WO2019030903A1 - Empilement de cellules et batterie redox - Google Patents

Empilement de cellules et batterie redox Download PDF

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Publication number
WO2019030903A1
WO2019030903A1 PCT/JP2017/029145 JP2017029145W WO2019030903A1 WO 2019030903 A1 WO2019030903 A1 WO 2019030903A1 JP 2017029145 W JP2017029145 W JP 2017029145W WO 2019030903 A1 WO2019030903 A1 WO 2019030903A1
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WIPO (PCT)
Prior art keywords
battery
end plate
length
cell stack
frame
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PCT/JP2017/029145
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English (en)
Japanese (ja)
Inventor
清明 林
毅 寒野
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住友電気工業株式会社
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Priority to PCT/JP2017/029145 priority Critical patent/WO2019030903A1/fr
Publication of WO2019030903A1 publication Critical patent/WO2019030903A1/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
    • H01M8/18—Regenerative fuel cells, e.g. redox flow batteries or secondary fuel cells
    • 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
    • H01M8/247—Arrangements for tightening a stack, for accommodation of a stack in a tank or for assembling different tanks
    • 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 cell stack and a redox flow battery.
  • an RF battery includes a positive electrode supplied with a positive electrode electrolyte, a negative electrode supplied with a negative electrode electrolyte, and a diaphragm (ion exchange membrane) interposed between both electrodes.
  • a battery cell comprising the A battery cell is constructed using a cell frame typically provided with a bipolar plate and a frame provided on the periphery of the bipolar plate (FIG. 7 of Patent Document 1).
  • An RF battery is typically used in a form called a cell stack in which a plurality of battery cells are stacked (FIG.
  • Patent Document 1 The cell stack is formed by sandwiching the stack of battery cells with a pair of end plates from both sides, and stacking in the stacking direction of the stack by a tightening shaft passing through both end plates and a nut provided at an end of the tightening shaft The body is tightened (Patent Document 1 [0004]).
  • the cell stack of the present disclosure is A laminate in which a plurality of redox flow battery cells are laminated; A pair of end plates sandwiching the laminate; And a plurality of clamping members disposed in outer edge regions of both end plates and clamping between the two end plates,
  • the end plate has a rectangular planar shape,
  • the length x of one side of the rectangle is 100 mm or more and 2000 mm or less,
  • the number y of the clamping members arranged on one side of the rectangle is It is a natural number that satisfies 0.0025x ⁇ y ⁇ 0.014x + 5.
  • the redox flow battery of the present disclosure is The above disclosed cell stack of the present disclosure.
  • the redox flow battery of embodiment WHEREIN It is a graph which shows the range of the length of the one side of the end plate with which a cell stack is equipped, and the number of clamping members. In Experiment 1, it is a graph which shows the relationship between the length of one side (long side) of an end plate, and the number of clamping members. In Experiment 1, it is a graph which shows the relationship between the length of one side (short side) of an end plate, and the number of clamping members. In Experiment 2, it is a graph which shows the relationship between the length of the one side of an end plate, and the number of clamping members.
  • the redox flow battery of embodiment WHEREIN It is explanatory drawing explaining the state which arrange
  • the rise in internal pressure is caused, for example, by changing the temperature when the operation of the RF battery is stopped in a state in which the battery cell is filled with the electrolytic solution, and the electrolysis is stored in the battery cell, typically in the cell frame. What arises due to thermal expansion of the liquid is mentioned.
  • the electrolyte is thermally expanded, a force is applied to each cell frame from the opening (window) side of the frame to the outer edge side.
  • the stress applied to the cell frame is increased by the above-described pressing force, and the internal pressure of the battery cell is increased.
  • An object of the present disclosure is to provide a cell stack that can suppress excessive deformation of the end plate and that the internal pressure of the battery cell is less likely to rise.
  • another object of the present disclosure is to provide a redox flow battery which can suppress excessive deformation of the end plate and which is difficult to increase the internal pressure of the battery cell.
