WO2014175117A1 - Accumulateur métal-air - Google Patents

Accumulateur métal-air Download PDF

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Publication number
WO2014175117A1
WO2014175117A1 PCT/JP2014/060705 JP2014060705W WO2014175117A1 WO 2014175117 A1 WO2014175117 A1 WO 2014175117A1 JP 2014060705 W JP2014060705 W JP 2014060705W WO 2014175117 A1 WO2014175117 A1 WO 2014175117A1
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WO
WIPO (PCT)
Prior art keywords
metal
electrolytic solution
air battery
electrode
cell
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Application number
PCT/JP2014/060705
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English (en)
Japanese (ja)
Inventor
宏隆 水畑
吉田　章人
正樹 加賀
友春 新井
Original Assignee
シャープ株式会社
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Publication of WO2014175117A1 publication Critical patent/WO2014175117A1/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
    • H01M12/00—Hybrid cells; Manufacture thereof
    • H01M12/04—Hybrid cells; Manufacture thereof composed of a half-cell of the fuel-cell type and of a half-cell of the primary-cell type
    • H01M12/06—Hybrid cells; Manufacture thereof composed of a half-cell of the fuel-cell type and of a half-cell of the primary-cell type with one metallic and one gaseous electrode
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/60—Arrangements or processes for filling or topping-up with liquids; Arrangements or processes for draining liquids from casings
    • H01M50/691—Arrangements or processes for draining liquids from casings; Cleaning battery or cell casings
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/70—Arrangements for stirring or circulating the electrolyte
    • H01M50/77—Arrangements for stirring or circulating the electrolyte with external circulating path
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M6/00—Primary cells; Manufacture thereof
    • H01M6/50—Methods or arrangements for servicing or maintenance, e.g. for maintaining operating temperature
    • H01M6/5077—Regeneration of reactants or electrolyte

Definitions

  • the present invention relates to a metal-air battery.
  • metal-air batteries Since metal-air batteries have high energy density, they are attracting attention as next-generation batteries.
  • the metal-air battery generates power by using a metal electrode containing an electrode active material as a fuel as an anode and an air electrode as a cathode.
  • a zinc-air battery using metal zinc as an electrode active material can be mentioned.
  • an electrode reaction of the following chemical formula 1 proceeds at the cathode. (Chemical formula 1): O 2 + 2H 2 O + 4e ⁇ ⁇ 4OH ⁇
  • the electrode reaction represented by the following chemical formulas 2 and 3 proceeds in the anode.
  • the reduced electrode active material is supplied to the metal-air battery as a metal electrode.
  • This used active material reduction process uses a reduction tank connected to the electrolyte tank of the metal-air battery by piping, etc., and transports the used active material from the electrolyte tank of the metal-air battery to the reduction tank through the pipe. However, it may be carried out, or the used active material may be transported to a reduction tank that is physically separated from the metal-air battery for reduction treatment.
  • the present invention has been made in view of such circumstances, and provides a metal-air battery capable of efficiently recovering a used active material without the need to circulate an electrolyte at a high flow rate.
  • the present invention includes an electrolytic bath, a metal electrode provided in the electrolytic bath and serving as an anode, an air electrode serving as a cathode, an injection channel for supplying an electrolytic solution to the electrolytic bath, and the electrolytic solution
  • a discharge channel for discharging the electrolyte from the tank the electrolyte tank has a slope on the bottom, and the opening inside the electrolyte tank of the discharge channel is near the lower edge of the slope
  • a metal-air battery is provided.
  • an electrolyte tank a metal electrode that is provided in the electrolyte tank and serves as an anode, and an air electrode that serves as a cathode are provided, so that the electrode reaction proceeds between the metal electrode and the air electrode.
  • An electromotive force can be generated.
  • the injection channel for supplying the electrolytic solution to the electrolytic solution tank and the discharge channel for discharging the electrolytic solution from the electrolytic solution tank are provided, the injection channel to the discharge channel in the electrolytic solution tank is provided. And the used active material generated in the electrolyte solution can be discharged together with the electrolyte solution from the discharge channel to the outside of the electrolyte bath.
  • the electrolytic bath has a slope at the bottom, the used active material generated and precipitated in the electrolytic solution is moved in a lower direction along the slope of the bottom of the electrolytic bath by the force of gravity. Can do.
  • the opening inside the electrolyte tank of the discharge channel is provided in the vicinity of the lower edge of the slope, the used active material that has moved along the slope at the bottom of the electrolyte tank is electrolyzed. It can easily flow into the discharge channel together with the liquid. As a result, the used active material can be efficiently removed from the electrolyte bath.
  • the flow of the used active material can be generated toward the opening inside the electrolyte tank of the discharge channel by using the force of gravity without circulating the electrolyte at a high flow rate.
  • the used active material can be removed from the electrolytic solution tank.
  • the used active material can be collected near the opening inside the electrolyte tank of the discharge channel using the force of gravity without always flowing the electrolyte, By performing the circulation, it becomes possible to remove the used active material from the electrolytic solution tank.
  • FIG. 1 is a schematic sectional drawing of the metal air battery of one Embodiment of this invention
  • FIG. 1 is a schematic sectional drawing of the metal air battery of one Embodiment of this invention
  • FIG. 1 is a schematic sectional drawing of the metal air battery of one Embodiment of this invention
  • FIG. 1 is a schematic sectional drawing of the metal air battery of one Embodiment of this invention
  • FIG. 1 is a schematic sectional drawing of the metal air battery of one Embodiment of this invention
  • FIG. 5 is a schematic cross-sectional view of the metal-air battery taken along broken line EE in FIG. 4. It is the figure which looked at the bottom of the electrolyte solution tank contained in the metal air battery shown in FIG. 4 from the top, and is explanatory drawing of the movement of a used active material, and the flow of electrolyte solution.
  • A) is a schematic sectional drawing of the metal air battery of one Embodiment of this invention
  • (b) is a schematic sectional drawing of the metal air battery in the broken line FF of (a)
  • (c) is (b) 2 is a schematic cross-sectional view of the metal-air battery taken along broken line GG in FIG.
  • (A) (b) (c) is a schematic sectional drawing of the metal air battery of one Embodiment of this invention, respectively. It is a schematic sectional drawing of the metal air battery of one Embodiment of this invention. It is a schematic sectional drawing of the metal air battery of one Embodiment of this invention. It is the figure which looked at the bottom of the electrolyte solution tank contained in the metal air battery shown in FIG. 9, 10 or 17 from the top, and is explanatory drawing of the movement of a used active material, and the flow of electrolyte solution.
  • (A) is a schematic sectional view of the metal-air battery of one embodiment of the present invention
  • (b) is a schematic sectional view of the metal-air battery taken along the broken line KK in (a)
  • (c) is (b) 2 is a schematic cross-sectional view of the metal-air battery taken along broken line LL in FIG.
  • It is a schematic sectional drawing of the metal air battery of one Embodiment of this invention. It is the figure which looked at the bottom of the electrolyte solution tank contained in the metal air battery shown in FIG. 13 from the top, and is explanatory drawing of the movement of a used active material, and the flow of electrolyte solution.
  • (A) is a schematic sectional drawing of the metal air battery of one Embodiment of this invention
  • (b) is a schematic sectional drawing of the metal air battery in the broken line PP of (a)
  • (c) is (b) 2 is a schematic cross-sectional view of the metal-air battery taken along one-dot chain line QQ.
  • (A) is a schematic cross-sectional view of the metal-air battery of one embodiment of the present invention
  • (b) is a schematic cross-sectional view of the metal-air battery at the two-dot chain line WW of (a)
  • (c) is (A) It is a schematic sectional drawing of the metal air battery in the dashed-dotted line XX
  • (d) is a schematic sectional drawing of the metal air battery in the broken line ZZ of (b). It is a schematic sectional drawing of the metal air battery of one Embodiment of this invention.
  • FIG. 1 A is a schematic sectional drawing of the metal air battery of one Embodiment of this invention
  • (b) is a schematic sectional drawing of the metal air battery in the broken line TT of (a)
  • (c) is (b) 2 is a schematic cross-sectional view of the metal-air battery taken along one-dot chain line SS
  • (d) is a schematic cross-sectional view of the metal-air battery taken along the broken line U-U in FIG.
  • It is a schematic sectional drawing of the metal air battery of one Embodiment of this invention. It is the figure which looked at the bottom of the electrolyte solution tank contained in the metal air battery shown in FIG.
  • the metal-air battery of the present invention includes an electrolytic bath, a metal electrode provided in the electrolytic bath and serving as an anode, an air electrode serving as a cathode, and an injection channel for supplying the electrolytic solution to the electrolytic bath.
