WO2022190460A1 - Batterie secondaire au zinc - Google Patents

Batterie secondaire au zinc Download PDF

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Publication number
WO2022190460A1
WO2022190460A1 PCT/JP2021/041503 JP2021041503W WO2022190460A1 WO 2022190460 A1 WO2022190460 A1 WO 2022190460A1 JP 2021041503 W JP2021041503 W JP 2021041503W WO 2022190460 A1 WO2022190460 A1 WO 2022190460A1
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WIPO (PCT)
Prior art keywords
negative electrode
positive electrode
current collecting
secondary battery
tab
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PCT/JP2021/041503
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English (en)
Japanese (ja)
Inventor
朋大 高橋
淳宣 松矢
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日本碍子株式会社
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Priority to JP2023505099A priority Critical patent/JPWO2022190460A1/ja
Publication of WO2022190460A1 publication Critical patent/WO2022190460A1/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
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/24—Alkaline accumulators
    • H01M10/28—Construction or manufacture
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/24—Alkaline accumulators
    • H01M10/30—Nickel accumulators
    • 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
    • H01M12/08—Hybrid cells; Manufacture thereof composed of a half-cell of a fuel-cell type and a half-cell of the secondary-cell type
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
    • 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
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/409—Separators, membranes or diaphragms characterised by the material
    • H01M50/431—Inorganic material
    • H01M50/434—Ceramics
    • 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
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/409—Separators, membranes or diaphragms characterised by the material
    • H01M50/446—Composite material consisting of a mixture of organic and inorganic materials
    • 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
    • H01M50/50—Current conducting connections for cells or batteries
    • H01M50/531—Electrode connections inside a battery casing
    • H01M50/533—Electrode connections inside a battery casing characterised by the shape of the leads or tabs
    • 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
    • H01M50/50—Current conducting connections for cells or batteries
    • H01M50/531—Electrode connections inside a battery casing
    • H01M50/54—Connection of several leads or tabs of plate-like electrode stacks, e.g. electrode pole straps or bridges

Definitions

  • the present invention relates to zinc secondary batteries.
  • a multi-layer cell type secondary battery is known in which a plurality of positive electrode plates and negative electrode plates with current collecting tabs are alternately stacked.
  • a configuration is known in which a plurality of current collecting tabs are bundled and connected to a current collecting terminal.
  • a current collecting tab has a curved portion that curves between an active material placement portion and a current collecting terminal, and a tip portion on the side opposite to the active material placement portion. and a secondary battery having a structure in which the tip portion is joined to a collector terminal.
  • Patent Document 2 International Publication No.
  • 2020/071049 discloses a secondary battery accommodated in a battery case in a state in which the current collecting tab is bent, and the current collecting tab is connected to the current collecting terminal. It is said to have a joint portion and a bent portion spaced from the joint portion and provided at a position on the side of the electrode assembly, and serving as a starting point for bending of the current collecting tab.
  • LDH-like compounds are known as hydroxides and/or oxides having a layered crystal structure similar to LDH, although they cannot be called LDH. It exhibits physical ion conduction properties.
  • Patent Document 5 International Publication No. 2020/255856 describes hydroxide ions containing a porous substrate and a layered double hydroxide (LDH)-like compound that closes the pores of the porous substrate. A conductive separator is disclosed.
  • Patent Document 6 International Publication No. 2019/069760
  • Patent Document 7 International Publication No.
  • the entire negative electrode active material layer is covered or wrapped with a liquid retaining member and an LDH separator, and the positive electrode active material layer
  • a zinc secondary battery having a structure in which a material layer is covered or wrapped with a liquid-retaining member has been proposed.
  • a nonwoven fabric is used as the liquid retaining member. According to such a configuration, a zinc secondary battery (especially a laminated battery thereof) capable of preventing the extension of zinc dendrites can be produced very simply and with high productivity by eliminating the need for complicated sealed bonding between the LDH separator and the battery container. It is said that it can be done.
  • the inventors of the present invention have recently found that a multi-layer zinc secondary battery in which short circuits are less likely to occur can be provided by adopting current collecting tabs that are not rounded and are bent in at least two locations. got
  • a positive electrode plate including a positive electrode active material layer and a positive electrode current collector; a positive current collecting tab extending in a predetermined direction from an end of the positive electrode plate; a negative electrode plate including a negative electrode current collector and a negative electrode active material layer containing at least one selected from the group consisting of zinc, zinc oxide, zinc alloys and zinc compounds; a negative electrode current collecting tab extending from an end portion of the negative electrode plate in the predetermined direction at a position not overlapping with the positive electrode current collecting tab; a hydroxide ion conductive separator separating the positive electrode plate and the negative electrode plate so as to conduct hydroxide ions; an electrolyte; A zinc secondary battery comprising a plurality of unit cells containing Each of the positive electrode current collecting tab and the negative electrode current collecting tab has a non-rounded shape that is bent in at least two places when viewed in cross section.
