WO2017033237A1 - 枠体、レドックスフロー電池用セルフレーム及びレドックスフロー電池 - Google Patents
枠体、レドックスフロー電池用セルフレーム及びレドックスフロー電池 Download PDFInfo
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- WO2017033237A1 WO2017033237A1 PCT/JP2015/073600 JP2015073600W WO2017033237A1 WO 2017033237 A1 WO2017033237 A1 WO 2017033237A1 JP 2015073600 W JP2015073600 W JP 2015073600W WO 2017033237 A1 WO2017033237 A1 WO 2017033237A1
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- slit
- frame
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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
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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
- H01M8/0258—Collectors; Separators, e.g. bipolar separators; Interconnectors characterised by the configuration of channels, e.g. by the flow field of the reactant or coolant
-
- 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
- H01M8/02—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
- H01M8/04—Auxiliary arrangements, e.g. for control of pressure or for circulation of fluids
- H01M8/04276—Arrangements for managing the electrolyte stream, e.g. heat exchange
- H01M8/04283—Supply means of electrolyte to or in matrix-fuel cells
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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
- H01M8/20—Indirect fuel cells, e.g. fuel cells with redox couple being irreversible
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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
- H01M8/2465—Details of groupings of fuel cells
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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 frame used for a redox flow battery cell, a cell frame for a redox flow battery, and a redox flow battery.
- a redox flow battery cell frame that can improve the heat dissipation of the electrolyte while reducing the shunt current loss through the electrolyte in the slit provided in the frame, and can suppress the occurrence of distortion at the slit forming portion.
- a redox flow battery cell frame that can improve the heat dissipation of the electrolyte while reducing the shunt current loss through the electrolyte in the slit provided in the frame, and can suppress the occurrence of distortion at the slit forming portion.
- a redox flow battery (hereinafter sometimes referred to as “RF battery”) is known (see Patent Documents 1 and 2).
- Applications of redox flow batteries include load leveling applications, applications such as instantaneous voltage drop compensation and emergency power supplies, and smoothing of natural energy output such as solar power generation and wind power generation that are being introduced in large quantities. Can be mentioned.
- An RF battery is a battery that performs charge and discharge using an electrolyte containing a metal ion (active material) whose valence is changed by oxidation and reduction in the positive electrode electrolyte and the negative electrode electrolyte.
- FIG. 9 shows an operation principle diagram of a vanadium-based RF battery 300 using a vanadium electrolyte containing V ions as an active material in the positive electrode electrolyte and the negative electrode electrolyte.
- a solid line arrow in the battery cell 100 in FIG. 9 indicates a charging reaction, and a broken line arrow indicates a discharging reaction.
- the RF battery 300 includes a cell 100 separated into a positive electrode cell 102 and a negative electrode cell 103 by an ion exchange membrane 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 negative electrode cell 103 contains a negative electrode 105 and is connected to a negative electrode electrolyte tank 107 for storing the negative electrode electrolyte via conduits 109 and 111. Then, the electrolytes stored in the tanks 106 and 107 are circulated and circulated to the cell 100 (the positive electrode cell 102 and the negative electrode cell 103) by the pumps 112 and 113 to perform charging and discharging.
- the RF battery 300 normally has a configuration including a cell stack in which a plurality of cells 100 are stacked.
- FIG. 10 is a schematic configuration diagram of a cell stack.
- a cell stack 10S illustrated in FIG. 10 includes a plurality of cell frames 20 each having a bipolar plate 21 provided inside a rectangular frame 22, a positive electrode 104, an ion exchange membrane 101, and a negative electrode 105.
- the laminate is sandwiched between two end plates 250 and tightened.
- An opening is formed inside the frame body 22, and the cell frame 20 has a recess formed inside the frame body 22 by fitting the bipolar plate 21 into the opening of the frame body 22.
- a recess (chamber) 24 is formed inside the frame body 22 by the inner peripheral surface of the frame body 22 and the surface of the bipolar plate 21, and the positive electrode 104 is provided on one surface side of the bipolar plate 21.
- the negative electrode 105 is disposed on the other surface side.
- the frame body 22 has a rectangular frame shape constituted by a pair of upper and lower long pieces facing each other and a pair of left and right short pieces connecting ends of the long pieces.
- An electrode (positive electrode 104 or negative electrode 105) is accommodated in a chamber 24 formed inside the frame 22, and an internal space of the chamber 24 surrounded by the bipolar plate 21, the frame 22, and the ion exchange membrane 101 is formed.
- a cell positive electrode cell or negative electrode cell.
- a pair of positive and negative electrodes 104 and 105 are arranged between adjacent cell frames 20 with an ion exchange membrane 101 interposed therebetween, thereby making one cell (single cell). 100 will be formed.
- the circulation of the electrolytic solution in the cell stack 10S is performed by the manifold 200 formed through the frame body 22 and the slit 210 formed on the surface of the frame body 22 and connecting the manifold 200 and the chamber 24.
- One end of the slit 210 is connected to the manifold 200, and the other end is connected to the chamber 24.
- the positive electrode electrolyte is stored in the chamber 24 in which the positive electrode 104 is accommodated from the liquid supply manifold 201 through the liquid supply slit 211 formed on the one surface side (paper surface side) of the frame body 22. , Flows through the chamber 24, and is discharged to the drainage manifold 203 through the drainage slit 213.
- the negative electrode electrolyte is supplied from the liquid supply manifold 202 to the chamber in which the negative electrode 105 is accommodated via the liquid supply slit 212 formed on the other surface side (the back side of the paper) of the frame body 22, and the liquid discharge slit.
- the liquid is discharged from the chamber to the drainage manifold 204 through 214.
- an annular seal member 50 such as an O-ring or a flat packing is disposed along the outer edge portion of the frame body 22 in order to suppress leakage of the electrolytic solution.
- JP 2013-80613 A Japanese Patent Laid-Open No. 2002-246061
- a shunt current flows through the electrolyte in the slit and a loss due to the shunt current (shunt current loss) occurs.
- One means for reducing this shunt current is to increase the electrical resistance of the electrolytic solution in the slit by increasing the length of the slit serving as the flow path of the electrolytic solution. Therefore, conventionally, from the viewpoint of reducing the shunt current loss, there is a case where means for increasing the length of the slit is provided by providing a curved portion in a part of the slit as compared with the linear slit. “The length of the slit” means the length measured along the slit from one end to the other end of the slit when the cell frame (frame body) is viewed in plan.
- the slit is provided with a curved part and the length of the slit is increased. If the electrolyte is filled in the slit, such as during operation or standby of the RF battery, the shunt current is small in the electrolyte. Will flow. Due to the shunt current, the electrolytic solution may generate heat, and the temperature of the electrolytic solution may increase. In particular, when the RF battery is on standby, since the electrolytic solution remains in the slit, the temperature of the electrolytic solution is likely to rise in the slit as compared with the operation in which the electrolytic solution is circulated.