  • a discharge flow path for discharging the electrolytic solution from the electrolytic solution tank, the electrolytic solution tank has a slope at the bottom, and the opening inside the electrolytic solution tank of the discharge flow path is below the slope. It is provided in the vicinity of the edge.
  • the slope provided in the bottom of the electrolytic solution tank may be provided in the whole bottom of the electrolytic solution tank, or may be provided in a part of the bottom of the electrolytic solution tank.
  • the region below the metal electrode in the gravitational direction is a region where used active material is likely to precipitate as a result of the reaction of the anode electrode. It is desirable that a slope be provided across.
  • the injection flow path is provided so as to supply an electrolytic solution into an electrolytic bath near the upper edge of the slope.
  • the electrolytic solution supplied into the electrolytic solution tank can be made to flow in the direction of the discharge channel along the slope of the slope.
  • the used active material precipitated on the bottom slope of the electrolyte bath can be moved in the direction of the discharge flow path by both movement by gravity and movement by the electrolyte flow on the used active material.
  • This used active material can be efficiently introduced into the discharge channel.
  • the used active material can be efficiently removed from the electrolyte bath.
  • the electrolyte bath has a groove at the bottom between the upper edge of the slope and the side wall, and the injection channel supplies the electrolyte into the groove. It is preferably provided. According to such a configuration, the electrolyte can be supplied to the electrolyte bath near the upper edge of the slope through the groove, and the used active material precipitated on the slope at the bottom of the electrolyte bath Further, it can be moved in the direction of the discharge flow path by both the movement of the used active material by gravity and the movement of the electrolyte solution.
  • the opening inside the electrolytic solution tank of the injection channel is provided at a position higher than the top of the air electrode or higher than the top of the metal electrode.
  • the electrolytic solution supplied to the electrolytic solution tank can flow between the metal electrode and the air electrode, and convection is generated in the electrolytic solution near the surface of the metal electrode and the surface of the air electrode.
  • Concentration of metal-containing ions on the surface of the metal electrode can be suppressed by the convection of the electrolyte near the surface of the metal electrode, and the used active material can adhere to the surface of the metal electrode as a passive state. Can be suppressed.
  • the used active material can be removed from the surface of the metal electrode by convection of the electrolytic solution. Moreover, it can suppress that a used active material adheres to the surface of an air electrode 9, or a pore by the convection of the electrolyte solution of the surface vicinity of an air electrode.
  • the metal-air battery of the present invention has a stack structure including a plurality of cells, and the cells include the electrolyte bath, the metal electrode, the air electrode, the injection channel, and the discharge channel. Of the two adjacent cells, the discharge channel of one cell is preferably connected to the injection channel of the other cell. According to such a configuration, a cell assembly composed of a plurality of cells can be formed, and the power generation capability of the metal-air battery can be easily increased. Moreover, since the electrolyte which flowed in the electrolyte tank contained in one cell among two adjacent said cells can be flowed in the electrolyte tank contained in the other cell, electrolyte solution of a cell assembly The used active material in the tank can be discharged efficiently.
  • the discharge channel or the injection channel is preferably a bent channel.
  • the position of the opening inside the electrolytic solution tank and the position of the opening outside the electrolytic solution tank of the discharge channel can be changed.
  • the position of the opening inside the electrolytic solution tank of the injection channel and the position of the opening outside the electrolytic solution tank can be changed. For this reason, of the two adjacent cells, the position of the opening outside the electrolyte bath of the discharge channel of one cell and the position of the opening of the outside of the electrolyte bath of the injection channel of the other cell
  • the discharge channel and the injection channel can be easily connected when forming the cell aggregate.
  • the metal-air battery 25 of the present embodiment includes an electrolytic solution tank 2, a metal electrode 5 provided in the electrolytic solution tank 2 and serving as an anode, an air electrode 9 serving as a cathode, and an electrolytic solution 3 in the electrolytic solution tank 2.
  • An injection flow path 15 to be supplied and a discharge flow path 16 for discharging the electrolytic solution 3 from the electrolytic solution tank 2 are provided.
  • the electrolytic solution tank 2 has a slope 18 at the bottom, and the electrolytic solution tank 2 of the discharge flow path 16. The inner opening is provided in the vicinity of the lower edge 22 of the slope 18.
  • the electrolytic solution tank 2, the metal electrode 5, the air electrode 9, the injection channel 15, and the discharge channel 16 may constitute the cell 4.
  • the metal-air battery 25 of the present embodiment may have a cell assembly in which a plurality of cells 4 are stacked. Further, the metal-air battery 25 of the present embodiment can include the metal electrode current collector 7, the air electrode current collector 10, an ion exchange membrane, a used active material recovery mechanism, and the like. Hereinafter, the metal-air battery 25 of the present embodiment will be described.
  • the cell 4 is a structural unit of the metal-air battery 25 and has an electrode pair that is provided in the electrolytic solution tank 2 and includes a metal electrode 5 serving as an anode and an air electrode 9 serving as a cathode.
  • the cell 4 may have, for example, an electrode pair in which one air electrode 9 and one metal electrode 5 are provided so as to sandwich the electrolytic solution 3, and the metal-air battery shown in FIG. As shown in FIG. 25, two air electrodes 9 may have an electrode pair provided so as to sandwich one metal electrode 5.
  • the cell 4 includes an electrolytic solution tank 2, a metal electrode 5 provided in the electrolytic solution tank 2 and serving as an anode, an air electrode 9 serving as a cathode, and an injection flow for supplying the electrolytic solution 3 to the electrolytic solution tank 2.
  • the metal-air battery 25 may have a single cell structure including one cell 4 or may have a cell assembly (stack structure) in which a plurality of cells 4 are stacked.
  • the metal-air battery 25 is, for example, as shown in FIGS. 1 (a) (b), 2 (a) (b), 3 (a) (b) (c), 7 (a) (b) (c), FIG. 8 (a) (b) (c), FIG. 12 (a) (b) (c), FIG. 15 (a) (b) (c), FIG. (A) (b) (c) (d), FIG. 18 (a) (b) (c) (d), FIG. 22 (a) (b) (c) (d) it can.
  • 1A is a schematic cross-sectional view of the metal-air battery 25 taken along a broken line BB in FIG. 1B, and FIG.
  • FIG. 1B is a view of the metal-air battery 25 taken along a broken line AA in FIG. It is a schematic sectional drawing.
  • 2A and 2B are schematic cross-sectional views of the metal-air battery 25 corresponding to the cross-sectional view of the metal-air battery 25 taken along the broken line AA in FIG. 3A is a schematic cross-sectional view of the metal-air battery 25 taken along a broken line DD in FIG. 3B, and FIG. 3B is a view of the metal-air battery 25 taken along a broken line CC in FIG. It is a schematic sectional drawing.
  • 3C is a schematic cross-sectional view of the metal-air battery 25 of the present embodiment, and corresponds to the cross-sectional view of the metal-air battery 25 taken along the broken line CC in FIG. 3A is a schematic cross-sectional view of the metal-air battery 25 taken along the broken line DD in FIG.
  • FIG. 7A is a schematic cross-sectional view of the metal-air battery 25 taken along the broken line HH in FIG. 7B
  • FIG. 7B is the metal air taken along the broken line FF in FIGS. 7A and 7C
  • FIG. 7C is a schematic cross-sectional view of the battery 25
  • FIG. 7C is a schematic cross-sectional view of the metal-air battery 25 taken along a broken line GG in FIG. 7B
  • FIGS. 8A and 8B are schematic cross-sectional views of the metal-air battery 25 corresponding to the cross-sectional view of the metal-air battery 25 taken along the broken line GG in FIG. 7B, respectively, and FIG. FIG.
  • FIG. 6B is a schematic cross-sectional view of the metal-air battery 25 corresponding to the cross-sectional view of the metal-air battery 25 taken along broken line HH in FIG. 12A is a schematic cross-sectional view of the metal-air battery 25 taken along the broken line MM in FIG. 12B, and FIG. 12B is the metal air taken along the broken line KK in FIGS. 12A and 12C.
  • FIG. 12C is a schematic cross-sectional view of the battery 25, and FIG. 12C is a schematic cross-sectional view of the metal-air battery 25 taken along a broken line LL in FIG. 12B.
  • FIG. 15A is a schematic cross-sectional view of the metal-air battery 25 taken along the two-dot chain line RR in FIGS. 15B and 15C
  • FIG. 15B is a broken line P in FIGS. 15A and 15C
  • FIG. 15C is a schematic cross-sectional view of the metal-air battery 25 taken along the dashed-dotted line QQ in FIGS. 15A and 15B
  • 16 (a) is a schematic cross-sectional view of the metal-air battery 25 taken along the broken line YY in FIGS. 16 (b) and 16 (c)
  • FIG. 16 (b) is a diagram of FIGS. 16 (a), (c) and (d).