  • each of the negative electrode current collecting tabs has at least two straight portions parallel to the positive electrode plate and the negative electrode plate and an inclined portion between the at least two straight portions;
  • the straight portions of the positive electrode current collecting tabs away from the positive electrode plate are stacked and joined to form a positive electrode tab joint portion, and the negative electrode current collecting tabs are separated from the negative electrode plate.
  • the straight portions on the other side are stacked and joined to form a negative electrode tab joint,
  • the positive electrode current collecting tab and/or the negative electrode current collecting tab are located in the same plane as the positive electrode tab joint portion and/or the negative electrode tab joint portion, the positive electrode current collecting tab is located in the same plane. and/or the zinc secondary battery is provided, wherein the negative electrode current collecting tab may exceptionally consist of only one straight portion parallel to the positive electrode plate and/or the negative electrode plate without being bent. be.
  • FIG. 1 is a schematic cross-sectional view showing an example of a zinc secondary battery according to the present invention
  • FIG. FIG. 2 is a diagram schematically showing a cross section of the zinc secondary battery shown in FIG. 1 taken along the line A-A'
  • FIG. 3 is an enlarged view of the joint structure of the current collecting tabs shown in FIG. 2
  • FIG. 2 is a perspective view schematically showing a battery element of the zinc secondary battery shown in FIG. 1
  • FIG. 2 is a cross-sectional view schematically showing a battery element of the zinc secondary battery shown in FIG. 1; It is a figure which shows the manufacturing procedure of the junction structure of the current collection tab by this invention.
  • FIG. 4 is a cross-sectional view showing the inclination angle of the inclined portion of the current collecting tab according to the present invention
  • FIG. 4 is a cross-sectional view conceptually showing the vicinity of a bent portion of the current collecting tab according to the present invention.
  • FIG. 2 is a cross-sectional view schematically showing an example of a conventional junction structure of current collecting tabs.
  • FIG. 10 is a cross-sectional view schematically showing another example of a conventional junction structure of current collecting tabs. It is a figure which shows typically the manufacturing procedure of the junction structure of the conventional current collection tab.
  • FIG. 3 is a cross-sectional view schematically showing the vicinity of a bent portion of a conventional current collecting tab.
  • the zinc secondary battery of the present invention is not particularly limited as long as it is a secondary battery using zinc as a negative electrode and using an alkaline electrolyte (typically an aqueous alkali metal hydroxide solution). Therefore, it can be a nickel-zinc secondary battery, a silver-zinc oxide secondary battery, a manganese-zinc oxide secondary battery, an air-zinc secondary battery, and various other alkaline zinc secondary batteries.
  • the positive electrode active material layer preferably contains nickel hydroxide and/or nickel oxyhydroxide, thereby making the zinc secondary battery a nickel-zinc secondary battery.
  • the positive electrode active material layer may be the air electrode layer, whereby the zinc secondary battery may form a zinc air secondary battery.
  • the zinc secondary battery 10 shown in these figures includes a battery element 11 in a battery case 20, a positive plate 12, a positive collector tab 12b, a negative plate 14, and a negative collector tab 14c. , a hydroxide ion-conducting separator 16 and an electrolyte 18 .
  • a plurality of unit cells 10a are stacked to form a multi-layer cell.
  • the positive electrode plate 12 includes a positive active material layer 12a and a positive current collector (not shown), and a positive current collecting tab 12b extends from the positive electrode plate 12 in a predetermined direction.
  • the negative plate 14 includes a negative active material layer 14a and a negative current collector 14b.
  • the negative electrode active material layer 14a contains at least one selected from the group consisting of zinc, zinc oxide, zinc alloys and zinc compounds.
  • the negative electrode current collecting tab 14c extends from the negative electrode plate 14 in a predetermined direction at a position not overlapping the positive electrode current collecting tab 12b.
  • the hydroxide ion conducting separator 16 separates the positive plate 12 and the negative plate 14 in a hydroxide ion conducting manner.
  • Each of the positive electrode current collecting tab 12b and the negative electrode current collecting tab 14c has a non-rounded shape that is bent at at least two points F when viewed in cross section.
  • Each of the 12b and the negative current collecting tab 14c has at least two straight portions S parallel to the positive electrode plate 12 and the negative electrode plate 14 and an inclined portion I between the at least two straight portions S.
  • the straight portions S of the positive electrode current collecting tabs 12b remote from the positive electrode plate 12 are stacked and joined together to form a positive electrode tab joint portion (not shown), and the negative electrode of the negative electrode current collecting tab 14c.
  • the straight portions S remote from the plate 14 are stacked and joined to form a negative electrode tab joint portion 30 .
  • the positive electrode current collecting tab 12b and/or the negative electrode current collecting tab 14c located in the same plane as the positive electrode tab joint portion and/or the negative electrode tab joint portion 30 exist, the positive electrode current collecting tab 12b and/or the positive electrode current collecting tab 12b and/or /Or the negative electrode current collecting tab 14c may exceptionally consist of only one straight portion parallel to the positive electrode plate 12 and/or the negative electrode plate 14 without being bent.