- the RF battery cell frame is subjected to tensile stress in the longitudinal and width directions of the pieces constituting the frame, and this stress. causes distortion.
- the slit forming part of the frame is thin and easily distorted, and if excessive stress is applied, such as stress concentration tends to occur at the corners of the slit cross section, cracks will start from the slit. easy. Therefore, it is desired to suppress the occurrence of distortion at the slit forming portion.
- “Slit cross section” means a cross section orthogonal to the flow direction of the electrolyte.
- the present invention has been made in view of the above circumstances, and one of the objects of the present invention is to reduce the shunt current loss through the electrolytic solution in the slit in the frame of the redox flow battery cell, and perform electrolysis.
- An object of the present invention is to provide a frame that can improve the heat dissipation of the liquid and suppress the occurrence of distortion at the slit forming portion.
- a frame according to an aspect of the present invention is a frame used for a redox flow battery cell, an opening formed inside the frame, a manifold through which an electrolyte flows, the manifold and the opening And a slit that forms a flow path for the electrolyte between the manifold and the opening.
- the slit has at least one curved portion, and the radius of curvature of the at least one curved portion is 2.0 mm or more and 200 mm or less.
- a cell frame for a redox flow battery includes the frame according to an aspect of the present invention and a bipolar plate fitted into an opening of the frame, and the frame and the bipolar plate A chamber is formed inside the frame.
- the redox flow battery according to one aspect of the present invention includes the cell frame for a redox flow battery according to one aspect of the present invention.
- the frame body can improve the heat dissipation of the electrolyte while reducing the shunt current loss through the electrolyte in the slit, and can suppress the occurrence of distortion at the slit forming portion.
- the cell frame for the redox flow battery and the redox flow battery can improve the heat dissipation of the electrolyte while reducing the shunt current loss through the electrolyte in the slit provided in the frame constituting the cell, and the slit forming portion. It is possible to suppress the occurrence of distortion in the case.
- FIG. 2 is a schematic front view of a frame according to Embodiment 1.
- FIG. It is a schematic front view of a cell frame provided with the frame concerning Embodiment 1.
- FIG. 3 is a schematic enlarged cross-sectional view illustrating a cross-sectional shape of a slit in the frame body according to the first embodiment.
- It is a schematic front view of the frame concerning Embodiment 2.
- It is a schematic front view of the frame concerning Embodiment 3.
- It is a model figure of the slit used for evaluation of the trial calculation example 1.
- FIG. It is a figure explaining the method of calculating the distortion amount of a music part in the trial calculation example 1.
- FIG. It is a model figure of the slit used for evaluation of the trial calculation example 2.
- FIG. It is an operation
- the present inventors can improve the heat dissipation of the electrolyte solution in the slit and, more particularly, the configuration of the curved portion that can suppress the occurrence of distortion at the slit forming portion, particularly with respect to the slit having the curved portion provided in the frame.
- the radius of curvature of the part was examined. And the following knowledge was acquired.
- the radius of curvature of the curved portion of the slit when the radius of curvature of the curved portion of the slit is large, when a tensile stress is applied to the frame due to hydraulic pressure or thermal expansion, it acts in the normal direction (slit width direction) at the curved portion of the slit.
- the force component increases.
- stress is applied in one direction (eg, the longitudinal direction) of the pieces constituting the frame, the curved portion of the slit is decomposed into force components in the normal direction and the tangential direction.
- the slit forming portion of the frame body is likely to be distorted with respect to the force in the width direction of the slit, when the curvature radius of the curved portion of the slit is large, distortion is likely to occur in the curved portion forming portion, and cracks are likely to occur. .
- a frame according to an aspect of the present invention is a frame used for a cell of a redox flow battery, wherein an opening formed inside the frame, a manifold through which an electrolyte flows, and the manifold And a slit for connecting the opening and forming a flow path for the electrolyte between the manifold and the opening.
- the slit has at least one curved portion, and the radius of curvature of the at least one curved portion is 2.0 mm or more and 200 mm or less.
- the slit has at least one curved portion, so that the length of the slit can be increased compared to the linear slit, and the shunt current loss through the electrolyte in the slit can be reduced. Can be reduced. Furthermore, since the curvature radius of a curved part satisfy
- the radius of curvature of the curved portion is 2.0 mm or more, the curved portion formation area in the plane of the frame is large, and the heat of the electrolyte easily escapes to the frame at the curved portion forming portion. It's hard to get stuck Therefore, the heat dissipation of the electrolytic solution can be improved, and the temperature rise of the electrolytic solution can be suppressed. Therefore, precipitation of the electrolyte component can be suppressed, and softening and deformation of the frame can be suppressed.
- the curvature radius of the curved portion is 200 mm or less
- the normal direction (slit width direction) of the curved portion of the slit Since the force is dispersed in the tangential direction, the stress acting in the width direction of the slit is reduced at the curved portion forming portion. Therefore, generation
- the curvature radius of the curved portion is preferably 10 mm or more and 60 mm or less, for example.
- the slit may have a connecting portion having a radius of curvature exceeding 200 mm between the curved portion located closest to the opening among the curved portions and the opening. Can be mentioned.
- the received inertia can be relaxed, and the disturbance of the flow of the electrolyte introduced into the chamber can be suppressed. Therefore, the rectifying effect that suppresses the disturbance of the flow of the electrolyte introduced into the chamber is obtained by the connecting portion.
- the flow rate distribution of the electrolyte in the chamber can be made uniform.
- the length of the said connection part is 5.0 mm or more and 200 mm or less.
- the length of the connecting portion when the length of the connecting portion is 5.0 mm or more, the disturbance of the flow of the electrolyte introduced into the chamber can be effectively suppressed, and a high rectifying effect can be obtained.
- the length of the connecting portion when the length of the connecting portion is 200 mm or less, when tensile stress is applied to the frame body due to fluid pressure or thermal expansion, the stress acting on the entire connecting portion of the slit is reduced. Therefore, generation
- the length of the connecting portion is preferably 10 mm or more and 50 mm or less, for example.
- the depth of the said slit is 0.5 mm or more and 10 mm or less.
- the depth of the slit when the depth of the slit is 10 mm or less, it is possible to suppress a decrease in strength due to a decrease in thickness in the slit forming portion of the frame, and it is possible to further suppress the occurrence of distortion and cracks due to hydraulic pressure and thermal expansion. . Moreover, when the depth of the slit is 10 mm or less, the stress acting on the slit is reduced, and the amount of strain is easily reduced.
- the depth of the slit is preferably, for example, from 1.0 mm to 5.0 mm.
- the “slit depth” means the length in the vertical direction (that is, the thickness direction of the frame) from the opening to the bottom of the slit in the slit cross section.
- the “slit width” means the width of the opening in the slit cross section.
- variety of the said slit is 0.5 mm or more and 20 mm or less.
- the slit width is 0.5 mm or more
- the depth of the slit is constant
- the cross-sectional area is increased, and the pressure loss can be reduced.