  • the cell stack of the present disclosure and the redox flow battery of the present disclosure can suppress excessive deformation of the end plate, and the internal pressure of the battery cell does not easily rise.
  • a cell stack according to an aspect of the present invention is A laminate in which a plurality of redox flow battery cells are laminated; A pair of end plates sandwiching the laminate; And a plurality of clamping members disposed in outer edge regions of both end plates and clamping between the two end plates,
  • the end plate has a rectangular planar shape,
  • the length x of one side of the rectangle is 100 mm or more and 2000 mm or less,
  • the number y of the clamping members arranged on one side of the rectangle is It is a natural number that satisfies 0.0025x ⁇ y ⁇ 0.014x + 5.
  • the clamping members arranged on one side of the rectangle are typically arranged uniformly (details will be described later).
  • the clamping member disposed in the outer edge region of the end plate and clamping the laminate satisfies the above-mentioned specific range, and is appropriately provided with a restraint point by the clamping member.
  • the laminate is not excessively restrained by the end plate by not having too many tightening members, and the cell frame constituting the laminate, in particular, the frame can be elastically deformed to some extent.
  • a redox flow battery provided with such a cell stack as described above, the temperature changes when the operation is stopped in a state in which the electrolytic solution is filled in the battery cell, and the electrolysis is stored in the battery cell Even when a force is generated to press each cell frame due to the thermal expansion of the liquid, the stress applied to the cell frame can be relaxed by elastically deforming each cell frame. Therefore, according to the above-described cell stack, it is possible to construct an RF battery in which the internal pressure of the battery cell is difficult to increase due to thermal expansion of the electrolyte, and the components of the battery cell are not easily damaged due to the increase of the internal pressure. . And, by not having too few clamping members, the laminate is properly restrained by the end plate.
  • the above cell stack can hold the laminate of the RF battery cells in a liquid-tight manner, and can construct an RF battery in which the electrolytic solution is unlikely to leak from between adjacent RF battery cells.
  • the number of the clamping members disposed on the long side of the rectangle may be equal to or greater than the number of the clamping members disposed on the short side of the rectangle.
  • the above-mentioned form tends to increase the number of tightening members disposed on the long side which is relatively less rigid among the long side and the short side of the end plate while reducing the rise of the internal pressure of the battery cell as described above In the above, it is easy to suppress excessive deformation of the end plate and the electrolyte is less likely to leak.
  • the number y of the fastening members may be in a form satisfying 0.00333x ⁇ y.
  • the number y of the fastening members may be such that y ⁇ 0.012x + 4.
  • the electrolytic solution is less likely to leak as described above, and the number of tightening members is smaller. Therefore, the above-described stress can be easily relieved, and the internal pressure of the battery cell is more difficult to increase.
  • the redox flow battery (RF battery) according to one aspect of the present invention is The cell stack according to any one of the above (1) to (4) is provided.
  • the above-described RF battery includes the above-described cell stack in which the restraint by the fastening member is appropriate, the internal pressure of the battery cell is unlikely to increase due to the thermal expansion of the electrolyte as described above. In addition to preventing damage to the components of the battery cell, it is easy to suppress excessive deformation of the end plate to prevent leakage of the electrolytic solution from between adjacent battery cells.
  • the RF battery 10 includes at least one battery cell (RF battery cell) 10C and a circulation mechanism for circulating and supplying the electrolytic solution to the battery cell 10C.
  • the RF battery 10 of the embodiment is a multi-cell battery including the cell stack 30 of the embodiment that mainly includes the laminate 100 in which the plurality of battery cells 10C are stacked.
  • the RF battery 10 is typically connected to the power generation unit 420 and a load 440 such as a power system or a customer via the AC / DC converter 400 or the transformation equipment 410, and the power generation unit 420 is supplied with power. It charges as a source and discharges the load 440 as a power supply target.