  • a zinc secondary battery can be provided.
  • the current collecting tabs for conventional multi-layer cells do not have folds F in the positive electrode current collecting tab 12b and the negative electrode current collecting tab 14c as shown in FIG. 12b and the negative electrode current collecting tab 14c have only one crease F. Both include rounded shapes (curved shapes).
  • the current collecting tabs are pulled.
  • the positive electrode plates 12 and the negative electrode plates 14 are alternately stacked to form a multi-layer cell, and the positive electrode current collecting tabs 12b or the negative electrode current collecting tabs 14c are bundled and pressed, and the positive electrode terminal 26 is formed.
  • the negative electrode active material layer 14a shrinks unevenly toward the center as charging and discharging are repeated, that is, the outer peripheral portion of the negative electrode active material layer 14a (ZnO layer) is unevenly eroded and lost. It is a phenomenon. There is a concern that the current collecting tab will be further pulled along with the deformation of the negative electrode plate edge due to this shape change, and the risk of short circuit will further increase.
  • each of the positive electrode current collecting tab 12b and the negative electrode current collecting tab 14c has at least two points when viewed in cross section, unlike the conventional current collecting tabs. It has a non-rounded shape folded at F.
  • each of the positive electrode current collecting tab 12b and the negative electrode current collecting tab 14c has at least two straight portions S parallel to the positive electrode plate 12 and the negative electrode plate 14 and an inclined portion I between the at least two straight portions S. have. Therefore, when the positive electrode plates 12 and the negative electrode plates 14 are alternately stacked, the straight portions S of the positive electrode current collecting tabs 12b remote from the positive electrode plates 12 can be stacked (that is, bundled) so that they are in contact with each other.
  • the straight portions S of the negative electrode current collecting tabs 14c remote from the negative electrode plate 14 can be stacked (that is, bundled) so that they are in contact with each other. Due to the presence of the inclined portion I, the position of the lamination method between the straight portion S closer to the positive electrode plate 12 or the negative electrode plate 14 and the straight portion S farther from the positive electrode plate 12 or the negative electrode plate 14 is changed. This is because the deviation (gap) is canceled. Since the gap differs for each positive electrode plate 12 or each negative electrode plate 14, the individual gaps can be conveniently canceled by individually setting the inclination angle of the inclined portion I.
  • the positive electrode current collecting tabs 12b and the negative electrode current collecting tabs 14c can be bundled together and joined to a member such as a terminal without pulling the positive electrode current collecting tabs 12b or the negative electrode current collecting tabs 14c. . That is, in contrast to FIG. 12 of the conventional manufacturing method, an excessive load is not applied to the ends of the positive electrode active material layer 12a and the negative electrode active material layer 14a as shown in FIG. , the defect D is less likely to occur in the negative electrode active material layer 14a and/or the separator 16, and the risk of short circuit is reduced.
  • the angle of inclination of the inclined portion I with respect to the straight portion S can be in the range of 0° to 90°, typically 0° to 85°, more typically 0° to 80°, more typically is 0° to 70°. Within such a range, even when a large number of positive electrode plates 12 and negative electrode plates 14 are stacked, the positive electrode current collecting tab 12b or the negative electrode current collecting tab 14c can be easily attached to a member such as a terminal without being pulled. can be spliced. If there are current collecting tabs with an inclination angle of 90°, the length of the straight part S is individually changed so that the inclined part I does not hit the adjacent current collecting tab. The tabs can be bundled and joined to a member such as a terminal.
  • the inclination angle of the inclined portion I with respect to the straight portion S is determined by using a plane parallel to the straight portion S arranged parallel to the plate surface of the positive electrode plate 12 or the negative electrode plate 14 as shown in FIG. is defined as the acute to 90° angle (i.e. not obtuse) formed by I and slope I. Therefore, in the case of a typical embodiment in which one inclined portion I exists between two straight portions S as shown in FIG. scientifically equivalent.
  • ⁇ 1 and ⁇ 2 do not have to be completely equal, and may be substantially equal with a tolerance to the extent that the straight S portion on the terminal side can be bundled without problems.
  • each inclined portion I of the positive electrode current collecting tab 12b and the negative electrode current collecting tab 14c is connected to a positive electrode tab joint portion (not shown) or a negative electrode tab joint portion 30 and the positive electrode plate 12 or the negative electrode plate.
  • the inclination angle with respect to the straight portion S is individually set so as to offset the positional deviation in the lamination direction between the plate 14 and the inclined portions of the adjacent positive electrode current collecting tab 12b and the negative electrode current collecting tab 14c. form different tilt angles.
  • the positive tab joint (not shown) and/or the negative tab joint
  • the inclination angles of the positive electrode current collecting tab 12b and the negative electrode current collecting tab 14c gradually decrease toward the same plane as 30 . Therefore, it is typical that the inclination angles of the positive electrode current collecting tab 12b and the negative electrode current collecting tab 14c gradually decrease from the outside toward the center of the multilayer cell, but the present invention is not limited to this.