- the larger the cross-sectional area the better the rectifying effect.
- the width of the slit is 20 mm or less, it is possible to suppress a decrease in strength in the slit forming portion of the frame, and it is possible to further suppress the occurrence of distortion and cracks due to hydraulic pressure and thermal expansion.
- variety of a slit is 20 mm or less, the emitted-heat amount of the electrolyte solution in a slit can be suppressed, and it is easy to suppress the temperature rise of electrolyte solution.
- the slit forming portion of the frame can be reduced by setting the slit width to 20 mm or less, the frame and thus the cell frame can be downsized.
- the width of the slit is preferably 1.0 mm or greater and 8.0 mm or less, for example.
- the frame has a pair of long pieces facing each other and a pair of short pieces connecting ends of the long pieces, and at least one of the curved portions is formed on the long pieces. It is mentioned that.
- a curved part forming piece When the curved part of the slit is formed on the long piece of the frame, compared with the case where it is formed on the short piece, one end of the piece in which the curved part is formed from the curved part (hereinafter referred to as a curved part forming piece) or the other The distance to the end can be increased. The longer the distance, the more the frame forming material that exists from the bent part to one end or the other end of the bent part forming piece, and therefore stress in the longitudinal direction of the bent part forming piece due to hydraulic pressure or thermal expansion. When this occurs, distortion hardly occurs and the generation of cracks is suppressed. Therefore, according to the said form, generation
- the frame body As one form of the frame body, it has a pair of long pieces facing each other and a pair of short pieces connecting the ends of the long pieces, and at the corner where the long pieces and the short pieces intersect. It is mentioned that at least one of the curved portions is formed.
- a cell frame for a redox flow battery includes the frame according to any one of (1) to (7) above and a bipolar plate that is fitted into an opening of the frame.
- a chamber is formed inside the frame by the frame and the bipolar plate.
- the frame according to one aspect of the present invention is provided, in the frame constituting the cell of the redox flow battery, it is possible to reduce the shunt current loss through the electrolytic solution in the slit while performing electrolysis.
- the heat dissipation of the liquid can be improved and the occurrence of distortion at the slit forming portion can be suppressed.
- a redox flow battery according to an aspect of the present invention includes the cell frame for a redox flow battery described in (8) above.
- the cell frame according to an aspect of the present invention since the cell frame according to an aspect of the present invention is provided, in the frame constituting the cell, the heat dissipation of the electrolyte can be reduced while reducing the shunt current loss through the electrolyte in the slit. And the generation of distortion at the slit forming portion can be suppressed.
- the frame body 22 illustrated in FIG. 1 has a rectangular frame shape having a pair of long pieces 22L facing each other and a pair of short pieces 22S connecting the ends of the long pieces 22L, and an opening 22o is formed inside thereof. ing. A bipolar plate 21 to be described later is fitted into the opening 22o.
- the frame body 22 may be formed of plastic or rubber such as vinyl chloride resin, polypropylene, polyethylene, fluorine resin, or epoxy resin.
- the frame body 22 is formed on the surface of the manifold 200 (manifolds 201 to 204) through which the electrolyte solution flows and passes through the front and back surfaces, and forms a flow path for the electrolyte solution between the manifold 200 and the opening 22o.
- Slit 210 slits 211 to 214.
- the manifold 200 and the slit 210 can be formed at the same time when the frame 22 is formed by injection molding, for example.
- the manifolds 201 and 202 are formed on one long piece 22L (the lower long piece in FIG. 1) of the frame 22, and the manifolds 203 and 204 are the other long piece 22L (the upper long piece in FIG. 1). ).
- the slits 211 and 213 are formed on one side of the frame 22, the slit 211 is formed on one long piece 22 ⁇ / b> L, and the slit 213 is formed on the other long piece 22 ⁇ / b> L.
- the slits 212 and 214 are formed on the other surface side of the frame 22, the slit 212 is formed in one long piece 22 ⁇ / b> L, and the slit 214 is formed in the other long piece 22 ⁇ / b> L.
- One end of each slit 211 to 214 is connected to each manifold 201 to 204, and the other end is connected to the opening 22o.
- Each slit 211 to 214 is formed inside each manifold 201 to 204 and the frame body 22, respectively. The opening 22o is connected.
- the cell frame 20 illustrated in FIG. 2 includes a frame body 22 and a bipolar plate 21 that is fitted into the opening 22o (see FIG. 1) of the frame body 22.
- a frame body 22 is formed so as to sandwich the peripheral portion of the bipolar plate 21 from the front and back, and the frame body 22 is integrated with the outer periphery of the bipolar plate 21 by injection molding or the like.
- a recess is formed by the frame body 22 and the bipolar plate 21.
- a chamber 24 in which an electrode (not shown) is accommodated inside the frame body 22 is formed by the inner peripheral surface of the frame body 22 and the surface of the bipolar plate 21.
- FIG. 2 only the chamber 24 on one side (the front side of the drawing) of the cell frame 20 is illustrated, but the chamber is also formed on the other side (the back side of the drawing).
- a positive electrode is housed in a chamber on one side of the cell frame 20
- a negative electrode is housed in a chamber on the other side
- a positive electrode is placed on one side of the bipolar plate 21, and a negative electrode is placed on the other side (see FIG. 10).
- the bipolar plate 21 can be made of plastic carbon.
- the manifolds 201 and 203 are a supply manifold and a discharge manifold for the positive electrode electrolyte
- the slits 211 and 213 are a supply slit for the positive electrode electrolyte and It is a drainage slit
- Manifolds 202 and 204 are a supply manifold and a drainage manifold for the negative electrode electrolyte
- slits 212 and 214 are a supply slit and a drainage slit for the negative electrode electrolyte.
- Each liquid supply slit 211, 212 extending from each liquid supply manifold 201, 202 is connected to the lower edge of the chamber 24 (opening 22o (see FIG. 1)), and each liquid discharge slit extending from each liquid discharge manifold 203, 204. 213 and 214 are connected to the upper edge of the chamber 24 (opening 22o). That is, the electrolytic solution is introduced into the chamber 24 from the lower side of the chamber 24, and the electrolytic solution is discharged from the upper side of the chamber 24.
- a rectification unit (not shown) is formed along the edge at the lower edge and the upper edge of the chamber 24.
- the rectifying unit diffuses the electrolyte introduced from the liquid supply slits 211 and 212 along the lower edge of the chamber 24, and discharges the electrolyte discharged from the upper edge of the chamber 24 to the drain slits 213 and 214. It has a function to aggregate. By this rectifying portion, the electrolyte solution flows in the chamber 24 from the lower edge portion of the chamber 24 toward the upper edge portion.
- positive and negative electrolytes known electrolytes can be used.
- a positive / negative electrolytic solution a combination of a V-based electrolytic solution containing V ions as a positive electrode and negative electrode active material, a Fe / Cr-based electrolytic solution containing Fe ions as a positive electrode active material, and Cr ions as a negative electrode active material
- a Ti / Mn electrolyte containing Mn ions as the positive electrode active material and Ti ions as the negative electrode active material.