  • FIG. 16 (a) is a schematic cross-sectional view of the metal-air battery 25 taken along the two-dot chain line RR in FIGS. 15B and 15C
  • FIG. 15B is a broken line P in FIGS. 15A and 15C
  • FIG. 15C is a schematic cross-sectional
  • FIG. 16C is a schematic cross-sectional view of the metal-air battery 25 taken along the dashed-dotted line WW
  • FIG. 16C is a schematic cross-sectional view of the metal-air battery 25 taken along the dashed-dotted line XX in FIGS. 16A, 16B, and 16D
  • FIG. 16D is a schematic cross-sectional view of the metal-air battery 25 taken along the broken line ZZ in FIGS. 16B and 16C.
  • 18A is a schematic cross-sectional view of the metal-air battery 25 taken along the two-dot chain line VV in FIGS. 18B, 18C, and 18D, and FIG. FIG.
  • FIG. 18C is a schematic cross-sectional view of the metal-air battery 25 taken along one-dot chain line SS in FIGS. 18A, 18B, and 18D.
  • FIG. 18D is a schematic cross-sectional view of the metal-air battery 25 taken along the broken line UU in FIGS. 18A and 18C.
  • 22A is a schematic cross-sectional view of the metal-air battery 25 taken along the two-dot chain line NN of FIGS. 22B and 22C.
  • FIG. 22B is a cross-sectional view of FIG.
  • FIG. 22C is a schematic cross-sectional view of the metal-air battery 25 taken along a broken line EE, and FIG.
  • FIG. 22C is a schematic cross-sectional view of the metal-air battery 25 taken along one-dot chain line JJ in FIGS. 22A, 22B, and 22D.
  • FIG. 22D is a schematic cross-sectional view of the metal-air battery 25 taken along the two-dot chain line OO in FIGS. 22B and 22C.
  • the cell assembly has a stack structure in which a plurality of cells 4 are stacked.
  • a plurality of cells 4 may be provided in one electrolytic solution tank 2, and each cell 4 may have the electrolytic solution tank 2.
  • the number of cells 4 constituting the cell assembly is not particularly limited, and the number of cells 4 may be determined according to the required power generation capacity.
  • the electrolytic solution tank 2 included in each cell 4 may be provided in the common housing 1, and each cell 4 is disposed in the housing. 1, and the electrolytic solution tank 2 may be provided in the housing 1.
  • two or three cells 4 may be provided in one casing 1 and a plurality of such casings 1 may be combined to form a cell aggregate.
  • the electrode pairs of the plurality of cells 4 included in the cell assembly may be connected in series or in parallel.
  • electrode pairs of four cells 4a to 4d are connected in series.
  • assembly can be formed by combining the some cell 4.
  • the cell assembly can combine a plurality of cells 4 such that the side surfaces of the casings 1 of two adjacent cells 4 face each other.
  • the plurality of cells 4 constituting the cell aggregate can be combined so that the injection flow path 15 and the discharge flow path 16 included in one of the two adjacent cells 4 are connected.
  • the electrolyte when the electrolyte is supplied to the electrolyte tank 2 of the cell 4 at the end of the plurality of cells 4, the electrolyte can be sequentially flowed to the combined cells 4.
  • the electrolytic solution can be efficiently distributed to the electrolytic solution tanks 2 of the plurality of cells 4 included in the cell assembly, and the used active material 20 in the electrolytic solution tank 2 can be efficiently discharged.
  • pouring flow path 15 and the discharge flow path 16 is connected so that electrolyte solution may not leak.
  • the opening outside the cell of the injection channel 15 and the opening outside the cell of the discharge channel 16 can be provided on the side wall of the electrolyte bath 2 adjacent to the other cell 4 or on this side wall when forming the cell assembly. .
  • the injection flow path 15 of one of the two adjacent cells and the discharge flow path 16 of the other cell can be easily connected. it can. That is, in such a case, the connection surface connecting the opening outside the cell of the injection channel 15 of one cell and the opening outside the cell of the discharge channel 16 of the other cell is the side wall of the electrolyte bath 2 of one cell.
  • an O-ring or packing can be disposed on the contact surface, that is, the connection surface. Therefore, liquid leakage from the connection surface of the flow path can be efficiently suppressed.
  • the position of the opening outside the cell of the injection channel 15 is determined so that the center surface of the cell 4 parallel to the side wall of the electrolyte bath 2 adjacent to another cell is a symmetrical plane when forming the cell assembly.
  • the position can be substantially symmetrical with the position of the opening outside the 16 cells.
  • the position of the opening outside the cell of the injection channel 15 and the position of the opening outside the cell of the discharge channel 16 are determined by injecting the cell 4 by rotating the cell 180 degrees about the center axis of the cell 4 in the vertical direction. It can arrange
  • two types of cells 4 having a three-dimensional structure substantially in a mirror image relation are alternately arranged to form a cell aggregate, thereby injecting one of two adjacent cells.
  • the flow path 15 and the discharge flow path of the other cell can be easily connected. For this reason, the manufacturing cost of a cell assembly can be reduced. In addition, the number of parts constituting the cell assembly can be reduced.
  • each cell 4 has a casing 1, and the casing 1 is provided with the electrolyte bath 2, the metal-air battery 25 is, for example, FIG. 9, 9, 10, 13, 17, 19, 21.
  • the cell assembly included in the metal-air battery 25 shown in FIGS. 4 and 5 is a cell assembly formed by stacking four cells 4 shown in FIGS.
  • FIG. 5 is a schematic cross-sectional view of the metal-air battery 25 taken along the broken line EE in FIG.
  • the position of the opening outside the cell of the injection flow path 15 is the position of the opening outside the cell of the discharge flow path 16 with the center plane of the cell 4 parallel to the side wall of the electrolyte bath 2 as a symmetry plane.
  • the position is substantially symmetric.
  • the four cells 4a to 4d have substantially the same structure and substantially the same shape, and the injection flow path 15 of one cell 4 and the discharge flow of the other cell 4 of the two adjacent cells 4
  • the path 16 is connected.
  • the metal-air battery 25 shown in FIGS. 4 and 5 has a used active material recovery mechanism and an air circulation mechanism.
  • the metal-air battery 25 shown in FIG. 9 is a metal-air battery 25 in which four cells 4 having the structure shown in FIG.
  • the metal-air battery 25 shown in FIG. 10 is a metal-air battery 25 in which four cells 4 having the structure shown in FIG.
  • the metal-air battery 25 shown in FIG. 13 is a metal-air battery 25 formed by stacking four cells 4 having the structure shown in FIG.
  • the metal-air battery 25 shown in FIG. 17 is a metal-air battery 25 formed by stacking four cells 4 having the structure shown in FIG. In each of the cells 4a to 4d of the metal-air battery 25 shown in FIG. 9, FIG. 10, FIG. 13 or FIG.
  • the position of the opening outside the cell of the injection flow path 15 and the position of the opening outside the cell of the discharge flow path 16 are The position of the opening outside the cell of the injection flow channel 15 of the cell 4 rotated 180 degrees around the center axis in the vertical direction of the cell 4 and the outside of the discharge flow channel 16 of the cell 4 not rotated It arrange
  • the cells 4a and 4c have substantially the same structure and substantially the same shape
  • the cells 4a to 4d are combined so that the injection flow path 15 of one cell 4 and the discharge flow path 16 of the other cell 4 of the two adjacent cells 4 are connected.
  • a metal air battery 25 shown in FIG. 19 is a metal air battery 25 formed by stacking four cells 4 having the structure shown in FIG.
  • the position of the opening outside the cell of the injection channel 15 is provided with the opening outside the cell of the discharge channel 16 with the center plane of the cell 4 parallel to the side wall of the electrolyte bath 2 as a symmetry plane.
  • the position is substantially symmetric with respect to the position.
  • the position of the opening outside the cell of the injection flow channel 15 ′ is the outside of the cell of the discharge flow channel 16 ′ with the center plane of the cell 4 parallel to the side wall of the electrolyte bath 2 as the symmetry plane.
  • the position is substantially symmetric with the position where the openings are provided.
  • the four cells 4a to 4d have substantially the same structure and substantially the same shape, and injection of one of the adjacent two cells 4 is performed.
  • the flow path 15 and the discharge flow path 16 of the other cell 4 are connected.