  • the power generation unit 420 include a solar power generator, a wind power generator, and other general power plants.
  • the battery cell 10C includes a positive electrode 14 to which a positive electrode electrolyte is supplied, a negative electrode 15 to which a negative electrode electrolyte is supplied, and a diaphragm 11 interposed between the positive electrode 14 and the negative electrode 15.
  • the positive electrode 14 and the negative electrode 15 are reaction sites to which an electrolytic solution containing an active material is supplied to cause a battery reaction of the active material (ion), and a porous material such as a fiber aggregate of a carbon material is used.
  • the diaphragm 11 is a member that separates the positive electrode 14 and the negative electrode 15 from each other and transmits a predetermined ion, and an ion exchange membrane or the like is used.
  • Battery cell 10C is typically constructed using cell frame 20 illustrated in FIG.
  • the cell frame 20 includes a bipolar plate 21 and a frame 22 provided on the periphery of the bipolar plate 21.
  • the bipolar plate 21 is a conductive member in which the positive electrode 14 is disposed on one side, the negative electrode 15 is disposed on the other side, and a current flows but an electrolyte does not pass.
  • the bipolar plate 21 is, for example, a conductive plastic plate containing graphite and the like and an organic material.
  • the frame 22 includes a window 22 w in which the positive electrode 14 and the negative electrode 15 and the bipolar plate 21 are disposed, a supply path for supplying an electrolytic solution to the positive electrode 14 and the negative electrode 15, and the positive electrode 14 and the negative electrode 15. And a discharge path for discharging the electrolyte solution from the In FIG. 6, the case where the positive electrode supply passage and the positive electrode discharge passage are provided on one surface side of the frame 22 and the negative electrode supply passage and the negative electrode discharge passage are provided on the other surface side of the frame 22 is illustrated.
  • the positive electrode supply passage and the negative electrode supply passage have liquid supply holes 24i and 25i, and slits 26i and 27i extending from the liquid supply holes 24i and 25i to the window 22w.
  • the positive electrode discharge path and the negative electrode discharge path include drain holes 24o and 25o, and slits 26o and 27o extending from the window 22w to the drain holes 24o and 25o.
  • Each of the holes 24 i, 24 o, 25 i, 25 o is a through hole penetrating the front and back of the frame 22.
  • the slits 26 i and 26 o on the positive electrode side are provided on one surface of the frame 22.
  • the slits 27 i and 27 o on the negative electrode side are provided on the other surface of the frame 22.
  • the plurality of cell frames 20 are stacked, whereby the liquid supply holes 24i and 25i and the drain holes 24o and 25o respectively form a flow channel of the electrolytic solution.
  • the frame 22 of this example surrounds the window 22w, and the seal material 18 is disposed on the outer edge side of the liquid supply holes 24i, 25i and the drain holes 24o, 25o.
  • the sealing material 18 is interposed between the frames 22 and 22 (see also FIG. 7).
  • the seal member 18 is made of an elastic material or the like, and the laminates 100 are clamped by the end plates 32 and 32 and the fastening members 33 as described later, thereby maintaining the frames 22 and 22 in a liquid tight manner.
  • the constituent material of the frame 22 is excellent in insulation, and does not react with the electrolytic solution, and a resin having resistance (chemical resistance, acid resistance, etc.) to the electrolytic solution, for example, vinyl chloride, polyethylene, polypropylene, etc. is used. .
  • the planar shape of the bipolar plate 21 (the window 22w), the frame 22, the positive electrode 14 and the negative electrode 15 described above is typically a rectangle shown in FIG.
  • the above-mentioned planar shape includes a curved shape such as a circle and an ellipse, and a polygonal shape such as a hexagon.
  • the laminated body 100 has a rectangular shape and is easy to handle.
