the frame 32, and the outer peripheral edge of the bipolar plate 31 is disposed at the stepped portion 51 as shown in FIG. 6.
  • the bipolar plate 31 is supported by the frame body 32.
  • a groove is formed in the outer peripheral edge portion of the bipolar plate 31 along the circumferential direction on the surface in contact with the stepped portion 51, and a seal member 52 is disposed in the groove.
  • the seal member 52 can suppress the electrolyte solution from moving between the one surface side and the other surface side of the bipolar plate 31.
  • the cell plate 3 When the cell plate 3 is configured by arranging the bipolar plate 31 in the opening 50 of the frame 32, the surface of the bipolar plate 31 and the inner peripheral surface of the frame 32 are placed inside the frame 32 as shown in FIG. 4. A recess 55 is formed. As shown in FIG. 6, the concave portions 55 are formed on both sides of the bipolar plate 31, and the positive electrode 104 and the negative electrode 105 are respectively stored in the concave portions 55. Each of the electrodes 104 and 105 is formed in substantially the same size as each of the recesses 55. In the case of the cell frame 3 shown in FIG. 4, the shape of the recess 55 provided on one surface side is substantially the same as the planar shape of the bipolar plate 31, and the positive electrode 104 accommodated in the recess 55 (see FIG.
  • the electrodes 104 and 105 are arranged on the cell frame 3, and the cell frame 3 is laminated via the diaphragm 101, whereby the cell stack 2 (see FIG. 3) is configured.
  • the bipolar plate 31 according to the embodiment has the following operational effects. Since the corner portion 40 in the plan view of the bipolar plate 31 is formed in a round shape and the corner R is 5 mm or more, it is possible to prevent the corner portion 40 from being cracked. Therefore, when the bipolar plate 31 is handled at the time of assembling the cell frame 3 or the like, the corner portion 40 is hardly cracked. From the viewpoint of suppressing cracking of the corner portion 40, the corner R is, for example, 10 mm or more.
  • both end portions (corner portions 41) in the width direction. , 42 and the region between the corners 43, 44) and the central portion in the width direction (region between the side portions 45, 46) are different in the flow path length of the electrolyte.
  • the flow path length L2 in the width direction center part of the bipolar plate 31 becomes longer than the flow path length L1 in both ends (L2> L1).
  • the flow path length L2 at the center in the width direction of the bipolar plate 31 is constant over the width direction.
  • the angle R is set to 100 mm or less, and the difference between the flow path length L2 at the center in the width direction and the flow path length L1 at both ends is set within a certain range. Has been. This is because the angle R is 100 mm or less, and the difference in the flow path length of the electrolyte solution between the central portion and both end portions in the 31 width direction of the bipolar plate is small. Electrolytic overcharge can be suppressed. Therefore, it is possible to suppress oxidative damage of the electrode and damage to the diaphragm accompanying heat generation due to overcharging of the electrolytic solution. From the viewpoint of suppressing damage to electrodes and the like due to overcharge, the angle R is, for example, 50 mm or less.
  • the ratio (L2 / L1) between the maximum flow path length L2 and the minimum flow path length L1 is, for example, 1.5 or less, 1.3 or less, and further 1.1 or less.
  • a bipolar plate having a rectangular planar shape was prepared.
  • the size (outside dimension) of the bipolar plate is 250 mm long ⁇ 600 mm wide ⁇ 10.0 mm thick.
  • a plurality of bipolar plates (see FIG. 5) having different corner radii of curvature (angles R) in plan view were prepared.
  • a cell frame (see FIG. 4) was prepared using each bipolar plate, and a plurality of RF batteries (test bodies A to G) were assembled using the cell frame. And about each test body, productivity and reliability were evaluated.
  • Evaluation of productivity was made by visually checking whether or not cracks occurred at the corners of the bipolar plate when 100 cell plates were prepared with each bipolar plate. And in 100 pieces, the case where there was no crack in the corner portion was evaluated as “A”, the case where the number of cracks generated in the corner portion was less than 5, “B”, and the case where it was more than “C” was evaluated. . The results are shown in Table 1.

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Abstract

La présente invention concerne une plaque bipolaire dans laquelle des électrodes d'une cellule à flux rédox sont agencées, les rayons de courbure des coins lorsque la plaque bipolaire est vue selon une vue en plan sont compris entre 5 et 100 mm inclus.
PCT/JP2017/001614 2017-01-18 2017-01-18 Plaque bipolaire, châssis de cellule, empilement de cellules et batterie à flux rédox WO2018134927A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
PCT/JP2017/001614 WO2018134927A1 (fr) 2017-01-18 2017-01-18 Plaque bipolaire, châssis de cellule, empilement de cellules et batterie à flux rédox

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
PCT/JP2017/001614 WO2018134927A1 (fr) 2017-01-18 2017-01-18 Plaque bipolaire, châssis de cellule, empilement de cellules et batterie à flux rédox

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WO2018134927A1 true WO2018134927A1 (fr) 2018-07-26

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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2002246061A (ja) * 2001-02-15 2002-08-30 Sumitomo Electric Ind Ltd レドックスフロー２次電池用セルフレーム構造およびその製造方法
JP2002260600A (ja) * 2001-02-28 2002-09-13 Tdk Corp 電気化学デバイス
JP2005228622A (ja) * 2004-02-13 2005-08-25 Sumitomo Electric Ind Ltd レドックスフロー電池セル
WO2009139389A1 (fr) * 2008-05-15 2009-11-19 株式会社アルバック Procédé de fabrication de module de pile solaire à couches minces et module de pile solaire à couches minces

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2002246061A (ja) * 2001-02-15 2002-08-30 Sumitomo Electric Ind Ltd レドックスフロー２次電池用セルフレーム構造およびその製造方法
JP2002260600A (ja) * 2001-02-28 2002-09-13 Tdk Corp 電気化学デバイス
JP2005228622A (ja) * 2004-02-13 2005-08-25 Sumitomo Electric Ind Ltd レドックスフロー電池セル
WO2009139389A1 (fr) * 2008-05-15 2009-11-19 株式会社アルバック Procédé de fabrication de module de pile solaire à couches minces et module de pile solaire à couches minces

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