- a plastic protection plate 40 that protects the ion exchange membrane may be disposed at a portion of the frame body 22 where the slits 211 to 214 are formed.
- the protection plate 40 is disposed on the surface of the long piece 22L of the frame 22 so as to cover the slits 211 to 214, and each protection plate 40 has a through-hole or notch at a position corresponding to each manifold 201 to 204. Is formed.
- the protection plate 40 disposed on one surface side of the frame 22 in which the slits 211 and 213 for the positive electrode electrolyte are formed is connected to the manifolds 201 and 203 for the positive electrode electrolyte.
- a circular through hole is formed, and rectangular notches are formed in the manifolds 202 and 204 for the negative electrode electrolyte.
- rectangular cutouts are formed with respect to the manifolds 201 and 203 for the positive electrode electrolyte.
- the protective plate 40 prevents the slits 211 to 214 from coming into contact with the ion exchange membrane. Can be prevented from being damaged.
- FIG. 2 only the protective plate 40 that covers the slits 211 and 213 formed on one surface side of the frame body 22 is illustrated, but a protective plate is also disposed on the other surface side of the frame body 22, and the slits 212, 214 is covered with a protective plate.
- (Slit planar shape) 1 is an enlarged plan view of the slit 210 (211) in the frame according to the first embodiment.
- the planar shape of the slit 211 is shown as a representative.
- FIG. 3 shows a cross-sectional shape of the slit 210, and is a schematic enlarged cross-sectional view taken along line III-III in the circled view of FIG.
- the slit 210 has at least one curved portion 35.
- the planar shape of the slit 210 according to the first embodiment will be described in more detail with reference to FIGS. 1 and 3.
- the slit 210 (211) of Embodiment 1 has one curved portion 35 and a connecting portion 36 between the curved portion 35 and the opening 22o (the chamber 24 in the cell frame 20 shown in FIG. 2).
- the slit 210 of the first embodiment is formed in an L shape as shown in FIG. 1, and the longitudinal direction of the long piece 22 ⁇ / b> L of the frame body 22 from the manifold 200 (201) (leftward in FIG. 1). ), A curved portion 35 connected to the linear portion, and a connecting portion 36 extending in the width direction of the long piece 22L (a direction orthogonal to the longitudinal direction).
- the curved portion 35 has a curvature radius r of 2.0 mm or more and 200 mm or less.
- the curved portion 35 has an arc shape, and the central angle ⁇ of the curved portion 35 is substantially a right angle (90 °).
- the “center angle of the curved portion” means an angle formed by two line segments respectively connecting the center of the radius of curvature of the curved portion and one end and the other end of the curved portion.
- the curvature radius r of the curved portion 35 is preferably 10 mm or more and 60 mm or less.
- the connecting portion 36 includes a case where the radius of curvature is more than 200 mm (the curvature is less than 1/200) and is linear (the curvature is 0). In the slit 210 shown in FIG. 1, the connecting portion 36 is linear.
- the length a of the connecting portion 36 is preferably 5.0 mm or greater and 200 mm or less, and more preferably 10 mm or greater and 50 mm or less.
- the cross-sectional shape of the slit 210 is rectangular as shown in FIG.
- the cross-sectional shape of the slit 210 is not limited to a rectangular shape, and may be, for example, a quadrangular shape such as an isosceles trapezoidal shape, a triangular shape such as an isosceles triangular shape, a semicircular shape or a semielliptical shape.
- the opening side is the bottom side, such as a trapezoidal shape with the opening as the long side and the bottom as the short side, or a triangle with the bottom as the apex and the opening as the base.
- the shape is wider than that.
- angular part of a slit cross section may be chamfered, and the corner
- the depth h of the slit 210 is preferably 0.5 mm or more and 10 mm or less, and more preferably 1.0 mm or more and 5.0 mm or less.
- the width w of the slit 210 is preferably 0.5 mm or more and 20 mm or less, and more preferably 1.0 mm or more and 8.0 mm or less.
- the frame body 22 (cell frame 20) according to the first embodiment has the curved portion 35 in a part of the slit 210, thereby making the slit length longer than that in the case of forming one linear slit. And the shunt current loss can be reduced. Furthermore, since the curvature radius r of the curved part 35 is 2.0 mm or more and 200 mm or less, the heat dissipation of the electrolyte solution in the slit can be improved and the occurrence of distortion at the slit forming part can be suppressed.
- the curvature radius r of the curved portion 35 is 2.0 mm or more, the formation region of the curved portion 35 on the plane of the frame body 22 (long side 22L) (hatching in the circled view in FIG. 1 is performed). And the heat capacity at the formation portion of the curved portion 35 is increased. Therefore, the amount of heat released from the electrolytic solution can be increased at the curved portion forming portion, and heat is hardly accumulated. Therefore, since the heat dissipation of the electrolytic solution can be improved and the temperature rise of the electrolytic solution can be suppressed, precipitation of the electrolytic solution component can be suppressed, and the softening and deformation of the frame can be suppressed.
- the radius of curvature r of the curved portion 35 is 200 mm or less
- the curved portion 35 of the slit 210 has a normal direction (slit The component of force acting in the width direction) is reduced.
- the stress acting in the width direction of the slit is reduced. Therefore, generation
- the slit 210 liquid supply slit 211
- the connection portion 36 since the slit 210 (liquid supply slit 211) has the connection portion 36, the inertia received when the electrolytic solution passes through the curved portion 35 is relaxed, and the flow of the electrolytic solution introduced into the chamber 24 is disturbed. Can be suppressed.
- the length a of the connecting portion 36 is 5.0 mm or more, the disturbance of the flow of the electrolyte introduced into the chamber 24 can be effectively suppressed, and a high rectifying effect can be obtained.
- the length a of the connecting portion 36 is 200 mm or less, the total stress acting in the vicinity of both sides of the slit of the connecting portion 36 can be reduced when a tensile stress is applied. Therefore, generation
- the cross-sectional area can be increased and the pressure loss can be reduced when the width w is constant. Further, since the width w of the slit 210 is 0.5 mm or more, the cross-sectional area can be increased and the pressure loss can be reduced when the depth h is constant. By reducing the pressure loss, the inertia received when the electrolytic solution passes through the curved portion 35 is reduced, so that the rectifying effect by the connecting portion 36 can be improved.
- the depth h of the slit 210 is 10 mm or less and the width w of the slit 210 is 20 mm or less, a decrease in strength at the slit forming portion of the frame body 22 can be suppressed, and distortion and cracks due to hydraulic pressure and thermal expansion are generated. Can be further suppressed.
- Embodiment 2 In the first embodiment illustrated in FIG. 1, the configuration in which the curved portion 35 of the slit 210 is formed in the long piece 22 ⁇ / b> L of the frame 22 has been described as an example.