  • the end plates 32 sandwiching the rectangular parallelepiped laminate 100 are rectangular as will be described later, and the fastening members 33 are equally arranged in the rectangular frame-like outer edge side area 35. Therefore, in the laminated body 100, the tightening member 33 is uniformly disposed in the circumferential direction, and the tightening force by the end plate 32 and the tightening member 33 tends to be uniformly applied.
  • the cell stack 30 includes a stacked body 100 in which a plurality of cell frames 20 (bipolar plates 21), a positive electrode 14, a diaphragm 11, and a negative electrode 15 are stacked in this order, a pair of end plates 32 and 32 sandwiching the stacked body 100, and both A plurality of clamping members 33 disposed in the outer peripheral area 35 of the end plates 32, 32 and clamping between the end plates 32, 32 are provided.
  • the end plates 32, 32 are tightened by the tightening member 33
  • the stacked body 100 is held in the stacked state by the tightening force in the stacking direction.
  • the laminated body 100 is held in a liquid-tight manner by crushing the sealing material 18 by the tightening force.
  • the number of battery cells 10C in the laminate 100 can be appropriately selected.
  • the end plate 32 is a member that sandwiches the stacked body 100, directly receives a tightening force by the tightening member 33, and causes the received force to act on the stacked body 100.
  • the end plate 32 has an annular outer edge region 35 extending from the outer edge of the laminate 100 to the outer edge 32 o of the end plate 32 when viewed through in the stacking direction of the laminate 100 with the laminate 100 interposed therebetween. And is larger than the outer edge of the laminate 100 (see also FIG. 5).
  • the outer edge area 35 is an arrangement area of the tightening member 33. The size of the outer edge side region 35 (protruding length from the laminate 100) may be adjusted according to the size of the laminate 100, the tightening member 33, and the like.
  • the cell stack 30 can include a stack 100 in which a predetermined number of battery cells 10C are used as a sub-cell stack and a plurality of sub-cell stacks are stacked.
  • the subcell stack can include an electrolyte supply / discharge plate portion.
  • FIG. 6 exemplifies a case where a plurality of subcell stacks including a supply and discharge plate portion are provided.
  • a bipolar plate 21 may be used or a current collector plate made of metal or the like may be arranged together with the bipolar plate 21. .
  • the circulation mechanism includes a positive electrode tank 16 storing positive electrode electrolyte to be supplied to the positive electrode 14, a negative electrode tank 17 storing the negative electrode electrolyte to be supplied to the negative electrode 15, and a positive electrode tank 16.
  • Piping 162, 164 which connects between the cell stacks 30, piping 172, 174 which connects between the negative electrode tank 17 and the cell stack 30, and pumps 160, 170 provided in the piping 162, 172 on the supply side are provided.
  • the pipes 162, 164, 172, and 174 are connected to flow channels by the liquid supply holes 24i and 25i and the drain holes 24o and 25o, respectively, to construct a circulation path of the electrolyte of each electrode.
  • materials, electrolyte solution and the like of the RF battery 10 known configurations, materials, electrolyte solution and the like can be appropriately used.
  • electrolytes other than the vanadium-based electrolyte illustrated in FIG. 7 can be used.
  • the end plate 32 provided in the RF battery 10 of the embodiment and the cell stack 30 of the embodiment has a rectangular planar shape as illustrated in FIG. 5.
  • the number of the fastening members 33 disposed in the rectangular frame-like outer edge side area 35 along the outer edge 32o satisfies the specific range described later.
  • the outer edge side area 35 is hatched with a two-dot chain line for easy understanding.
  • the tightening members 33 (a to e, A to D) are indicated by white circles.
  • the rectangle here also includes a square (as well as the components of the above-described laminate 100).
  • the length x of one side of the rectangle drawn by the outer edge 32 o of the end plate 32 that is, the length L of the long side and the length H of the short side can be appropriately selected according to the size of the laminate 100.
  • the length x of at least one of the long side length L and the short side length H may be 100 mm or more and 2000 mm or less (however, the short side length H ⁇ long side length L) .