  • the injection flow path 15 ′ of one cell 4 and the discharge flow path 16 ′ of the other cell 4 of the two adjacent cells 4 are connected.
  • the metal-air battery 25 can also have a structure as shown in FIG. In each of the cells 4a to 4d included in the metal-air battery 25 shown in FIG.
  • the position of the opening outside the cell of the injection channel 15 is set so that the center plane of the cell 4 parallel to the side wall of the electrolyte bath 2 is a plane of symmetry.
  • the position of the discharge channel 16 is substantially symmetrical with the position of the opening outside the cell.
  • the four cells 4a to 4d have substantially the same structure and substantially the same shape, and the injection flow path 15 of one cell 4 and the discharge flow of the other cell 4 of the two adjacent cells 4 The path 16 is connected.
  • Electrolytic Solution 3 is a liquid having ionic conductivity by dissolving an electrolyte in a solvent.
  • the electrolytic solution 3 is stored in the electrolytic solution tank 2 or circulates in the electrolytic solution tank 2.
  • the type of the electrolytic solution 3 varies depending on the type of the electrode active material contained in the metal electrode 5, but may be an electrolytic solution (aqueous electrolyte solution) using a water solvent, or an electrolytic solution (organic electrolytic solution) using an organic solvent. ).
  • an alkaline aqueous solution such as an aqueous sodium hydroxide solution or an aqueous potassium hydroxide solution can be used as the electrolytic solution.
  • an aqueous sodium chloride solution can be used.
  • an organic electrolyte can be used.
  • the electrolytic solution tank 2 may have a partition made of a solid electrolyte, and an electrolyte aqueous solution may be stored on one side partitioned by the partition and an organic electrolyte may be stored on the other side.
  • the metal electrode 5 is an electrode that serves as an anode, and contains a metal that is an electrode active material. Moreover, the metal electrode 5 may consist of an electrode active material part containing an electrode active material.
  • the electrode active material contained in the metal electrode 5 is a metal that chemically changes to a metal compound (used active material 20) by the discharge reaction of the battery.
  • the used active material 20 is deposited in the electrolyte solution in the form of fine particles, acicular particles, plate particles, or the like.
  • the electrode active material is metallic zinc
  • the used active material is zinc oxide or zinc hydroxide.
  • the electrode active material is metallic aluminum, and the used active material is aluminum hydroxide.
  • the electrode active material is metallic iron, and the used active material is iron oxide hydroxide or iron oxide.
  • the electrode active material is metallic magnesium and the used active material is magnesium hydroxide.
  • the electrode active materials are metallic lithium, metallic sodium, and metallic calcium, respectively, and the used active materials are oxides and hydroxides of these metals. is there.
  • the electrode active material and the used active material 20 are not limited to these examples, What is necessary is just a metal air battery.
  • the electrode active material contained in the metal electrode 5 mentioned the metal which consists of a kind of metal element in said example the metal electrode 5 may consist of an alloy.
  • the chemical change from the electrode active material to the used active material 20 due to the progress of the discharge reaction of the battery may occur on the surface of the metal electrode 5 or may occur both on the surface of the metal electrode 5 and in the electrolytic solution 3. .
  • a metal that is an electrode active material reacts with ions contained in the electrolytic solution 3, ions containing the metal are generated in the electrolytic solution 3, and ions containing the metal are decomposed.
  • the used active material 20 may be generated.
  • the metal which is an electrode active material may melt
  • a metal that is an electrode active material may react with ions contained in the electrolytic solution 3 to generate a used active material 20.
  • the metal that is the electrode active material is dissolved in the first electrolytic solution as metal ions, and the metal ions move into the second electrolytic solution, A used active material 20 may be generated. Two or more kinds of electrolytes can be separated by a solid electrolyte.
  • the used active material 20 When the used active material 20 is generated in this way, the used active material 20 is accumulated in the electrolytic solution tank 2, and the used active material 20 may possibly inhibit the electrode reaction. For this reason, it is necessary to remove the used active material 20 in the electrolytic solution tank 2.
  • the flow of the used active material is generated toward the opening inside the electrolytic solution tank of the discharge channel by using only the gravity or the flow of gravity and the electrolytic solution.
  • the used active material 20 in the electrolytic solution tank 2 can be removed by discharging the electrolytic solution from the discharge channel.
  • the used active material 20 may generate
  • the metal electrode 5 can be fixed on the main surface of the metal electrode current collector 7.
  • the shape of the metal electrode current collector 7 is not limited as long as it has conductivity and can fix the metal electrode 5.
  • a plate shape, a cylindrical shape, a spherical shape, a linear shape, a mesh shape, a punching metal, etc. can do.
  • the metal electrode current collector 7 can be formed of, for example, a metal plate having corrosion resistance against the electrolytic solution.
  • the material of the metal electrode current collector 7 is, for example, nickel, gold, silver, copper, stainless steel or the like.
  • the metal electrode current collector 7 may be a conductive base material subjected to nickel plating treatment, gold plating treatment, silver plating treatment, or copper plating treatment.
  • the metal electrode 5 may be fixed on the main surface of the metal electrode current collector 7 by pressing metal particles or lumps as electrode active materials against the surface of the metal electrode current collector 7.
  • a metal may be deposited on the electrode current collector 7 by plating or the like.
  • the metal electrode current collector 7 may be connected to a lid member that closes an electrode insertion opening into which the metal electrode 5 is inserted into the electrolytic solution tank 2.
  • the metal electrode 5 can be inserted into the electrolytic solution tank 2 and the electrode insertion port can be closed, and the reaction between the components in the atmosphere and the electrolytic solution 3 can be suppressed.
  • an alkaline electrolytic solution is used as the electrolytic solution, carbon dioxide gas in the atmosphere can be prevented from being dissolved in the electrolytic solution and neutralizing the alkaline electrolytic solution.
  • Electrolytic solution tank 2 is an electrolytic cell in which the electrolytic solution 3 is stored or circulated, and has corrosion resistance to the electrolytic solution. Moreover, the electrolytic solution tank 2 has a structure in which the metal electrode 5 can be installed. Further, when the metal-air battery 25 has a cell assembly composed of a plurality of cells 4, each cell 4 may have a separate electrolyte tank 2, and the electrolyte tank 2 of each cell 4 is a flow path. The plurality of cells 4 may share one electrolytic solution tank 2. In the metal-air battery 25 shown in FIG. 1 and the like, the bottom part and a part of the side wall of the electrolytic solution tank 2 are the casing 1, and the part of the side wall of the electrolytic solution tank 2 is the air electrode 9.
  • the metal-air battery 25 may have a mechanism for causing the electrolyte solution in the electrolyte tank 2 to flow.
  • the battery reaction in the metal electrode 5 and the electrolytic solution 3 can be promoted, and the performance of the metal-air battery 25 can be improved.
  • the electrolytic solution 3 may be circulated using the pump 31 as in the metal-air battery 25 shown in FIG. 4 to flow the electrolytic solution 3 in the electrolytic solution tank 2.
  • the metal-air battery 25 may include a movable part that can physically move the electrolyte 3 in the electrolyte bath 2 such as a stirrer, a wiper, or a vibrator.
  • the material of the casing 1 constituting the electrolytic solution tank 2 is not particularly limited as long as the material has corrosion resistance to the electrolytic solution.
  • the material of the casing 1 constituting the electrolytic solution tank 2 is not particularly limited as long as the material has corrosion resistance to the electrolytic solution.
  • polyvinyl chloride (PVA) polyvinyl alcohol (PVA), polyvinyl acetate, ABS, vinylidene chloride, polyacetal, polyethylene, polypropylene, polyisobutylene, fluororesin, epoxy resin, etc.
  • the electrolytic solution tank 2 has a slope 18 at the bottom.
  • the used active material 20 precipitated on the bottom of the electrolytic solution tank 2 can be moved downward along the slope of the slope 18 by gravity.
  • the electrolytic cell 2 has a slope 18 having an upper edge 23 and a lower edge 22 at the bottom.
  • the used active material 20 that has settled on the bottom of the electrolytic solution tank 2 follows the inclination due to gravity as shown by the dotted arrow in FIG. Can be moved downward. As shown in FIG.
  • the slope 18 may be provided at the bottom of the electrolyte bath 2, and the two slopes 18a and 18b may be provided as shown in FIGS. It may be provided at the bottom of the electrolytic solution tank 2. Further, the slope 18 may be provided on substantially the entire bottom of the electrolytic solution tank 2. Further, the inclined surface 18 may be an inclined plane or a curved surface. Further, the inclined surface 18 may be inclined in the direction in which the lower edge of the metal electrode 5 extends, as in the metal-air battery 25 shown in FIGS. Further, the inclined surface 18 may be inclined in the direction in which the metal electrode 5 and the air electrode 9 are laminated, like the cell 4 included in the metal-air battery 25 shown in FIG.