  • the positive current collecting The inclination angles of the tab 12b and the negative electrode current collecting tab 14c may gradually decrease. Therefore, it is also possible to employ a configuration in which the inclination angle gradually decreases from one outside of the multilayer cell to the other outside.
  • the positive electrode plate 12 includes a positive electrode active material layer 12a.
  • the positive electrode active material forming the positive electrode active material layer 12a is not particularly limited, and may be appropriately selected from known positive electrode materials according to the type of zinc secondary battery. For example, in the case of a nickel-zinc secondary battery, a positive electrode containing nickel hydroxide and/or nickel oxyhydroxide may be used. Alternatively, in the case of a zinc-air secondary battery, the air electrode may be used as the positive electrode.
  • the positive electrode plate 12 further includes a positive current collector (not shown), and the positive electrode current collector extends in a predetermined direction (eg, upward) from an end (eg, upper end) of the positive electrode plate 12 . It preferably has a tab 12b.
  • the positive electrode current collector include nickel porous substrates such as foamed nickel plates.
  • a positive electrode plate composed of a positive electrode/positive current collector can be preferably produced by uniformly applying a paste containing an electrode active material such as nickel hydroxide onto a nickel porous substrate and drying the paste.
  • the positive electrode plate 12 shown in FIG. 5 includes a positive electrode current collector (for example foamed nickel), it is not shown.
  • the positive electrode collector tab 12b may be made of the same material as the positive electrode collector, or may be made of a different material.
  • the positive electrode current collector is a nickel porous substrate such as a foamed nickel plate, it can be processed into a tab shape by pressing. In any case, such a tab may be supplemented with another current collecting member such as a tab lead to extend the positive electrode current collecting tab 12b.
  • a plurality of positive electrode current collecting tabs 12b are joined to one positive electrode terminal 26 or a member electrically connected thereto to form a positive electrode tab joining portion (not shown). By doing so, current collection can be performed with good space efficiency with a simple configuration, and connection to the positive electrode terminal 26 is also facilitated.
  • the positive electrode current collecting tab 12b and a member such as a terminal may be joined using a known joining method such as ultrasonic welding (ultrasonic joining), laser welding, TIG welding, or resistance welding.
  • the positive electrode plate 12 may contain at least one additive selected from the group consisting of silver compounds, manganese compounds, and titanium compounds, whereby the positive electrode reaction absorbs hydrogen gas generated by the self-discharge reaction. can promote Moreover, the positive electrode plate 12 may further contain cobalt. Cobalt is preferably contained in the positive electrode plate 12 in the form of cobalt oxyhydroxide. In the positive electrode plate 12, cobalt functions as a conductive aid, thereby contributing to an improvement in charge/discharge capacity.
  • the negative electrode plate 14 includes a negative electrode active material layer 14a.
  • the negative electrode active material forming the negative electrode active material layer 14a contains at least one selected from the group consisting of zinc, zinc oxide, zinc alloys, and zinc compounds. Zinc may be contained in any form of zinc metal, zinc compound, and zinc alloy as long as it has electrochemical activity suitable for the negative electrode. Preferred examples of the negative electrode material include zinc oxide, zinc metal, calcium zincate, etc., and a mixture of zinc metal and zinc oxide is more preferred.
  • the negative electrode active material may be configured in a gel form, or may be mixed with the electrolytic solution 18 to form a negative electrode mixture. For example, a gelled negative electrode can be easily obtained by adding an electrolytic solution and a thickener to the negative electrode active material. Examples of the thickener include polyvinyl alcohol, polyacrylate, CMC, alginic acid, etc. Polyacrylic acid is preferable because of its excellent chemical resistance to strong alkali.
  • the zinc alloy it is possible to use a zinc alloy that does not contain mercury and lead, which is known as a zinc-free zinc alloy.
  • a zinc alloy containing 0.01 to 0.1% by mass of indium, 0.005 to 0.02% by mass of bismuth, and 0.0035 to 0.015% by mass of aluminum has the effect of suppressing hydrogen gas generation. Therefore, it is preferable.
  • Indium and bismuth are particularly advantageous in terms of improving discharge performance.
  • the use of a zinc alloy for the negative electrode slows down the rate of self-dissolution in an alkaline electrolyte, thereby suppressing the generation of hydrogen gas and improving safety.
  • the shape of the negative electrode material is not particularly limited, it is preferably powdered, which increases the surface area and enables high-current discharge.
  • the average particle size of the preferred negative electrode material is in the range of 3 to 100 ⁇ m in minor axis. It is easy to mix uniformly with the agent, and is easy to handle during battery assembly.
  • the negative plate 14 further includes a negative current collector 14b.
  • the negative electrode current collector 14b is provided inside and/or on the surface of the negative electrode active material layer 14a except for the portion extending as the negative electrode current collecting tab 14c. That is, the negative electrode active material layer 14a may be arranged on both sides of the negative electrode current collector 14b, or the negative electrode active material layer 14a may be arranged only on one side of the negative electrode current collector 14b. good.