- the curved part 35 is formed in the corner
- the slit 210 of the second embodiment shown in FIG. 4 is formed in a J shape, the curved portion 35 is a semicircular arc, and the central angle of the curved portion 35 is approximately 180 °.
- the connection portion 36 of the liquid supply slits 211 and 212 is connected to the lower end portion of the side edge of the opening 22o, and the connection portion 36 of the drainage slits 213 and 214 is the opening 22o. It is connected to the upper end of the side edge.
- the corner portion 22C of the frame body 22 is not easily deformed by tensile stress caused by hydraulic pressure or thermal expansion.
- the curved portion 35 of the slit 210 is formed in the corner portion 22C, distortion is hardly generated in the curved portion forming portion.
- Embodiment 3 In the first embodiment illustrated in FIG. 1, the configuration in which the slit 210 includes one curved portion 35 has been described as an example, but the number of the curved portions 35 may be plural. In Embodiment 3 shown in FIG. 5, a configuration in which the slit 210 has a plurality of curved portions 35 will be described.
- the slit 210 of the third embodiment shown in FIG. 5 has a plurality of curved portions 35, and has a connecting portion 36 between the curved portion 35c located closest to the opening 22o and the opening 22o among the curved portions 35. Since the slit 210 has the plurality of curved portions 35, the slit length can be made longer and the shunt current loss can be further reduced. Examples of the central angle of the curved portion 35 include 60 ° to 300 °, and more preferably 80 ° to 280 °.
- a redox flow battery including the cell frame according to the embodiment described above will be described.
- the cell frame When the cell frame is applied to a redox flow battery, it is used in the form of a cell stack (see FIG. 10) in which a plurality of cell frames, positive electrodes, ion exchange membranes, and negative electrodes are stacked. And it is mentioned that a redox flow battery is set as the structure provided with this cell stack.
- Example 1 The heat radiation performance and the amount of distortion when the curvature radius of the curved portion in the slit was changed were evaluated.
- the evaluation conditions are as follows.
- the heat dissipation performance and the amount of strain in the were analyzed and evaluated.
- the cross-sectional shape of the slit 210 was rectangular, the depth h was 1 mm, and the width w was 4 mm.
- Heat dissipation performance The heat dissipation performance was evaluated by the ratio (the temperature increase rate ⁇ T described later) between the calorific value of the electrolyte in the curved portion 35 and the heat capacity of the portion of the frame 22 where the curved portion 35 is formed.
- the calorific value Q of the electrolyte in the bent portion 35 and the heat capacity C of the portion where the bent portion 35 is formed were determined as follows.
- the calorific value of the electrolyte is obtained from the electric resistance R ( ⁇ ) of the electrolyte in the curved portion 35 and the slit voltage v (V).
- the electrical resistance R is calculated by the following equation, where the resistivity of the electrolytic solution is ⁇ ( ⁇ ⁇ cm).
- R ⁇ ⁇ ( ⁇ r / 2) ⁇ (1 / wh)
- the calorific value Q is calculated by the following equation.
- the resistivity ⁇ used in the above formula is 3.82 ⁇ ⁇ cm based on the resistivity of the V-based electrolyte used as the electrolyte for the RF battery.
- the voltage v between the slits is set to 10.5 V from a voltage obtained by stacking 30 cells of a general RF battery.
- the heat capacity of the curved part formation The heat capacity C (J / ° C.) is obtained from the specific heat capacity Cp (J / cm 3 ⁇ ° C.) of the frame body 22 and the volume V (cm 3 ) of the curved portion forming portion.
- the volume V is a volume in the formation region of the curved portion 35 in the frame body 22 (region indicated by cross-hatching in FIG. 6), and is calculated by the following equation.
- the thickness t of the frame body 22 is 5 mm.
- V ( ⁇ r 2/ 4) ⁇ t
- the heat capacity C is calculated by the following formula.
- the specific heat c and specific gravity d used in the above calculation formula assume that the frame 22 is made of vinyl chloride resin, and the specific heat c is 840 J / kg ⁇ ° C. and the specific gravity d is 1.4 g / cm 3 .
- the load P (N) is a load due to a unit hydraulic pressure p (N / mm) applied to a minute section of the central angle d ⁇ of the curved portion 35 on the XY plane, 0 ⁇ ⁇ ⁇ ⁇ / 2. It was obtained by integrating in the range of.
- the load P when the load P is divided into the X direction and the Y direction shown in FIG. 7, the load P can be expressed as a product of the unit hydraulic pressure p and the curvature radius r by the following equation.
- Example 2 The rectifying effect and the amount of distortion were evaluated when the length of the connecting portion in the slit was changed.
- the evaluation conditions are as follows.
- the length a of the connecting portion 36 is changed in the range of 1.0 mm to 300 mm using the model of the slit 210 having the curved portion 35 and the connecting portion 36 as shown in FIG.
- the rectification effect and distortion amount at the connection portion 36 were analyzed and evaluated.
- the cross-sectional shape of the slit 210 was rectangular, the depth h was 1 mm, and the width w was 4 mm.
- the rectifying effect was evaluated by the ratio of the centrifugal force acting on the electrolyte passing through the curved portion 35 and the length of the connecting portion 36 (a drifting action D described later).
- the centrifugal force F acting on the electrolytic solution was determined as follows.
- Centrifugal force of electrolyte Centrifugal force F (N / m 3 ) is calculated by the following equation, where m (kg / m 3 ) is the specific gravity of the electrolyte and u (m / s) is the flow rate of the electrolyte.
- F m ⁇ (u 2 / r)
- the flow velocity u (m / s) is given by the following equation when the flow rate of the electrolyte is Q (L / min).
- u Q / (h ⁇ w)
- the specific gravity m used in the above formula is 1400 kg / m 3 and the flow rate Q is 1 L / min.
- the amount of strain was evaluated based on the total load P due to the hydraulic pressure applied to the formation part of the connection part 36.
- the unit hydraulic pressure p (N / mm) is given by [ ⁇ ⁇ h] as the product of the hydraulic pressure ⁇ (MPa) and the slit depth h (mm), as in the trial calculation example 1.
- the hydraulic pressure ⁇ is 0.5 MPa.
- the connecting portion 36 is linear and has a length a of 50 mm.
- the slit 210 has a rectangular cross section and a width w of 4 mm.
- the rectifying effect is calculated by using the calculation formula described in the trial calculation example 2 and calculating the drifting action D (N / m 4 ) when the slit depth h is changed in the range of 0.1 mm to 15 mm. Based on the evaluation.
- the evaluation of the rectifying effect is “A” when the value of the drift action D is 5.0 ⁇ 10 7 (N / m 4 ) or less, and “B” when the value of 1.0 ⁇ 10 8 (N / m 4 ) or less. ”And the others were designated“ C ”.
- Table 3 shows the value of the drift action D and the evaluation of the rectification effect.
- Example 4 The rectification effect and heat dissipation performance when the width of the slit was changed were evaluated.
- the evaluation conditions are as follows.