  • the slope 18 at the bottom of each electrolyte bath 2 is inclined in substantially the same direction.
  • the slope 18 at the bottom of the electrolytic solution tank 2 of the two adjacent cells 4 may be inclined substantially in the opposite direction.
  • the slope 18 at the bottom of the electrolytic solution tank 2 of each cell 4 included in the cell assembly may be inclined toward the side surface of the cell assembly.
  • the slopes 18a to 18d at the bottom of the electrolyte bath 2 of the four cells 4a to 4d are the side surfaces of the cell assembly.
  • Inclined in substantially the same direction. 6 is an explanatory diagram of the flow of the electrolyte and the movement of the used active material 20 in the metal-air battery 25 shown in FIGS. 20 is an explanatory diagram of the flow of the electrolyte and the movement of the used active material 20 in the metal-air battery 25 shown in FIG.
  • the slopes 18a to 18d are inclined in the direction of the dotted arrow shown in FIG. 6 or FIG. 20, and the used active material 20 deposited on the bottom of the electrolyte bath 2 moves downward along this inclination by gravity. .
  • the slope 18 at the bottom of the electrolytic solution tank 2 of the two adjacent cells 4 is inclined substantially in the opposite direction.
  • the slope 18 at the bottom of the electrolyte tank 2 included in the cells 4a and 4c is inclined in substantially the same direction toward the side surface of the cell assembly, and the electrolyte tank 2 included in the cells 4b and 4d.
  • the bottom slope 18 is inclined in the opposite direction to the bottom slope 18 of the electrolyte bath 2 of the cells 4a and 4c toward the side surface of the cell assembly.
  • 11 is an explanatory diagram of the flow of the electrolyte and the movement of the used active material 20 in the metal-air battery 25 shown in FIG. FIG.
  • FIG. 14 is an explanatory view of the flow of the electrolytic solution and the movement of the used active material 20 in the metal-air battery 25 shown in FIG.
  • the slopes 18a to 18d are inclined in the direction of the dotted arrow shown in FIG. 11 or FIG. 14, and the used active material 20 deposited on the bottom of the electrolytic solution tank 2 moves downward along this inclination.
  • the injection channel 15 included in the metal-air battery 25 of the present embodiment is provided so as to supply the electrolyte solution to the electrolyte tank 2, and the discharge channel 16 included in the metal-air battery 25 of the present embodiment extends from the electrolyte tank 2. It is provided to discharge the electrolytic solution. Thereby, the electrolytic solution in the electrolytic solution tank 2 can be circulated. Further, when the metal-air battery 25 has a cell assembly formed by overlapping a plurality of cells 4, the injection flow path 15 included in one cell 4 of the two adjacent cells 4 and the other cell 4 The included discharge flow path 16 can be connected.
  • circulated the electrolyte solution tank 2 contained in one cell 4 among the two adjacent cells 4 can be made to distribute
  • the used active material 20 in the electrolyte bath 2 can be efficiently discharged.
  • the electrolytic solution discharged to the outside of the cell 4 or the outside of the cell assembly is supplied to the inside of the cell 4 or the inside of the cell assembly again from the injection channel 15 after removing the used active material 20 in the electrolytic solution,
  • the liquid may be circulated.
  • the electrolyte solution can be circulated like the metal-air battery 25 shown in FIG. Further, a new electrolytic solution may be supplied from the injection channel 15 into the electrolytic solution tank 2.
  • emitted from the cell 4 or the cell assembly can be removed by the used active material collection
  • the injection flow path 15 and the discharge flow path 16 may be formed by providing holes in the casing 1 or the electrolytic solution tank 2, or may be formed by providing piping.
  • the amount of the electrolytic solution injected into the electrolytic solution tank 2 from the injection flow channel 15 and the amount of the electrolytic solution discharged from the discharge flow channel 16 may be substantially the same. Thereby, the electrolytic solution 3 in the electrolytic solution tank 2 can be circulated without reducing the amount of the electrolytic solution 3 in the electrolytic solution tank 2. Further, the injection of the electrolyte from the injection channel 15 into the electrolyte bath 2 and the discharge of the electrolyte from the discharge channel 16 may be performed continuously or at intervals.
  • the distance between the opening inside the electrolytic solution tank of the injection channel 15 and the opening inside the electrolytic solution tank of the discharge channel 16 and the lowest part of the metal electrode 5 or the lowest part of the air electrode 9 is the electrolyte solution.
  • the distance can be increased as compared with the case where the bottom surface of the electrolytic solution tank 2 is not inclined.
  • the cell assembly it is possible to increase the distance that ions are conducted in the electrolytic solution between the electrode included in one of the two adjacent cells and the electrode included in the other cell. . Thereby, the electrical resistance between these electrodes can be increased, and a shunt current can be prevented from flowing between these electrodes.
  • the opening inside the electrolytic solution tank of the discharge channel 16 is provided in the vicinity of the lower edge 22 of the slope 18.
  • the used active material 20 that has moved downward along the slope 18 can flow into the discharge channel 16 together with the electrolytic solution, and the used active material 20 in the electrolytic solution tank can be efficiently contained in the electrolytic solution. It can be discharged out of the tank.
  • generated in the electrolyte solution tank 2 can be collect
  • the cell assembly is formed by providing the opening inside the electrolytic solution tank of the discharge channel 16 in the vicinity of the lower edge 22 of the slope 18, one cell 4 of the two adjacent cells 4 is formed.
  • the distance in which ions are conducted in the electrolyte solution between the electrode contained in the electrode and the electrode contained in the other cell can be increased.
  • the opening inside the electrolytic solution tank of the discharge channel 16 is, for example, in the vicinity of the lower edge 22 of one inclined surface 18 as shown in FIGS. 1B, 2A, 3A, and 3B.
  • it may be provided near the lower edge 22 of the two inclined surfaces 18 as shown in FIGS.
  • one discharge channel 16 may be provided in the cell 4 as shown in FIGS. 1A and 1B, and a plurality of discharge channels 16 may be provided in the cell 4 as shown in FIG. 2A, for example.
  • the opening inside the electrolytic solution tank of the discharge channel 16 may be provided at the edge of the bottom of the electrolytic solution tank 2 as shown in FIGS. 1B and 2A, for example.
  • the opening inside the electrolytic solution tank of the discharge channel 16 may be provided in the central portion of the bottom of the electrolytic solution tank 2, for example, as shown in FIG.
  • the distance until the used active material 20 accumulated on the slope at the bottom of the electrolyte bath 2 flows into the discharge channel 16 can be shortened, and the used active material 20 can be efficiently recovered. Can do.
  • the discharge channel 16 can be provided so as to penetrate the bottom of the electrolytic solution tank 2 as shown in FIGS. 1 (a) and 1 (b) and FIGS. 2 (a) and 2 (b), for example. As a result, the used active material 20 in the electrolytic solution tank can be efficiently introduced into the discharge channel 16. Moreover, the discharge flow path 16 can also be provided so that the side wall of the electrolyte tank 2 may be penetrated like FIG. 3 (a) (b) (c), FIG. 7 (a). As a result, when the metal-air battery 25 has a cell assembly including a plurality of cells 4, the injection channel 15 and the discharge channel 16 of the two adjacent cells can be easily connected. Further, the discharge channel 16 can be provided horizontally. As a result, it is possible to prevent the used active material 20 from accumulating in the discharge channel 16.
  • the position of the injection channel 15 is not limited as long as the electrolyte can be supplied into the electrolyte bath 2.
  • the side wall of the electrolyte bath 2 is provided. It can provide so that it may penetrate.
  • the injection channel 15 and the discharge channel 16 of the two adjacent cells 4 can be easily connected.
  • the injection channel 15 can be provided horizontally. Further, for example, as shown in FIG. 3, the injection flow path 15 is such that the injection flow path 15 penetrates one side wall and the discharge flow path 16 penetrates the other side wall of the two opposite side walls of the electrolytic solution tank 2.
  • a discharge channel 16 can also be provided.
  • the injection channel 15 and the discharge channel 16 of the two adjacent cells 4 can be easily connected.
  • the electrolyte solution 3 in the electrolytic solution tank 2 can be circulated from one side wall side to the other side wall side of the two opposing side walls, the used active material 20 in the electrolytic solution tank 2 is allowed to flow. It is possible to efficiently flow into the discharge channel 16.