  • the RF battery 10 may be provided with an end plate 32 having a length x of less than 100 mm or more than 2000 mm.
  • the practical RF battery 10 can be obtained.
  • the laminate 100 is also larger, and the RF battery 10 with high output can be obtained.
  • the length x is 2000 mm or less, particularly if the length L of the long side is 2000 mm or less, the components of the laminate 100 and the cell stack 30 are not too large, and it is easy to construct them.
  • both the long side length L and the short side length H are 100 mm or more and 2000 mm or less, it is easy to construct, and it is easy to make the high-power RF battery 10.
  • the above-mentioned length x may be 200 mm or more, 300 mm or more, and particularly, the long side length L may be 400 mm or more, 500 mm or more. From the viewpoint of ease of handling and reduction of manufacturing errors, the length x may be, for example, 1900 mm or less, or 1800 mm or less.
  • FIG. 1 is a graph showing the relationship between the length x (mm) of one side and the number y of the fastening members 33 on one side, in which a region satisfying 0.0025x ⁇ y ⁇ 0.014x + 5 is hatched. .
  • the horizontal axis indicates the length x (mm) of one side of the rectangle
  • the vertical axis indicates the number y of clamping members disposed on one side of the rectangle.
  • the length x of one side is long and the fastening member is long even if the large end plate 32 is provided.
  • the number y of 33 is not too small, and the stack member 100 can be appropriately restrained by the fastening member 33.
  • the number y of the fastening members satisfies 0.00333x ⁇ y, it is possible to further suppress excessive deformation of the end plate 32.
  • the length x is less than 400 mm, the value of 0.0025 x is less than 1, but it is practical to set the number y to 2 or more.
  • the fastening members 33 arranged on the long side and the short side satisfies y ⁇ 0.014x + 5
  • the fastening members are long even if the length x of one side is long and the large end plate 32 is provided.
  • the number y of 33 is not too large, and the clamping member 33 can exert an appropriate restraining force on the end plate 32. Therefore, when the operation of the RF battery 10 is stopped in a state where the battery cell 10C is filled with the electrolytic solution, the electrolytic solution in the battery cell 10C thermally expands due to a temperature change, and the frame 22 is viewed from the window 22w side Even when pressed to the outer edge side, the frame 22 can be elastically deformed.
  • the elastic deformation can relieve the stress applied to the cell frame 20. This stress relaxation can make it difficult to increase the internal pressure of the battery cell 10C. Therefore, damage to the components of the battery cell 10C, such as cracks or cracks in the frame 22, due to the increase in the internal pressure can be prevented.
  • the number y of the fastening members satisfies y ⁇ 0.012x + 4, the internal pressure of the above-described battery cell 10C is more difficult to increase.
  • the number y1 of the fastening members 33 arranged on the long side of the rectangle can be equal to or more than the number ys of the fastening members 33 arranged on the short side of the rectangle Number of sides y).
  • the long side is considered to be more easily deformed because the length is longer than the short side (H ⁇ L). If ys ⁇ yl is satisfied, it is easy to increase the number y of the fastening members 33 disposed on the long side. Therefore, it is easier to suppress the above-mentioned excessive deformation of the end plate 32 and the like, and it is easier to prevent the leakage of the electrolytic solution from between the adjacent battery cells 10C and 10C.
  • the number yl of the fastening members 33 on the long side can also be smaller than the number ys of the fastening members 33 on the short side (however, 0.0025x ⁇ yl ⁇ 0.014x + 5 is satisfied).
  • a region constrained by the long side of the end plate 32 is easily elastically deformed, and it is expected that the above-described reduction effect of the rise in internal pressure is more easily obtained.
  • the number y1 of the fastening members 33 on the long side is, for example, 2 to 25 or less, the fastening on the short side
  • the number ys of the members 33 is, for example, about 2 or more and 20 or less.
  • the clamping members 33 of the number y arranged on one side of the length x are typically arranged evenly.