  • the negative electrode collector tab 14c extends from the end (eg, upper end) of the negative electrode plate 14 in a predetermined direction (eg, upward) at a position that does not overlap the positive electrode collector tab 12b.
  • the negative electrode current collecting tab 14c is preferably provided at a position not overlapping the positive electrode current collecting tab 12b.
  • the negative electrode collector tab 14c may be made of the same material as the negative electrode collector 14b, or may be made of a different material. In any case, such a tab may be supplemented with another current collecting member such as a tab lead to extend the negative electrode current collecting tab 14c. In any case, it is preferable that a plurality of negative electrode current collecting tabs 14c are joined to one negative electrode terminal 28 or a member electrically connected thereto to constitute the negative electrode tab joining portion 30. FIG. By doing so, it is possible to collect current with a simple structure and with good space efficiency, and the connection to the negative electrode terminal 28 is also facilitated.
  • the bonding between the negative electrode current collecting tab 14c and a member such as a terminal may be performed using a known bonding method such as ultrasonic welding (ultrasonic bonding), laser welding, TIG welding, resistance welding, or the like.
  • a metal plate having a plurality (or a large number) of openings as the negative electrode current collector 14b.
  • Preferred examples of such a negative electrode current collector 14b include expanded metal, punched metal, metal mesh, and combinations thereof, more preferably copper expanded metal, copper punched metal, and combinations thereof, especially Copper expanded metal is preferred.
  • a mixture comprising zinc oxide powder and/or zinc powder and, if desired, a binder (for example, polytetrafluoroethylene particles) is applied onto a copper expanded metal to form a negative electrode composed of a negative electrode/a negative electrode current collector. Plates can be preferably made.
  • the expanded metal is a mesh-like metal plate obtained by expanding a metal plate with zigzag cuts by an expander and forming the cuts into a diamond shape or a tortoiseshell shape.
  • a perforated metal is also called a perforated metal, and is made by punching holes in a metal plate.
  • a metal mesh is a metal product with a wire mesh structure, and is different from expanded metal and perforated metal.
  • the hydroxide ion-conducting separator 16 is provided so as to separate the positive electrode plate 12 and the negative electrode plate 14 so that hydroxide ions can be conducted.
  • the negative electrode plate 14 may be covered or wrapped with a hydroxide ion conductive separator 16 .
  • a simple configuration in which the hydroxide ion conductive separator 16 is arranged on one side of the positive electrode plate 12 or the negative electrode plate 14 may also be used.
  • the hydroxide ion-conducting separator 16 is not particularly limited as long as it can separate the positive electrode plate 12 and the negative electrode plate 14 so that hydroxide ions can be conducted, but typically includes a hydroxide ion-conducting solid electrolyte. , is a separator that allows hydroxide ions to pass through exclusively by utilizing hydroxide ion conductivity.
  • Preferred hydroxide ion-conducting solid electrolytes are layered double hydroxides (LDH) and/or LDH-like compounds. Therefore, hydroxide ion conducting separator 16 is preferably an LDH separator.
  • LDH separator refers to a separator containing LDH and/or LDH-like compounds, which selectively removes hydroxide ions by exclusively utilizing the hydroxide ion conductivity of LDH and/or LDH-like compounds.
  • LDH-like compounds are hydroxides and/or oxides of layered crystal structure similar to LDH, although they may not be called LDH, and can be said to be equivalents of LDH.
  • LDH can be interpreted as including not only LDH but also LDH-like compounds.
  • the LDH separator is preferably composited with the porous substrate.
  • the LDH separator further includes a porous substrate, and the LDH and/or the LDH-like compound are combined with the porous substrate in a form in which the pores of the porous substrate are filled.
  • preferred LDH separators are those in which LDH and/or LDH-like compounds are porous so as to exhibit hydroxide ion conductivity and gas impermeability (and thus function as LDH separators exhibiting hydroxide ion conductivity). block the pores of the base material.
  • the porous substrate is preferably made of a polymeric material, and it is particularly preferable that the LDH is incorporated throughout the entire thickness direction of the porous substrate made of polymeric material.
  • LDH separators as disclosed in Patent Documents 1-7 can be used.
  • the thickness of the LDH separator is preferably 5-100 ⁇ m, more preferably 5-80 ⁇ m, still more preferably 5-60 ⁇ m, particularly preferably 5-40 ⁇ m.
  • each of the positive plate 12, the positive current collecting tab 12b, the negative plate 14, the negative current collecting tab 14c, and the hydroxide ion conducting separator 16 are arranged vertically,
  • the multilayer cells are thereby preferably laterally multilayered.
  • the positive electrode current collecting tab 12b and the negative electrode current collecting tab 14c extend upward.
  • the zinc secondary battery 10 may further include a liquid retaining member 17 that contacts the positive electrode plate 12 and/or the negative electrode plate 14 .
  • a liquid retaining member 17 that contacts the positive electrode plate 12 and/or the negative electrode plate 14 .