  • the opening inside the electrolyte tank of the injection channel 15 and the opening inside the electrolyte tank of the discharge channel 16 are formed at the lower edge of the same slope 18. It can also be provided in the vicinity. Further, the injection flow channel 15 and the discharge flow channel 16 can be provided so that the opening inside the electrolytic solution tank of the injection flow channel 15 and the opening inside the electrolytic solution tank of the discharge flow channel 16 face each other. As a result, a flow along the lower edge of the inclined surface 18 can be formed in the electrolytic solution in the electrolytic solution tank 2.
  • the used active material 20 that has moved downward along the slope 18 can be caused to flow into the discharge flow channel 16 on the flow of the electrolyte solution from the injection flow channel 15 toward the discharge flow channel 16. 2 can be efficiently discharged to the outside.
  • the position of the opening outside the cell of the injection channel 15 is symmetrical with respect to the center plane of the cell 4 parallel to the side wall of the electrolyte bath 2. As a position substantially symmetric to the position where the opening outside the cell of the discharge channel 16 is provided.
  • the metal-air battery 25 shown in FIGS. 4 and 5 having a cell assembly in which four cells 4 shown in FIGS. 3 (a) and 3 (b) are combined as shown by a dotted line arrow shown in FIG.
  • the spent active material 20 in the electrolytic solution tank 2 can be moved to the vicinity of the lower edge of the slopes 18a to 18d by the slopes 18a to 18d at the bottom of the tank 2, and this movement is indicated by the solid arrows in FIG.
  • the used active material 20 can be efficiently discharged out of the cell assembly by the electrolyte flowing along the lower edge of the slopes 18a to 18d.
  • the opening inside the electrolyte tank of the injection channel 15 and the opening inside the electrolyte tank of the discharge channel 16 are arranged in the electrolyte tank.
  • 2 is provided in the vicinity of the corner of the bottom, but as shown in FIG. 3C, the opening inside the electrolyte tank of the injection channel 15 and the opening inside the electrolyte tank of the discharge channel 16 are arranged in the electrolyte tank. You may provide in the center part of 2 bottom. Thereby, the distance until the used active material 20 accumulated on the slope 18 at the bottom of the electrolytic solution tank 2 flows into the discharge channel 16 can be shortened, and the used active material 20 is efficiently recovered. be able to.
  • the injection channel 15 can be provided so as to supply the electrolyte into the electrolyte bath in the vicinity of the upper edge of the slope 18.
  • the direction of the flow of the electrolytic solution in the electrolytic solution tank 2 from the injection flow channel 15 toward the discharge flow channel 16 and the inclination direction of the inclined surface 18 can be made substantially the same.
  • the used active material 20 precipitated at the bottom of the electrolytic solution tank 2 is moved in the direction of the opening inside the electrolytic solution tank of the discharge channel 16 by both the gravity applied to the used active material 20 and the flow of the electrolytic solution.
  • the used active material 20 in the electrolytic solution tank can be efficiently discharged.
  • the opening inside the electrolyte bath of the injection channel 15 is in the vicinity of the upper edge of the inclined surface 18 as in the metal-air battery 25 shown in FIGS. 7, 8B, 9C, 9 and 10, for example.
  • the metal-air battery 25 shown in FIG. 8A may be provided on the upper edge of the upper surface of the slope 18.
  • the upper side of the slope 18 as shown in FIGS. It may be provided below the edge.
  • the injection channel 15 penetrates the side wall of the electrolytic solution tank 2, and the opening inside the electrolytic solution tank of the injection channel 15 is near the upper edge of the slope 18. It is provided to be arranged.
  • the discharge channel 16 is provided so as to pass through the side wall opposite to the side wall through which the injection channel 15 passes, and the opening inside the electrolyte tank of the discharge channel 16 is arranged in the vicinity of the lower edge of the slope 18. It has been. With such a structure, the electrolyte can be supplied in the vicinity of the upper edge of the slope 18, and the electrolyte can be discharged from the vicinity of the lower edge of the slope 18. Thereby, the used active material 20 in the electrolytic solution tank 2 can be efficiently discharged to the outside of the cell 4.
  • the metal-air battery 25 shown in FIG. 8A is a metal-air battery 25 having a structure in which the position of the injection channel 15 of the metal-air battery 25 shown in FIG. An opening inside the tank is provided in the upper part of the upper edge of the slope 18. Even with such a structure, the electrolytic solution can be supplied in the vicinity of the upper edge of the inclined surface 18, and the used active material 20 in the electrolytic solution tank 2 can be efficiently discharged to the outside of the cell 4.
  • the metal air battery 25 shown in FIG. 8B is a metal air battery 25 having a structure in which the injection flow path 15 of the metal air battery 25 shown in FIG. 7 is bent.
  • the metal-air battery 25 shown in FIG. 8C is a metal-air battery 25 having a structure in which the discharge channel 16 of the metal-air battery 25 shown in FIG. 7 is bent.
  • the position of the opening outside the cell of the injection flow channel 15 and the position of the opening of the discharge flow channel 16 outside the cell are 180 degrees with the central axis in the vertical direction of the cell 4 as the rotation axis.
  • the position of the opening outside the cell of the injection flow path 15 of the cell 4 rotated by the degree of rotation and the position of the opening outside the cell of the discharge flow path 16 of the cell 4 not rotated are arranged so as to substantially overlap. .
  • the electrolyte can be supplied to the vicinity of the upper edge of the slope 18 in each cell 4. For this reason, as shown by the solid line arrows and the dotted line arrows shown in FIG. 11, the flow direction of the electrolytic solution in the electrolytic solution tank 2 from the injection channel 15 to the discharge channel 16 and the inclination direction of the inclined surface 18 are substantially set.
  • the used active material 20 can be efficiently discharged outside the cell assembly.
  • the cell assembly includes the electrode included in one cell 4 and the other cell 4 of the two adjacent cells 4.
  • the distance that ions are conducted in the electrolyte solution between the electrodes can be increased. Thereby, the electrical resistance between these electrodes can be increased, and a shunt current can be prevented from flowing between these electrodes.
  • the slope 18 is provided at the bottom of the electrolytic solution tank 2, and a groove is provided between the upper edge 23 of the slope 18 and the side wall perpendicular to the electrode stacking surface.
  • the injection channel 15 penetrates the side wall of the electrolytic solution tank 2 and is provided so that the opening inside the electrolytic solution tank of the injection channel 15 is disposed in the vicinity of the bottom of the groove.
  • the discharge channel 16 passes through the side wall opposite to the side wall through which the injection channel 15 passes, and the opening inside the electrolyte tank of the discharge channel 16 is arranged in the vicinity of the lower edge 22 of the inclined surface 18. Is provided.
  • the electrolyte flowing in the groove can be supplied to the vicinity of the upper edge 23 of the slope 18 and discharged from the vicinity of the lower edge 22 of the slope 18. Can do. Thereby, the used active material 20 in the electrolytic solution tank 2 can be efficiently discharged to the outside of the cell 4.
  • the metal-air battery 25 shown in FIG. 13 having a cell assembly in which four cells 4 having the same structure as the cell 4 shown in FIG. 12 are combined, in each cell 4, the upper edge 23 of the slope 18 is An electrolyte can be supplied in the vicinity. For this reason, as shown by the solid line arrows and the dotted line arrows shown in FIG. 14, the flow direction of the electrolytic solution in the electrolytic solution tank 2 from the injection channel 15 to the discharge channel 16 and the inclination direction of the inclined surface 18 are substantially set. The used active material 20 can be efficiently discharged outside the cell assembly.
  • the slope 18 at the bottom of the electrolyte tank 2 of the cell 4 included in the metal-air battery 25 shown in FIGS. 12 and 13 is inclined in the direction in which the lower edge of the metal electrode 5 extends.
  • the slope 18 at the bottom of the electrolytic solution tank 2 may be inclined in the direction in which the metal electrode 5 and the air electrode 9 are laminated.
  • a slope 18 is provided at the bottom of the electrolytic solution tank 2, and a groove is formed between the upper edge 23 of the slope 18 and a side wall parallel to the electrode stacking surface. Is provided.
  • the injection channel 15 penetrates the side wall of the electrolytic solution tank 2 and is provided so that the opening inside the electrolytic solution tank of the injection channel 15 is disposed in the vicinity of the bottom of the groove.
  • the discharge channel 16 passes through the side wall opposite to the side wall through which the injection channel 15 passes, and the opening inside the electrolyte tank of the discharge channel 16 is arranged in the vicinity of the lower edge 22 of the inclined surface 18. Is provided. With such a structure, the electrolyte flowing in the groove can be supplied to the vicinity of the upper edge 23 of the slope 18 and discharged from the vicinity of the lower edge 22 of the slope 18. Can do. Further, in the metal-air battery 25 shown in FIG.