- the width of the slit 210 is changed in the range of 0.1 mm to 25 mm, the rectification effect by the connection part 36 and the curved part 35 are obtained.
- the heat dissipation performance at was analyzed and evaluated.
- the connecting portion 36 is linear and has a length a of 100 mm.
- the cross-sectional shape of the slit 210 was rectangular, and the depth h was 1 mm.
- the rectifying effect is calculated based on the drifting action D (N / m 4 ) when the slit width w is changed in the range of 0.1 mm to 25 mm using the calculation formula described in the trial calculation example 2. And evaluated. Evaluation of the rectifying effect is “A” when the value of the drifting action D is 5.0 ⁇ 10 8 (N / m 4 ) or less, and “B” when the value of 1.0 ⁇ 10 10 (N / m 4 ) or less. ”And the others were designated“ C ”. Table 4 shows the value of the drifting action D and the evaluation of the rectifying effect.
- the heat dissipation performance was calculated based on the temperature rise rate ⁇ T (° C / s) when the slit width w was changed in the range of 0.1 mm to 25 mm using the calculation formula described in the trial calculation example 1. And evaluated.
- the evaluation of heat dissipation performance is “A” when the temperature rise rate ⁇ T is 5.0 (° C./s) or less, “B” when it is 8.0 (° C./s) or less, and “C” otherwise.
- Table 4 shows the value of the temperature rise rate ⁇ T and the evaluation of the heat dissipation performance.
- the frame body and cell frame of the present invention can be suitably used as a component part of a redox flow battery.
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Abstract
Description
本発明者らは、枠体に設けられた曲部を有するスリットに関して、スリット内の電解液の放熱を改善できると共に、スリット形成部分での歪の発生を抑制できる曲部の構成、特に、曲部の曲率半径について検討を試みた。そして、以下のような知見を得た。
本発明の実施形態に係る枠体、並びにレドックフロー電池用セルフレームの具体例を、以下に図面を参照しつつ説明する。図中の同一符号は同一又は相当部分を示す。なお、本発明はこれらの例示に限定されるものではなく、特許請求の範囲によって示され、特許請求の範囲と均等の意味および範囲内でのすべての変更が含まれることが意図される。
〈枠体〉
図1~図3を参照して、実施形態1に係る枠体及びセルフレームについて説明する。図1に例示する枠体22は、互いに対向する一対の長片22Lと、長片22Lの端部同士を繋ぐ一対の短片22Sとを有する矩形枠状であり、その内側に開口22oが形成されている。この開口22oには、後述する双極板21が嵌め込まれる。枠体22は、例えば塩化ビニル樹脂、ポリプロピレン、ポリエチレン、フッ素樹脂、エポキシ樹脂などのプラスチックやゴムで形成することが挙げられる。
マニホールド201,202は枠体22の一方の長片22L(図1では下側の長片)に形成され、マニホールド203,204は枠体22の他方の長片22L(図1では上側の長片)に形成されている。スリット211,213は枠体22の一面側に形成されており、スリット211は一方の長片22Lに形成され、スリット213は他方の長片22Lに形成されている。スリット212,214は枠体22の他面側に形成されており、スリット212は一方の長片22Lに形成され、スリット214は他方の長片22Lに形成されている。各スリット211~214の一端はそれぞれ各マニホールド201~204に繋がり、他端は開口22oに繋がっており、各スリット211~214はそれぞれ、各マニホールド201~204と枠体22の内側に形成された開口22oとを接続する。
図2を参照して、図1に示す実施形態1に係る枠体を備えるセルフレームについて説明する。図2に例示するセルフレーム20は、枠体22と、枠体22の開口22o(図1参照)に嵌め込まれる双極板21とを備える。セルフレーム20は、双極板21の周縁部を表裏から挟むように枠体22が形成され、双極板21の外周に枠体22が射出成形などにより一体化されている。枠体22の開口22oに双極板21が嵌め込まれることで、枠体22及び双極板21により凹部(チャンバー24)が形成される。具体的には、セルフレーム20は、枠体22の内周面及び双極板21の表面により枠体22の内側に電極(図示せず)が収納されるチャンバー24が形成されている。図2では、セルフレーム20の一面側(紙面表側)のチャンバー24のみ図示しているが、他面側(紙面裏側)にもチャンバーが形成されている。セルフレーム20の一面側のチャンバーに正極電極、他面側のチャンバーに負極電極が収納され、双極板21の一面側に正極電極、他面側に負極電極が配置される(図10参照)。双極板21には、プラスチックカーボン製のものが利用できる。
セルフレーム20には、枠体22のスリット211~214が形成された部分に、イオン交換膜(図10参照)を保護するプラスチック製の保護板40が配置されていてもよい。保護板40は、各スリット211~214を覆うように枠体22の長片22Lの表面にそれぞれ配置され、各保護板40には、各マニホールド201~204に対応する位置に貫通孔又は切欠きが形成されている。図2に例示する保護板40の場合、正極電解液用のスリット211,213が形成された枠体22の一面側に配置される保護板40については、正極電解液用のマニホールド201,203に対して円形状の貫通孔が形成され、負極電解液用のマニホールド202,204に対しては矩形状の切欠きが形成されている。逆に、負極電解液用のスリット212,214が形成された枠体22の他面側に配置される保護板40では、正極電解液用のマニホールド201,203に対して矩形状の切欠きが形成され、負極電解液用のマニホールド202,204に対しては円形状の貫通孔が形成されている。セルフレーム20を用いてレドックスフロー電池のセル(図10参照)を構成したとき、この保護板40によって、各スリット211~214がイオン交換膜に接触することがなくなり、スリットの凹凸によってイオン交換膜が損傷することを防止できる。図2では、枠体22の一面側に形成されたスリット211,213を覆う保護板40のみ図示しているが、枠体22の他面側にも保護板が配置されており、スリット212,214が保護板で覆われている。