  • the positive electrode plate 12 and/or the negative electrode plate 14 are covered or wrapped with the liquid retaining member 17 .
  • a simple configuration in which the liquid retaining member 17 is arranged on one side of the positive electrode plate 12 or the negative electrode plate 14 may be employed.
  • the electrolytic solution 18 can be evenly present between the positive electrode plate 12 and/or the negative electrode plate 14 and the hydroxide ion conductive separator 16. and/The transfer of hydroxide ions between the negative electrode plate 14 and the hydroxide ion conductive separator 16 can be performed efficiently.
  • the liquid holding member 17 is not particularly limited as long as it can hold the electrolytic solution 18, but is preferably a sheet-like member.
  • Preferred examples of the liquid-retaining member 17 include nonwoven fabrics, water-absorbing resins, liquid-retaining resins, porous sheets, and various spacers, but nonwoven fabrics are particularly preferable in that a negative electrode structure with good performance can be produced at low cost. be.
  • the liquid retaining member 17 or the nonwoven fabric preferably has a thickness of 10 to 200 ⁇ m, more preferably 20 to 200 ⁇ m, still more preferably 20 to 150 ⁇ m, particularly preferably 20 to 100 ⁇ m, most preferably 20 ⁇ m. ⁇ 60 ⁇ m.
  • a sufficient amount of the electrolytic solution 18 can be retained in the liquid retaining member 17 while keeping the overall size of the positive electrode structure and/or the negative electrode structure compact without waste.
  • the positive electrode plate 12 and/or the negative electrode plate 14 are covered or wrapped with the liquid retaining member 17 and/or the separator 16, their outer edges (sides from which the positive electrode current collecting tab 12b and the negative electrode current collecting tab 14c extend) except) preferably closed.
  • the liquid-retaining member 17 and/or the separator 16 has a closed outer edge by bending the liquid-retaining member 17 and/or the separator 16 or by sealing the liquid-retaining members 17 and/or the separators 16 together.
  • Preferred examples of sealing techniques include adhesives, heat welding, ultrasonic welding, adhesive tapes, sealing tapes, and combinations thereof.
  • an LDH separator containing a porous substrate made of a polymeric material has the advantage of being easy to bend because of its flexibility.
  • Thermal welding and ultrasonic welding may be performed using a commercially available heat sealer or the like.
  • the outer peripheral portion of the liquid retaining member 17 should be sandwiched between the LDH separators forming the outer peripheral portion. It is preferable to perform heat welding and ultrasonic welding by using the same method because more effective sealing can be performed.
  • commercially available adhesives, adhesive tapes and sealing tapes may be used, but those containing an alkali-resistant resin are preferable in order to prevent deterioration in an alkaline electrolyte.
  • examples of preferable adhesives include epoxy resin adhesives, natural resin adhesives, modified olefin resin adhesives, and modified silicone resin adhesives. It is more preferable because it is particularly excellent in alkalinity.
  • a product example of the epoxy resin-based adhesive includes the epoxy adhesive Hysol (registered trademark) (manufactured by Henkel).
  • the outer edge of one side, which is the upper end of the separator 16 is open.
  • This open-top configuration makes it possible to deal with the problem of overcharging in nickel-zinc batteries and the like. That is, when a nickel-zinc battery or the like is overcharged, oxygen (O 2 ) may be generated in the positive electrode plate 12, but the LDH separator has a high degree of denseness that substantially allows only hydroxide ions to pass. Impervious to O2 .
  • O 2 can escape to the upper side of the positive electrode plate 12 and be sent to the negative electrode plate 14 side through the upper open portion, thereby can oxidize Zn in the negative electrode active material and return it to ZnO.
  • overcharge resistance can be improved by using the open-top battery element 11 in a sealed zinc secondary battery.
  • a ventilation hole may be opened after sealing the outer edge of one side, which is the upper end of the LDH separator, or a part of the outer edge may be unsealed so that a ventilation hole is formed during sealing. good.
  • the electrolytic solution 18 preferably contains an aqueous alkali metal hydroxide solution.
  • the electrolytic solution 18 is only shown locally in FIG.
  • alkali metal hydroxides include potassium hydroxide, sodium hydroxide, lithium hydroxide and ammonium hydroxide, with potassium hydroxide being more preferred.
  • Zinc compounds such as zinc oxide and zinc hydroxide may be added to the electrolytic solution in order to suppress self-dissolution of zinc and/or zinc oxide.
  • the electrolyte may be mixed with the positive electrode active material and/or the negative electrode active material to exist in the form of a positive electrode mixture and/or a negative electrode mixture.
  • the electrolyte may be gelled to prevent leakage of the electrolyte.
  • the gelling agent it is desirable to use a polymer that absorbs the solvent of the electrolytic solution and swells, and polymers such as polyethylene oxide, polyvinyl alcohol and polyacrylamide, and starch are used.