  • the electrolyte is supplied to the vicinity of the upper edge 23 of the slope 18 in each cell 4. Can do. For this reason, as shown by the solid line arrows and the dotted line arrows shown in FIG. 21, the flow direction of the electrolytic solution in the electrolytic solution tank 2 from the injection channel 15 to the discharge channel 16 and the inclination direction of the inclined surface 18 are substantially set.
  • the used active material 20 can be efficiently discharged outside the cell assembly.
  • the opening inside the electrolyte bath of the injection channel 15 can be provided at a position higher than the uppermost portion of the air electrode 9 or higher than the uppermost portion of the metal electrode 5.
  • the electrolytic solution in the electrolytic solution tank 2 can flow between the metal electrode 5 and the air electrode 9, and convection is generated in the electrolytic solution near the surface of the metal electrode 5 and the surface of the air electrode 9. be able to.
  • the convection of the electrolyte solution in the vicinity of the surface of the metal electrode 5 it is possible to suppress the formation of an electrolyte solution having a locally high concentration of metal-containing ions, and the used active material 20 adheres to the metal electrode surface as a passive state. This can be suppressed.
  • the used active material 20 can be removed from the metal electrode surface by convection of the electrolytic solution. Moreover, it can suppress that the used active material 20 adheres to the surface of the air electrode 9, or the inside of a pore by the convection of the electrolyte solution of the surface vicinity of the air electrode 9. FIG. Even if the used active material 20 adheres to the surface of the air electrode 9, the used active material 20 can be removed from the surface of the air electrode 9 by convection of the electrolytic solution. For this reason, it can suppress that the used active material 20 inhibits an electrode reaction. Moreover, the used active material 20 in the electrolytic solution tank 2 can be efficiently recovered.
  • the opening inside the electrolytic solution tank of the injection channel 15 is provided at a position higher than the uppermost part of the air electrode 9 and the uppermost part of the metal electrode 5 as in the metal-air battery 25 shown in FIGS. be able to.
  • the electrolytic solution can flow in the direction of the solid arrow shown in FIG. 15B, and convection is generated in the electrolytic solution near the surface of the metal electrode 5 and the electrolytic solution near the surface of the air electrode 9.
  • the used active material 20 can be moved toward the bottom of the electrolytic solution tank 2 by this flow.
  • the used active material 20 that has been moved is discharged from the discharge channel 16 to the outside of the cell 4 together with the electrolytic solution.
  • the metal air battery 25 shown in FIG. 16 is a metal air battery 25 having a structure in which the injection flow path 15 of the metal air battery 25 shown in FIG. 15 is bent.
  • the position of the opening outside the cell of the injection flow path 15 and the position of the opening outside the cell of the discharge flow path 16 are 180 degrees with the central axis in the vertical direction of the cell 4 as the rotation axis.
  • the position of the opening outside the cell of the injection flow path 15 of the rotated cell 4 and the position of the opening outside the cell of the discharge flow path 16 of the non-rotated cell 4 are arranged so as to substantially overlap.
  • the electrolytic solution in the electrolytic solution tank 2 can be allowed to flow between the metal electrode 5 and the air electrode 9, and the used active material 20 on the surface of the metal electrode 5 can be removed by flowing into the electrolytic solution.
  • the metal-air battery 25 shown in FIG. 17 having a cell assembly in which four cells 4 having the same structure as the cell 4 shown in FIG. 16 are combined, in each cell 4, the electrolytic solution in the electrolytic solution tank 2 Can be allowed to flow between the metal electrode 5 and the air electrode 9, and the used active material 20 on the surface of the metal electrode 5 can be removed by flowing into the electrolytic solution.
  • the used active material 20 flows into the electrolytic solution tank 2 together with the electrolyte from the injection channel 15, and the used active material 20 is also The used active material 20 circulates between the metal electrode 5 and the air electrode 9, but the used active material 20 has a great influence on the convection generated in the electrolyte near the surface of the metal electrode 5 and the convection generated in the electrolyte near the surface of the air electrode 9. Is not considered to be given.
  • the injection flow path 15 is bent, in the cell assembly, between the electrodes included in one cell 4 and the electrodes included in the other cell 4 of the two adjacent cells 4. It is possible to increase the distance that ions are conducted in the electrolytic solution. Thereby, the electrical resistance between these electrodes can be increased, and a shunt current can be prevented from flowing between these electrodes.
  • a partition wall 17 that partitions the inside of the electrolytic solution tank 2 is provided, and a groove 19 is provided by the partition wall 17.
  • the injection channel 15 is provided so as to penetrate the side wall of the electrolytic solution tank 2 and supply the electrolytic solution to the vicinity of the bottom of the groove 19.
  • the partition wall 17 is provided so that the electrolytic solution supplied into the groove 19 passes over the partition wall 17 and flows toward the discharge channel 16.
  • the electrolytic solution in the electrolytic solution tank 2 can flow between the metal electrode 5 and the air electrode 9, and convection is generated in the electrolytic solution near the surface of the metal electrode 5 and the surface of the air electrode 9. be able to.
  • the position of the opening outside the cell of the injection flow path 15 and the position of the opening outside the cell of the discharge flow path 16 are set so that the center axis in the vertical direction of the cell 4 is the rotation axis.
  • the position of the opening outside the cell of the injection flow path 15 of the cell 4 rotated by 180 degrees and the position of the opening outside the cell of the discharge flow path 16 of the cell 4 not rotated are arranged so as to substantially overlap. Yes.
  • a plurality of injection channels 15 and discharge channels 16 may be provided.
  • the plurality of injection channels 15 and the plurality of discharge channels 16 can be provided, for example, like the metal-air battery 25 shown in FIG. In the metal-air battery 25 shown in FIG. 18, the two injection channels 15 and 15 ′ penetrate the side wall of the electrolyte bath 2, and the opening inside the electrolyte bath of the injection channel 15 is the lower edge of the slope 18.
  • the opening inside the electrolytic solution tank of the injection channel 15 ′ is arranged at a position higher than the uppermost part of the metal electrode 5 and the uppermost part of the air electrode 9.
  • the two discharge channels 16 and 16 ′ pass through the side wall opposite to the side wall through which the injection channels 15 and 15 ′ pass, and the opening inside the electrolyte tank of the discharge channel 16 is below the slope 18. It is arrange
  • the electrolytic solution in the electrolytic solution tank 2 in each cell 4, the electrolytic solution in the electrolytic solution tank 2 , The used active material 20 on the surface of the metal electrode 5 can be removed, and the used active material 20 in the electrolytic solution tank 2 can be efficiently discharged.
  • the air electrode 9 is an electrode serving as a cathode.
  • hydroxide ions (OH ⁇ ) are generated from oxygen gas, water, and electrons in the atmosphere.
  • the air electrode 9 includes, for example, a conductive porous carrier and an air electrode catalyst supported on the porous carrier.
  • oxygen gas, water, and electrons can coexist on the air electrode catalyst, and the electrode reaction can proceed.
  • the water used for the electrode reaction may be supplied from the atmosphere or may be supplied from an electrolytic solution.
  • the air electrode 9 may be produced by applying a porous carrier carrying an air electrode catalyst to a conductive porous substrate.
  • the air electrode 9 can be produced by applying carbon carrying an air electrode catalyst to carbon paper or carbon felt.
  • This conductive porous substrate may function as the air electrode current collector 10.
  • the metal-air battery 25 may include an air electrode current collector 10 that collects charges of the air electrode 9. As a result, the charge generated at the air electrode 9 can be efficiently extracted to the external circuit.
  • the air electrode current collector 10 may be the same member as the member that forms the air flow path 12.
  • the material of the air electrode current collector 10 is not particularly limited as long as it is corrosion resistant to the electrolytic solution, and examples thereof include nickel, gold, silver, copper, and stainless steel.
  • the air electrode current collector 10 may be a conductive base material subjected to nickel plating, gold plating, silver plating, or copper plating.
  • the shape of the air electrode current collector 10 can be, for example, a plate shape, a mesh shape, a punching metal, or the like.
  • a method of joining the air electrode current collector 10 to the porous carrier or the conductive porous substrate a method of pressure bonding by screwing through a frame or a method of bonding using a conductive adhesive Etc.
  • the air electrode 9 included in one cell 4 may be provided only on one side of the metal electrode 5, and provided on both sides of the metal electrode 5 as shown in FIGS. 1 (a) and 3 (a). Also good.
  • the porous carrier contained in the air electrode 9 include carbon black such as acetylene black, furnace black, channel black and ketjen black, and conductive carbon particles such as graphite and activated carbon.