  • the uniform arrangement means that the distance between the adjacent tightening members 33, 33 is equal to one side of the length x so that the geometrically uniform length can be obtained by the length x / (number y-1). It means that the fastening member 33 of y is arrange
  • a portion may be included in which the distance between the adjacent tightening members 33, 33 is 70% or more and 130% or less of the equal length. This will be specifically described with reference to FIG.
  • the adjacent clamping members (a, b), (b, c), (c, d), (d) The intervals La, Lb, Lc, and Ld of and e) are each equal to L / 4 if they have an equal length.
  • the intervals H A , H B and H c are respectively H / 3 if they have an equal length.
  • the short side can also include a portion having a substantially uniform length, as in the case of the long side described above.
  • the end plate 32 is provided with a flat plate body and ribs projecting from the plate body as shown in FIG. 6, the strength can be enhanced and the weight can be reduced even if the thickness of the plate body is reduced to some extent. be able to.
  • the grid-like rib is illustrated in FIG. 6, the shape of the rib can be changed as appropriate. If the ribs are omitted and only the plate body is used, a thick plate can increase the strength.
  • the fastening member 33 includes, for example, a bolt 330 screwed at both ends and provided with a bolt 330 disposed between the end plates 32, 32 and a nut 332 attached to the end of the bolt 330. .
  • a bolt 330 and the nut 332 those having sizes standardized by JIS or ISO can be appropriately used.
  • the outer edge area 35 of the end plate 32 becomes large, and the weight of the end plate 32 tends to increase.
  • the size is typically a certain size.
  • the bolt 330 and the nut 332 of (for example, M20) can be commonly used.
  • the constituent material of the end plate 32 and the fastening member 33 is excellent in strength if it is a metal, particularly an iron-based material such as steel.
  • the RF battery 10 is a storage battery for the purpose of stabilizing the fluctuation of the power generation output, storing power when surplus of generated power, load leveling, etc. for power generation of natural energy such as solar power generation and wind power generation. Available.
  • the RF battery 10 of the embodiment is juxtaposed to a general power plant, and can be used as a storage battery for the purpose of the countermeasure against the instantaneous drop / blackout and the load leveling.
  • the number y of the fastening members 33 disposed in the outer edge area 35 of the end plate 32 corresponds to the length x of one side of the rectangular end plate 32.
  • the above-described specific range is satisfied, and the restraint point by the fastening member 33 is appropriately provided. Therefore, the temperature of the RF battery 10 changes when the operation is stopped in a state where the battery cell 10C is filled with the electrolytic solution, and the electrolytic solution stored in the battery cell 10C is thermally expanded. It is difficult for the internal pressure of the battery cell 10C to rise due to the thermal expansion of the electrolytic solution.
  • the RF battery 10 can suppress excessive deformation of the end plate 32 during operation.
  • the distance between adjacent bolts on the long side is the beam length a, adjacent bolts on the short side Distance (short side length H / (short side side number of bolts ys-1)) width of the beam, thickness of the end plate height of the beam t, Young's modulus of the end plate Young's modulus of the beam E, the maximum deflection ⁇ max of the free end static determination beam whose hydraulic load is the distributed load P of the beam is determined.
  • the distance between the adjacent bolts on the short side is the beam length a
  • the adjacent bolts on the long side is the beam length a
  • the maximum deflection ⁇ max of the free end stationary beam is determined in the same manner as the long side, assuming that the interval of (long side length L / (long side side bolt number yl-1)) is the beam width b.
  • the crushing margin of the sealing material is preferably about 8% to 40% of the thickness of the sealing material, although it depends on the size of the cell stack and the sealing material.
  • the change width of the desirable crushing margin range 0.76 mm. Therefore, here, with respect to the range of the crushing margin of the sealing material, 0.38 mm, which is the maximum change width due to the deformation of the end plate being 1/2 at maximum, is taken as the allowable upper limit value of the maximum deflection ⁇ MAX.