  • the battery element 11 includes a plurality of positive electrode plates 12, a plurality of negative electrode plates 14, and a plurality of separators 16, and the unit of positive plate 12/separator 16/negative plate 14 is It is in the form of a positive/negative electrode laminate that is laminated so that the are repeated. That is, the zinc secondary battery 10 has a plurality of unit cells 10a, whereby the plurality of unit cells 10a form a multilayer cell as a whole. This is a so-called assembled battery or laminated battery configuration, and is advantageous in that a high voltage and a large current can be obtained.
  • the battery case 20 is preferably made of resin.
  • the resin constituting the battery case 20 is preferably a resin having resistance to alkali metal hydroxides such as potassium hydroxide, more preferably polyolefin resin, ABS resin, or modified polyphenylene ether, and still more preferably ABS resin. or modified polyphenylene ether.
  • the battery case 20 has an upper lid 20a.
  • the battery case 20 (for example, the upper lid 20a) may have a pressure release valve for releasing gas.
  • a case group in which two or more battery cases 20 are arranged may be accommodated in an outer frame to constitute a battery module.
  • Example 1 A positive electrode plate, a positive electrode current collecting tab, a negative electrode plate, a negative electrode current collecting tab, an LDH separator, a nonwoven fabric, a battery case, and an electrolytic solution shown below are prepared.
  • ⁇ Positive electrode plate A positive electrode paste containing nickel hydroxide and a binder is filled in the pores of foamed nickel and dried (there is an uncoated portion where the positive electrode paste is not applied near one side of the foamed nickel) ).
  • ⁇ Positive electrode current collecting tab The uncoated portion of foamed nickel constituting the positive electrode plate is compressed by a roll press to be processed into a tab, and a tab lead (made of pure nickel, thickness: 100 ⁇ m) is ultrasonically welded to this tab. extended one.
  • Negative electrode plate A negative electrode paste containing ZnO powder, metal Zn powder, polytetrafluoroethylene (PTFE) and propylene glycol is pressure-bonded to a current collector (copper expanded metal) (near one side of the copper expanded metal) There is an uncoated part where the negative electrode paste is not coated).
  • - Negative electrode current collecting tab A tab lead (made of copper, thickness: 100 ⁇ m) connected to an uncoated portion of expanded copper metal by ultrasonic welding.
  • ⁇ LDH separator Ni-Al-Ti-LDH (layered double hydroxide) deposited in the pores and on the surface of a polyethylene microporous membrane by hydrothermal synthesis and roll-pressed, thickness: 20 ⁇ m
  • Non-woven fabric Made of polypropylene, thickness 100 ⁇ m
  • Battery case Housing made of modified polyphenylene ether resin (equipped with a pressure release valve that allows the gas generated inside the case to be released)
  • ⁇ Electrolyte solution 5.4 mol/L KOH aqueous solution in which 0.4 mol/L ZnO is dissolved
  • the positive electrode plate is wrapped with non-woven fabric so as to cover both sides, and the non-woven fabric protrudes slightly from the remaining three sides except for one side where the positive electrode current collecting tab extends.
  • the surplus portions of the nonwoven fabric protruding from the three sides of the positive electrode plate are thermally fused and sealed with a heat seal bar to obtain a positive electrode structure.
  • the negative electrode plate is wrapped with the nonwoven fabric and the LDH separator in this order from both sides so that the nonwoven fabric and the LDH separator protrude slightly from the remaining three sides except for one side where the negative electrode current collecting tab extends.
  • the nonwoven fabric protruding from three sides of the negative electrode plate and the surplus portions of the LDH separator are thermally fused and sealed with a heat seal bar to obtain a negative electrode structure.
  • a total of 19 electrode structures consisting of 9 positive electrode structures and 10 negative electrode structures are prepared.
  • each of the positive electrode current collecting tab 12b and the negative electrode current collecting tab 14c has two straight portions S parallel to the positive electrode plate 12 and the negative electrode plate 14 when viewed in cross section, and an inclined portion between the two straight portions S. is plastically deformed (formed) to have I.
  • the electrode structures provided with the current collecting tabs plastically deformed by forming in this way are stacked in serial number order as shown in FIGS.
  • the nine positive electrode current-collecting tabs 12b and the ten negative electrode current-collecting tabs 14c extend from different positions from the electrode current collector in plan view. Since the design is such that the nine positive electrode current collecting tabs 12b are overlapped with each other, the ten negative electrode current collecting tabs 14c are overlapped with each other at a different position. In this way, the overlapping portions of the straight portions S of the nine positive electrode current collecting tabs 12b on the side away from the positive electrode plate 12 are collectively joined to the positive electrode terminal 26 by laser welding to form a positive electrode tab joint portion (not shown).
  • a stack of electrode structures including positive electrode current collecting tabs 12b and negative electrode current collecting tabs 14c having inclined portions I with various inclination angles ⁇ 1 and ⁇ 2 shown in Table 1 is obtained as a battery element 11 .
  • this battery element 11 is placed in a battery case 20, an electrolytic solution 18 is injected to impregnate the battery element 11, and the lid 20a is closed and sealed.
  • Example 2 A total of 23 electrode structures consisting of 11 positive electrode structures and 12 negative electrode structures were prepared.