  • carbon fibers such as vapor grown carbon fiber (VGCF), carbon nanotube, carbon nanowire, and the like can be used.
  • the air electrode catalyst examples include fine particles made of platinum, iron, cobalt, nickel, palladium, silver, ruthenium, iridium, molybdenum, manganese, a metal compound thereof, and an alloy containing two or more of these metals. .
  • This alloy is preferably an alloy containing at least two of platinum, iron, cobalt, and nickel.
  • the porous carrier contained in the air electrode 9 may be subjected to a surface treatment so that a cationic group exists as a fixed ion on the surface thereof.
  • the air electrode 9 may have an anion exchange resin supported on a porous carrier. Thereby, since hydroxide ions can be conducted through the anion exchange resin, the hydroxide ions generated on the air electrode catalyst are easily moved.
  • the air electrode 9 may be provided so as to be in direct contact with the atmosphere, or may be provided so that air flowing through the air flow path 12 is supplied to the air electrode 9. As a result, oxygen gas can be supplied to the air electrode 9.
  • water can be supplied to the air electrode 9 together with oxygen gas by flowing humidified air through the air flow path 12.
  • air flow path 12 can be provided so that air is supplied to the flow path 12.
  • the air flow path 12 can be provided in the housing 1 included in the metal-air battery 25 shown in FIGS.
  • the air electrode 9 may be provided so as to contact the electrolytic solution 3 in the electrolytic solution tank 2.
  • hydroxide ions generated at the air electrode 9 can easily move to the electrolytic solution 3.
  • water necessary for the electrode reaction at the air electrode 9 is easily supplied from the electrolyte 3 to the air electrode 9.
  • the air electrode 9 may be provided so as to be in contact with an ion exchange membrane that is in contact with the electrolytic solution 3 stored in the electrolytic solution tank 2.
  • the ion exchange membrane can be provided so as to partition the electrolytic solution 3 in the electrolytic solution tank 2 and the air electrode 9.
  • the ion exchange membrane may be an anion exchange membrane.
  • the ion exchange membrane By providing the ion exchange membrane, ion species moving between the air electrode 9 and the electrolytic solution 3 can be limited.
  • the ion exchange membrane is an anion exchange membrane, since the anion exchange membrane has a cation group that is a fixed ion, the cation in the electrolytic solution cannot be conducted to the air electrode 9.
  • the hydroxide ion generated at the air electrode 9 is an anion, it can be conducted to the electrolytic solution.
  • the battery reaction of the metal-air battery 25 can proceed, and the cations in the electrolyte 3 can be prevented from moving to the air electrode 9. Thereby, precipitation of the metal and carbonate compound in the air electrode 9 can be suppressed.
  • the ion exchange membrane By providing the ion exchange membrane, it is possible to suppress excessive supply of water contained in the electrolytic solution to the air electrode 9.
  • the ion exchange membrane include perfluorosulfonic acid, perfluorocarboxylic acid, styrene vinylbenzene, and quaternary ammonium solid polymer electrolyte membranes (anion exchange membranes).
  • the metal-air battery 25 can include a used active material recovery mechanism for recovering the used active material 20 discharged together with the electrolyte from the cell 4 or the cell assembly.
  • the used active material recovery mechanism is not particularly limited as long as it is a mechanism that can recover the used active material 20.
  • an electrolyte channel 26 that circulates the electrolyte in the electrolyte tank 2 is provided, It may be a mechanism for recovering the used active material 20 when the electrolytic solution is circulated.
  • the metal-air battery 25 shown in FIG. 4 has a used active material recovery mechanism including a recovery tank 30 and a filtration unit 33.
  • the electrolytic solution 3 discharged from the cell assembly flows into the recovery tank 30 together with the used active material 20 so that the used active material 20 contained in the electrolytic solution 3 flowing in the recovery tank 30 is precipitated. It is configured. Further, the electrolytic solution 3 after the used active material 20 is precipitated is configured to flow into the electrolytic solution tank 2 by a pump 31. By setting it as such a structure, the used active material 20 which precipitated in the electrolyte solution tank 2 can be moved to the collection tank 30. FIG. The used active material 20 precipitated in the collection tank 30 can be collected as a residue on the filter 34 by flowing the used active material 20 together with the electrolyte 3 into the filtration unit 33 as shown in FIG.
  • Electrolyte tank 3 Electrolyte solution 4: Cell 5: Metal electrode 7: Metal electrode current collector 9: Air electrode 10: Air electrode current collector 12: Air flow channel 15: Injection flow channel 16: Discharge flow path 17: Bulkhead 18: Slope 19: Groove 20: Used active material 22: Lower edge of the slope 23: Upper edge of the slope 25: Metal air battery 26: Electrolyte flow path 30: Collection tank 31: Pump 33: Filtration section 34: Filter 35: Valve

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Hybrid Cells (AREA)

Abstract

L'invention concerne un accumulateur métal-air caractérisé en ce qu'il comprend un réservoir de solution d'électrolyte, une électrode métallique qui est disposée dans le réservoir de solution d'électrolyte et sert d'anode, une électrode oxydoréductrice qui sert de cathode, un canal d'injection permettant d'alimenter le réservoir de solution d'électrolyte en solution d'électrolyte, et un canal d'évacuation permettant d'évacuer la solution d'électrolyte du réservoir de solution d'électrolyte. Cet accumulateur métal-air est également caractérisé en ce que le fond du réservoir de solution d'électrolyte comporte une surface inclinée et en ce que l'ouverture du canal d'évacuation dans le réservoir de solution d'électrolyte est disposée à proximité du bord inférieur de la surface inclinée.
PCT/JP2014/060705 2013-04-25 2014-04-15 Accumulateur métal-air WO2014175117A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2013-092540 2013-04-25
JP2013092540 2013-04-25

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WO2014175117A1 true WO2014175117A1 (fr) 2014-10-30

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WO (1) WO2014175117A1 (fr)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107204499A (zh) * 2017-06-03 2017-09-26 上海博暄能源科技有限公司 一种新型金属空气电池系统
JP2017538274A (ja) * 2014-10-31 2017-12-21 深▲ふん▼市謳徳新能源技術有限公司Ｓｈｅｎｚｈｅｎ Ｏｕｄｅ Ｎｅｗ Ｅｎｅｒｇｙ Ｔｅｃｈｎｏｌｏｇｙ Ｃｏ．， Ｌｔｄ 燃料電池スタック、燃料電池および殻体
CN110313101A (zh) * 2017-02-03 2019-10-08 藤仓复合材料科技有限公司 金属空气电池及其使用方法

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS519230A (fr) * 1974-07-12 1976-01-24 Kogyo Gijutsuin
JPS5223628A (en) * 1975-08-19 1977-02-22 Matsushita Electric Ind Co Ltd Air cell
JP2010140749A (ja) * 2008-12-11 2010-06-24 Equos Research Co Ltd 空気電池
JP2011258489A (ja) * 2010-06-11 2011-12-22 National Institute Of Advanced Industrial & Technology 固体電解質膜・空気極用電解液間に陽イオン交換膜を具備するリチウム−空気電池
JP2013225443A (ja) * 2012-04-23 2013-10-31 Sharp Corp 金属空気電池およびエネルギーシステム

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS519230A (fr) * 1974-07-12 1976-01-24 Kogyo Gijutsuin
JPS5223628A (en) * 1975-08-19 1977-02-22 Matsushita Electric Ind Co Ltd Air cell
JP2010140749A (ja) * 2008-12-11 2010-06-24 Equos Research Co Ltd 空気電池
JP2011258489A (ja) * 2010-06-11 2011-12-22 National Institute Of Advanced Industrial & Technology 固体電解質膜・空気極用電解液間に陽イオン交換膜を具備するリチウム−空気電池
JP2013225443A (ja) * 2012-04-23 2013-10-31 Sharp Corp 金属空気電池およびエネルギーシステム

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2017538274A (ja) * 2014-10-31 2017-12-21 深▲ふん▼市謳徳新能源技術有限公司Ｓｈｅｎｚｈｅｎ Ｏｕｄｅ Ｎｅｗ Ｅｎｅｒｇｙ Ｔｅｃｈｎｏｌｏｇｙ Ｃｏ．， Ｌｔｄ 燃料電池スタック、燃料電池および殻体
CN110313101A (zh) * 2017-02-03 2019-10-08 藤仓复合材料科技有限公司 金属空气电池及其使用方法
CN107204499A (zh) * 2017-06-03 2017-09-26 上海博暄能源科技有限公司 一种新型金属空气电池系统

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