  • a case where the width is at most 1/2 or less, that is, 0.38 mm or less is evaluated as G.
  • the variation width is 0.076 mm, which is the maximum 1/10, as the preferable allowable upper limit value of the maximum deflection ⁇ MAX described above, and the variation is the maximum 1/10 or less, that is, the case where it is 0.076 mm or less.
  • sample nos. 1 to No. In all cases 10, the maximum deflection ⁇ MAX is small (here, 0.38 mm or less), and the evaluation is G or VG. It can be seen that the end plate is unlikely to undergo excessive deformation even when receiving hydraulic pressure or the like. Sample No. 4 to No. 10 shows that the maximum deflection ⁇ MAX is smaller (here, less than 0.076 mm), and the end plate is more difficult to deform. On the other hand, for sample no. 101 to No. In all cases, the maximum deflection ⁇ max is large (here, 0.47 mm or more, and the maximum deflection ⁇ MAX is 0.75 mm or more), and the evaluation is B. 1 to No. It turns out that it is easier to deform than 10.
  • FIG. 2 is a graph showing the relationship between the length of one side of the end plate (here, the length of the long side) and the number of tightening members disposed on this side.
  • FIG. 3 is a graph showing the relationship between the length of one side of the end plate (here, the length of the short side) and the number of tightening members disposed on this side.
  • the horizontal axis represents the length x (mm) of one side
  • the vertical axis represents the number y of clamping members.
  • the battery cell has a cell frame (see the above-mentioned FIG. 6 and the like) including a bipolar plate and a frame as a component, the frame and its opening (window) have a rectangular shape, and the width of the frame h f ) is uniform on both the long side and the short side.
  • the deformation (deflection ⁇ x) of the frame caused by the increase ⁇ P of the internal pressure of the battery cell due to the thermal expansion of the electrolyte is determined as follows using the deflection formula of the beam.
  • the maximum deflection ⁇ max of the long side of the frame due to the above-mentioned increase ⁇ P in internal pressure is expressed as follows.
  • the distance between adjacent bolts is the beam length a f
  • the frame thickness is the beam width t f
  • the frame width is the beam height h f
  • ⁇ max 5 ⁇ ⁇ P ⁇ (t f) ⁇ (a f 4) / (384 ⁇ E f ⁇ I f)
  • the area S of the opening of the frame is determined by (length of long side of frame-width of frame h f ⁇ 2) x (length of short side-width of frame h f ⁇ 2).
  • ⁇ x [5 ⁇ ⁇ P ⁇ (t f ) ⁇ x / (24 ⁇ E f ⁇ I f )] ⁇ [(a f 3 ) ⁇ 2 ⁇ (a f ) ⁇ x 2 + x 3 ]
  • the area S (mm 2 ) of the opening, the second moment of area I f , the increase in internal pressure ⁇ P (MPa), and the area change ⁇ S of the opening are shown in Table 2.
  • sample nos. 11 to No. In all cases 20, the value of internal pressure Pi is small (here, 0.9 MPa or less), and the evaluation is G or VG. Even if the electrolyte stored in the battery cell thermally expands due to temperature change, it is restrained by the end plate It can be seen that the internal pressure of the battery cell does not easily rise, preferably does not substantially rise. Sample No. 16 to No. 20 shows that the value of the internal pressure Pi is smaller (here, 0 MPa), and substantially no increase in internal pressure due to the above-described thermal expansion of the electrolyte occurs. On the other hand, for sample no. 105-No. In all cases, the value of the internal pressure Pi is large (in this case, 5.2 MPa or more). 11 to No. It is understood that the above-mentioned increase in internal pressure is more likely to occur than 20.
  • FIG. 4 is a graph showing the relationship between the length of one side of the end plate and the number of tightening members arranged on one side, where the horizontal axis is the length x (mm) of one side, and the vertical axis is the tightening member Indicates the number y of As shown in the graph of FIG. 11 to No. Sample No. 15 with an evaluation of B; 105-No. Focusing on 109, it can be said that the length x of one side and the number y of the fastening members are correlated.