図1の丸囲み図は、実施形態1に係る枠体におけるスリット210(211)の拡大平面図である。図1では、代表してスリット211の平面形状を示している。また、図3は、スリット210の断面形状を示しており、図1の丸囲み図におけるIII-III線に沿う概略拡大断面図である。図1に示すように、スリット210は、少なくとも1つの曲部35を有する。以下、図1,図3を参照して、実施形態1のスリット210の平面形状について、より詳しく説明する。
曲部35は、曲率半径rが2.0mm以上200mm以下である。図1に示す実施形態1のスリット210では、曲部35が円弧状であり、曲部35の中心角θが略直角(90°)である。「曲部の中心角」とは、曲部の曲率半径の中心と曲部の一端及び他端とをそれぞれ結ぶ2つの線分がなす角度を意味する。曲部35の曲率半径rは10mm以上60mm以下であることが好ましい。
接続部36は、曲率半径が200mm超(曲率が1/200未満)であり、直線状(曲率が0)の場合も含む。図1に示すスリット210では、接続部36が直線状である。接続部36の長さaは5.0mm以上200mm以下であることが好ましく、10mm以上50mm以下であることがより好ましい。
スリット210の断面形状は、図3に示すように矩形状である。スリット210の断面形状は、矩形状に限定されるものではなく、例えば、等脚台形状などの四角形状、二等辺三角形状などの三角形状、半円形状や半楕円形状などであってもよい。具体的には、スリット断面において、開口部を長辺、底部を短辺とする台形状や、底部を頂点とし、開口部を底辺とする三角形状であるなど、開口部側の方が底部側よりも幅広の形状であることが挙げられる。また、スリット断面の角部が面取りされていてもよく、角部が曲面状に形成されていてもよい。
スリット210の深さhは、例えば0.5mm以上10mm以下、更に1.0mm以上5.0mm以下であることが好ましい。スリット210の幅wは、例えば0.5mm以上20mm以下、更に1.0mm以上8.0mm以下であることが好ましい。
実施形態1に係る枠体22(セルフレーム20)は、スリット210の一部に曲部35を有することで、1本の直線状のスリットを形成する場合に比較して、スリット長を長くすることができ、シャント電流損失を低減できる。更に、曲部35の曲率半径rが2.0mm以上200mm以下であることで、スリット内の電解液の放熱を改善できると共に、スリット形成部分での歪の発生を抑制できる。具体的には、曲部35の曲率半径rが2.0mm以上であることで、枠体22(長辺22L)の平面における曲部35の形成領域(図1の丸囲み図におけるハッチングを施した領域)を大きくでき、曲部35の形成部分での熱容量が大きくなる。したがって、曲部形成部分において電解液からの放熱量を増やすことができ、熱がこもり難い。よって、電解液の放熱を改善でき、電解液の温度上昇を抑制できるため、電解液成分の析出を抑制したり、枠体の軟化、変形を抑制できる。
図1に示す実施形態1では、枠体22の長片22Lにスリット210の曲部35が形成されている形態を例に挙げて説明した。図4に示す実施形態2では、長片22Lと短片22Sとが交差する枠体22の角部22Cに曲部35が形成されている。
図1に示す実施形態1では、スリット210が1つの曲部35を有する形態を例に挙げて説明したが、曲部35の数は複数であってもよい。図5に示す実施形態3では、スリット210が複数の曲部35を有する形態を説明する。
スリットにおける曲部の曲率半径を変化させたときの放熱性能及び歪量を評価した。評価条件を次に示す。
放熱性能は、曲部35内の電解液の発熱量と枠体22における曲部35の形成部分の熱容量との比(後述する温度上昇速度ΔT)で評価した。曲部35内の電解液の発熱量Q及び曲部35の形成部分の熱容量Cは、次のようにして求めた。
発熱量Q(W)は、曲部35内の電解液の電気抵抗R(Ω)とスリット間電圧v(V)から求める。電気抵抗Rは、電解液の抵抗率をρ(Ω・cm)として、次式により算出する。
[式1]R=ρ×(πr/2)×(1/wh)
そして、発熱量Qは次式により算出する。
[式2]Q=v2/R=v2×(2wh/ρπr)
熱容量C(J/℃)は、枠体22の比熱容量Cp(J/cm3・℃)と曲部形成部分の体積V(cm3)から求める。比熱容量Cpは、枠体22の比熱c(J/kg・℃)と比重d(g/cm3)から次式により算出する。
[式3]Cp=c×d
体積Vは、枠体22における曲部35の形成領域(図6のクロスハッチングで示す領域)での体積とし、次式により算出する。枠体22の厚さtは5mmとする。
[式4]V=(πr2/4)×t
そして、熱容量Cは次式により算出する。
[式5]C=Cp×V=Cp×(πr2t/4)
上記計算式を用いて算出した発熱量Q(W)と熱容量C(J/℃)から、次式により温度上昇速度ΔT(℃/s)を算出する。
[式6]ΔT=Q/C=(v2×2wh/ρπr)/(Cp×(πr2t/4))=(v2×2wh×4)/(ρπr×Cp×πr2t)=(8v2/ρπ2Cp)×(wh/r3t)
曲部35の曲率半径rを1.0mm~300mmの範囲で変化させたときの温度上昇速度ΔT(℃/s)を算出し、これに基づいて放熱性能を評価した。温度上昇速度ΔTが小さいほど、放熱性能が高いことを意味する。放熱性能の評価は、温度上昇速度ΔTの値が10(℃/s)以下の場合を「A」、500(℃/s)以下の場合を「B」、それ以外を「C」とした。温度上昇速度ΔTの値と放熱性能の評価を表1に示す。
歪量は、曲部35の形成部分に加わる液圧による総荷重Pで評価した。荷重P(N)は、図7に示すように、XY平面上での曲部35の中心角dθの微小区間に加わる単位液圧p(N/mm)による荷重を0≦θ≦π/2の範囲で積分することで求めた。この場合、荷重Pを図7に示すX方向とY方向に分けて考えると、次式により、荷重Pは単位液圧pと曲率半径rとの積として表すことができる。
[式7]
(X方向)P=∫(p×r・cosθdθ)=p×r
(Y方向)P=∫(p×r・sinθdθ)=p×r
単位液圧p(N/mm)は、液圧σ(MPa)とスリット深さh(mm)の積として、次式で与えられる。液圧σは0.5MPaとする。
[式8]p=σ×h
次式により曲部35での荷重P(N)を算出し、この荷重PをPrとする。
[式9]P=p×r=σ×h×r
曲部35の曲率半径rを1.0mm~300mmの範囲で変化させたときの荷重Pr(N)を算出し、これに基づいて歪量を評価した。荷重Prが小さいほど、曲部35での歪量が小さいことを意味する。歪量の評価は、荷重Prの値が50(N)以下の場合を「A」、100(N)以下の場合を「B」、それ以外を「C」とした。荷重Prの値と歪量の評価を表1に示す。
表1に示す各曲率半径の曲部について、放熱性能及び歪量の評価に基づいて総合評価を行った。総合評価は、放熱性能及び歪量の全ての評価が「A」である(「B」、「C」がない)場合を「A」、少なくとも1つの評価が「B」であり、「C」がない場合を「B」、少なくとも1つの評価が「C」である場合を「C」とした。その結果を表1に示す。