  • Example 4 Three multi-layer nickel-zinc secondary batteries were produced in the same manner as in Example 3, except that the crease F was not formed, that is, plastic deformation (forming) was not performed.
  • the multi-layer cell of Example 3 fabricated by plastic deformation (forming) in accordance with the present invention is more susceptible to short circuits than the multi-layer cell of Example 4 (comparative example) fabricated by conventional techniques. It was difficult. It is believed that this is because the load on the end of the electrode plate from which the short-circuit current collecting tab extends is less likely to cause a short circuit not only during manufacture but also during use (especially when negative electrode shape change occurs). Also in Examples 1 and 2, since the current collecting tabs having a non-rounded shape that are bent at two points and are produced through forming are adopted, the current collecting tabs can be bundled together without pulling the current collecting tabs. Since the active material layer can be joined to the terminal by pressing, an excessive load is not applied to the end portion of the active material layer, and therefore, it can be said that a short circuit is less likely to occur as in Example 3.

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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)
  • Inorganic Chemistry (AREA)
  • Ceramic Engineering (AREA)
  • Composite Materials (AREA)
  • Materials Engineering (AREA)
  • Secondary Cells (AREA)
  • Connection Of Batteries Or Terminals (AREA)

Abstract

L'invention concerne une batterie secondaire au zinc à cellules multicouches dans laquelle un court-circuit ne se produit pas facilement même avec une structure assemblée dans laquelle des languettes de collecteur sont regroupées. Cette batterie secondaire au zinc comprend une pluralité de cellules unitaires, comprenant chacune une plaque d'électrode positive, une languette de collecteur d'électrode positive s'étendant à partir de la plaque d'électrode positive, une plaque d'électrode négative, une languette de collecteur d'électrode négative s'étendant à partir de la plaque d'électrode négative, un séparateur et une solution électrolytique, la pluralité de cellules unitaires étant empilées pour former une cellule multicouche. Vue en coupe transversale, chacune des languettes de collecteur d'électrode positive et des languettes de collecteur d'électrode négative a une forme courbée non arrondie dans au moins deux endroits et ainsi chacune des languettes de collecteur d'électrode positive et des languettes de collecteur d'électrode négative a au moins deux parties droites et une partie inclinée entre celles-ci. Dans les languettes de collecteur d'électrode positive, les parties droites qui sont plus loin des plaques d'électrode positive sont empilées et jointes les unes aux autres et dans les languettes de collecteur d'électrode négative, les parties droites qui sont plus éloignées des plaques d'électrode négative sont empilées et jointes les unes aux autres.
PCT/JP2021/041503 2021-03-12 2021-11-11 Batterie secondaire au zinc WO2022190460A1 (fr)

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Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH08111216A (ja) * 1994-10-12 1996-04-30 Sanyo Electric Co Ltd 電池の製造方法
JP2013045795A (ja) * 2011-08-22 2013-03-04 Jm Energy Corp 蓄電デバイス
JP2017022060A (ja) * 2015-07-15 2017-01-26 株式会社豊田自動織機 蓄電装置
JP2017059529A (ja) * 2015-09-14 2017-03-23 日本碍子株式会社 ラミネート型ニッケル亜鉛電池セルパック及びそれを用いた電池
JP2019128987A (ja) * 2018-01-19 2019-08-01 日本碍子株式会社 亜鉛二次電池
WO2019230930A1 (fr) * 2018-06-01 2019-12-05 積水化学工業株式会社 Batterie empilée et procédé de fabrication de batterie empilée
CN111540872A (zh) * 2020-05-12 2020-08-14 远景动力技术(江苏)有限公司 无汇流排电池模组、无汇流排电池模组组装方法和电池包
WO2021193436A1 (fr) * 2020-03-23 2021-09-30 日本碍子株式会社 Batterie secondaire au zinc et module de batterie

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH08111216A (ja) * 1994-10-12 1996-04-30 Sanyo Electric Co Ltd 電池の製造方法
JP2013045795A (ja) * 2011-08-22 2013-03-04 Jm Energy Corp 蓄電デバイス
JP2017022060A (ja) * 2015-07-15 2017-01-26 株式会社豊田自動織機 蓄電装置
JP2017059529A (ja) * 2015-09-14 2017-03-23 日本碍子株式会社 ラミネート型ニッケル亜鉛電池セルパック及びそれを用いた電池
JP2019128987A (ja) * 2018-01-19 2019-08-01 日本碍子株式会社 亜鉛二次電池
WO2019230930A1 (fr) * 2018-06-01 2019-12-05 積水化学工業株式会社 Batterie empilée et procédé de fabrication de batterie empilée
WO2021193436A1 (fr) * 2020-03-23 2021-09-30 日本碍子株式会社 Batterie secondaire au zinc et module de batterie
CN111540872A (zh) * 2020-05-12 2020-08-14 远景动力技术(江苏)有限公司 无汇流排电池模组、无汇流排电池模组组装方法和电池包

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