  • This elastic deformation can alleviate the pressing force applied to the frame due to the thermal expansion, and is considered to be easy to reduce the rise in the internal pressure of the battery cell. Also, for sample no. 16 to No. In each case 20, since the number y of the fastening members is 0.012x + 4 or less (y ⁇ 0.012x + 4), it is considered that the rise in the internal pressure of the battery cell can be further easily reduced. On the other hand, for sample no. 105-No. In each case, since the number y of tightening members exceeds 0.014x + 5 (0.014x + 5 ⁇ y), sample No. 11 to No. It is considered that the internal pressure of the battery cell is more likely to rise than 20. For these sample nos. 105-No. At 109, it is considered that the cell frame, particularly the frame, may cause breakage of the battery cell components such as cracking or cracking.

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Abstract

Cet empilement de cellules est pourvu : d'un corps empilé dans lequel sont empilées une pluralité de cellules de batterie redox ; d'une paire de plaques d'extrémité prenant en sandwich le corps empilé ; et d'une pluralité d'éléments de liaison qui sont agencés dans des régions de bord externe des deux plaques d'extrémité, et qui fixent ensemble les plaques d'extrémité. Les plaques d'extrémité ont une forme plane rectangulaire. La longueur x d'un côté du rectangle n'est pas inférieure à 100 mm et est inférieure ou égale à 2 000 mm. Le nombre y des éléments de liaison disposés sur un côté du rectangle est un nombre entier naturel tel que la relation 0,0025 x ≤ y ≤ 0,14 x + 5 est satisfaite.
PCT/JP2017/029145 2017-08-10 2017-08-10 Empilement de cellules et batterie redox WO2019030903A1 (fr)

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Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH06251794A (ja) * 1993-02-26 1994-09-09 Sumitomo Electric Ind Ltd 電池セルスタック
JP2002367660A (ja) * 2001-06-12 2002-12-20 Sumitomo Electric Ind Ltd レドックスフロー電池用セルスタック
JP2002367659A (ja) * 2001-06-12 2002-12-20 Sumitomo Electric Ind Ltd 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
JP2002367658A (ja) * 2001-06-12 2002-12-20 Sumitomo Electric Ind Ltd 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
JP2006324117A (ja) * 2005-05-18 2006-11-30 Sumitomo Electric Ind Ltd 電解液循環型電池
US20160204460A1 (en) * 2013-10-07 2016-07-14 Board Of Regents, The University Of Texas System A redox flow battery that uses complexes of cobalt and iron with amino-alcohol ligands in alkaline electrolytes to store electrical energy
JP2017010791A (ja) * 2015-06-23 2017-01-12 住友電気工業株式会社 セルフレーム、セルスタック、及びレドックスフロー電池

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH06251794A (ja) * 1993-02-26 1994-09-09 Sumitomo Electric Ind Ltd 電池セルスタック
JP2002367660A (ja) * 2001-06-12 2002-12-20 Sumitomo Electric Ind Ltd レドックスフロー電池用セルスタック
JP2002367659A (ja) * 2001-06-12 2002-12-20 Sumitomo Electric Ind Ltd 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
JP2002367658A (ja) * 2001-06-12 2002-12-20 Sumitomo Electric Ind Ltd 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
JP2006324117A (ja) * 2005-05-18 2006-11-30 Sumitomo Electric Ind Ltd 電解液循環型電池
US20160204460A1 (en) * 2013-10-07 2016-07-14 Board Of Regents, The University Of Texas System A redox flow battery that uses complexes of cobalt and iron with amino-alcohol ligands in alkaline electrolytes to store electrical energy
JP2017010791A (ja) * 2015-06-23 2017-01-12 住友電気工業株式会社 セルフレーム、セルスタック、及びレドックスフロー電池

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