スリットにおける接続部の長さを変化させたときの整流効果及び歪量を評価した。評価条件を次に示す。
整流効果は、曲部35を通過する電解液に作用する遠心力と接続部36の長さとの比(後述する偏流作用D)で評価した。電解液に作用する遠心力Fは、次のようにして求めた。
遠心力F(N/m3)は、電解液の比重をm(kg/m3)、電解液の流速をu(m/s)として、次式により算出する。
[式10]F=m×(u2/r)
流速u(m/s)は、電解液の流量をQ(L/min)とするとき、次式で与えられる。
[式11]u=Q/(h×w)
電解液に作用する遠心力F(N/m3)と接続部36の長さa(mm)との比を偏流作用Dと定義し、次式により偏流作用D(N/m4)を算出する。
[式12]D=F/a
接続部36の長さaを1.0mm~300mmの範囲で変化させたときの偏流作用D(N/m4)を算出し、これに基づいて整流効果を評価した。偏流作用Dが小さいほど、整流効果が高いことを意味する。整流効果の評価は、偏流作用Dの値が5.0×107(N/m4)以下の場合を「A」、1.0×108(N/m4)以下の場合を「B」、それ以外を「C」とした。偏流作用Dの値と整流効果の評価を表2に示す。
歪量は、接続部36の形成部分に加わる液圧による総荷重Pで評価した。接続部36での荷重P(N)は、単位液圧p(N/mm)と長さa(mm)との積として、次式により表される。
[式13]P=p×a
単位液圧p(N/mm)は、試算例1と同様に、液圧σ(MPa)とスリット深さh(mm)の積として、[σ×h]で与えられる。液圧σは0.5MPaとする。
次式により接続部36での荷重P(N)を算出し、この荷重PをPaとする。
[式14]P=p×a=σ×h×a
接続部36の長さaを1.0mm~300mmの範囲で変化させたときの荷重Pa(N)を算出し、これに基づいて歪量を評価した。荷重Paが小さいほど、接続部での歪量が小さいことを意味する。歪量の評価は、荷重Paの値が50(N)以下の場合を「A」、100(N)以下の場合を「B」、それ以外を「C」とした。荷重Paの値と歪量の評価を表2に示す。
表2に示す各長さの接続部について、整流効果及び歪量の評価に基づいて総合評価を行った。総合評価は、整流効果及び歪量の全ての評価が「A」である(「B」、「C」がない)場合を「A」、少なくとも1つの評価が「B」であり、「C」がない場合を「B」、少なくとも1つの評価が「C」である場合を「C」とした。その結果を表2に示す。
スリットの深さを変化させたときの整流効果及び歪量を評価した。評価条件を次に示す。
整流効果は、試算例2で説明した計算式を用いて、スリットの深さhを0.1mm~15mmの範囲で変化させたときの偏流作用D(N/m4)を算出し、これに基づいて評価した。整流効果の評価は、偏流作用Dの値が5.0×107(N/m4)以下の場合を「A」、1.0×108(N/m4)以下の場合を「B」、それ以外を「C」とした。偏流作用Dの値と整流効果の評価を表3に示す。
歪量は、試算例1で説明した計算式を用いて、スリットの深さhを0.1mm~15mmの範囲で変化させたときの荷重Pr(N)を算出し、これに基づいて評価した。歪量の評価は、荷重Prの値が50(N)以下の場合を「A」、100(N)以下の場合を「B」、それ以外を「C」とした。荷重Prの値と歪量の評価を表3に示す。
表3に示す各深さのスリットについて、整流効果及び歪量の評価に基づいて総合評価を行った。総合評価は、整流効果及び歪量の全ての評価が「A」である(「B」、「C」がない)場合を「A」、少なくとも1つの評価が「B」であり、「C」がない場合を「B」、少なくとも1つの評価が「C」である場合を「C」とした。その結果を表3に示す。
スリットの幅を変化させたときの整流効果及び放熱性能を評価した。評価条件を次に示す。
整流効果は、試算例2で説明した計算式を用いて、スリットの幅wを0.1mm~25mmの範囲で変化させたときの偏流作用D(N/m4)を算出し、これに基づいて評価した。整流効果の評価は、偏流作用Dの値が5.0×108(N/m4)以下の場合を「A」、1.0×1010(N/m4)以下の場合を「B」、それ以外を「C」とした。偏流作用Dの値と整流効果の評価を表4に示す。
放熱性能は、試算例1で説明した計算式を用いて、スリットの幅wを0.1mm~25mmの範囲で変化させたときの温度上昇速度ΔT(℃/s)を算出し、これに基づいて評価した。放熱性能の評価は、温度上昇速度ΔTの値が5.0(℃/s)以下の場合を「A」、8.0(℃/s)以下の場合を「B」、それ以外を「C」とした。温度上昇速度ΔTの値と放熱性能の評価を表4に示す。
表4に示す各幅のスリットについて、整流効果及び放熱性能の評価に基づいて総合評価を行った。総合評価は、整流効果及び放熱性能の全ての評価が「A」である(「B」、「C」がない)場合を「A」、少なくとも1つの評価が「B」であり、「C」がない場合を「B」、少なくとも1つの評価が「C」である場合を「C」とした。その結果を表4に示す。
101 イオン交換膜
102 正極セル 104 正極電極
103 負極セル 105 負極電極
106 正極電解液用タンク
108,110 導管 112 ポンプ
107 負極電解液用タンク
109,111 導管 113 ポンプ
20 セルフレーム
21 双極板 22 枠体
22L 長片 22S 短片 22C 角部
22o 開口
24 チャンバー
200 マニホールド
201,202 給液マニホールド
203,204 排液マニホールド
210 スリット
211,212 給液スリット
213,214 排液スリット
35,35a~35c 曲部
36 接続部
40 保護板
50 シール部材
10S セルスタック
250 エンドプレート
300 レドックスフロー電池(RF電池)
Claims (9)
- レドックスフロー電池のセルに用いられる枠体であって、
前記枠体の内側に形成された開口と、
電解液が流通するマニホールドと、
前記マニホールドと前記開口とを接続し、前記マニホールドと前記開口との間で前記電解液の流路を形成するスリットとを備え、
前記スリットは、少なくとも1つの曲部を有し、
少なくとも1つの前記曲部の曲率半径が2.0mm以上200mm以下である枠体。 - 前記スリットは、前記曲部のうち、最も前記開口側に位置する曲部と前記開口との間に、曲率半径が200mm超の接続部を有する請求項1に記載の枠体。
- 前記接続部の長さが5.0mm以上200mm以下である請求項2に記載の枠体。
- 前記スリットの深さが0.5mm以上10mm以下である請求項1~請求項3のいずれか1項に記載の枠体。
- 前記スリットの幅が0.5mm以上20mm以下である請求項1~請求項4のいずれか1項に記載の枠体。
- 互いに対向する一対の長片と、前記長片の端部同士を繋ぐ一対の短片とを有し、
前記長片に、少なくとも1つの前記曲部が形成されている請求項1~請求項5のいずれか1項に記載の枠体。 - 互いに対向する一対の長片と、前記長片の端部同士を繋ぐ一対の短片とを有し、
前記長片と前記短片とが交差する角部に、少なくとも1つの前記曲部が形成されている請求項1~請求項6のいずれか1項に記載の枠体。 - 請求項1~請求項7のいずれか1項に記載の枠体と、
前記枠体の開口に嵌め込まれる双極板とを備え、
前記枠体及び前記双極板により前記枠体の内側にチャンバーが形成されているレドックスフロー電池用セルフレーム。 - 請求項8に記載のレドックスフロー電池用セルフレームを備えるレドックスフロー電池。
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