JP2017027735A - Negative electrode composite of metal air battery and metal air battery - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a negative electrode composite for a metal air battery that facilitates joint of a solid electrode and a laminate film and enables long-term stable discharging, and a metal air battery.SOLUTION: A negative electrode composite for a metal-air battery comprises a laminate including a metal negative electrode 3, a negative electrode current collector 2 which is electrically connected to the metal negative electrode 3, and solid electrolyte 5 having metal ion conductivity, and an exterior package body 6 in which the laminate is housed and which has an opening portion through which a part of the laminate is exposed to the surface. The outer package body 6 includes a laminate film having at least a resin layer 6b as an outer layer and a metal layer 6a inside the resin layer 6b. The opening portion and the solid electrolyte 5 are provided so as to overlap with each other, and the metal layer 6a of the laminate film and the solid electrolyte 5 are joined to each other.SELECTED DRAWING: Figure 1

Description

  The present invention relates to a negative electrode composite for a metal-air battery and a metal-air battery.

  The metal-air battery uses, for example, metal Li (lithium) as a negative electrode active material and oxygen in the atmosphere as a positive electrode active material. Metal-air batteries have a high energy density. In particular, lithium-air batteries are expected as batteries capable of obtaining an energy density of 700 Wh / kg, which is necessary for the spread of full-scale electric vehicles (EVs). This energy density is seven times higher than lithium-ion batteries that are currently being installed in vehicles.

  Lithium-air batteries use metal lithium or an alloy or compound containing metal lithium as a main component for the negative electrode active material. Lithium-air batteries are being actively researched because of their high energy density. Lithium-air batteries are roughly classified into two types, an aqueous solution type and a non-aqueous solution type (non-aqueous type), depending on the type of electrolytic solution.

Compared to non-aqueous lithium-ion batteries, aqueous lithium-air batteries have the advantages that they are not affected by moisture in the air and that the electrolyte is inexpensive and non-combustible.
However, since metallic lithium, which is a negative electrode active material, reacts when it comes into contact with oxygen or water, it is necessary to provide an isolation layer having lithium ion conductivity to protect metallic lithium from the atmosphere or aqueous solution in an aqueous lithium battery. is there. For this isolation layer, a solid electrolyte having water resistance such as glass ceramics is used.

  The structure of an aqueous lithium battery includes a positive electrode made of a current collector carrying a catalyst, an aqueous electrolyte, an isolation layer (solid electrolyte), and a negative electrode. Since the solid electrolyte used as the isolation layer often deteriorates by reacting with metallic lithium, a nonaqueous electrolytic solution or a polymer electrolyte is used between the metallic lithium of the negative electrode and the solid electrolyte. The isolation layer and the negative electrode are collectively called a negative electrode composite.

Patent Document 1 describes a negative electrode structure of a lithium-air battery having a solid electrolyte. In this negative electrode structure, the negative electrode outer layer has a three-layer metal foil laminate film structure of nylon resin film (outermost layer) / metal foil layer (barrier layer) / PP resin film (innermost layer / thermal welding layer), and the laminate film is three-dimensionally molded. The outer peripheral edge of the acid-modified PP resin film, which is the innermost layer, and the ceramic diaphragm are heat sealed.
With the technique described in Patent Document 1, the solid electrolyte and the laminate film can be joined. However, pressurization is required during heat sealing. For thin ceramic materials, problems such as cracking during pressurization and low bonding strength between acid-modified polyolefin-based heat-welded sheets and ceramic materials was there.

  Non-Patent Document 1 describes a lithium-air battery using an aqueous electrolyte. In this lithium-air battery, an aluminum laminate film in which a resin film is bonded to both surfaces of an aluminum foil is used as an exterior body of the negative electrode composite. In order to ensure lithium ion conductivity inside and outside the aluminum laminate film, a solid electrolyte is bonded and closed to the opening of the laminate film as a window material having lithium ion conductivity. Here, it is possible to join the combination of PP resin or PE resin capable of heat welding of the laminate film and the solid electrolyte (glass ceramic) of the negative electrode composite with an adhesive. However, there is a problem that the gas barrier property of the joint and the solvent resistance against the electrolyte solution are unstable with respect to long-time charge / discharge.

JP 2012-113993 A

Yasuo Takeda, Masayuki Imanishi, Osamu Yamamoto, “Current Status and Problems of Aqueous Lithium / Air Battery”, GS Yuasa Technical Report, June 2010, Vol. 7, No. 1, p. 1-6

  In view of the above circumstances, an object of the present invention is to provide a metal-air battery negative electrode composite and a metal-air battery that facilitate the joining of a solid electrolyte and a laminate film and that can be stably discharged for a long time. To do.

  In order to solve the above problems, the present invention provides, in one aspect, a negative electrode composite of a metal-air battery, wherein the negative-electrode composite of the metal-air battery is electrically connected to the metal negative electrode and the metal negative electrode. A laminate including a negative electrode current collector and a metal ion conductive solid electrolyte, and an exterior body that contains the laminate and has an opening that exposes a part of the laminate to the surface. The outer package includes a laminate film having at least an outer resin layer and a metal layer inside the resin layer, and is provided so that the opening and the solid electrolyte overlap with each other, and the metal layer of the laminate film The solid electrolyte is joined.

  If it is the negative electrode composite body of a metal air battery provided with such a side surface, joining of a solid electrolyte and an inner metal layer is easy, and workability | operativity can be improved. In addition, it is possible to make the joint with high airtightness, water resistance, and solvent resistance, so the possibility of moisture entering from the joint part between the solid electrolyte and the inner metal layer can be reduced, and stable long-term discharge can be achieved. Can be possible.

In one embodiment of the negative electrode composite of a metal-air battery according to the present invention, the metal negative electrode is made of metal lithium, an alloy containing lithium as a main component, or a compound containing lithium as a main component.
Thus, even if the metal negative electrode is made of metal lithium, an alloy containing lithium as a main component, or a compound containing lithium as a main component, according to the negative electrode composite of a metal battery according to the present invention, the ceramic and the metal layer Thus, the possibility of moisture entering between the two can be reduced, and metal lithium and the like can be prevented from reacting with moisture.

Moreover, the negative electrode composite body of the metal-air battery according to the present invention is, in one embodiment, the length of the metal negative electrode in the stacking direction of the laminate is 200 μm or more.
Thus, if the length of the metal negative electrode in the stacking direction is 200 μm or more, the energy density can be improved and the discharge capacity can be increased. Here, even when the thickness of the metal negative electrode is reduced, according to the negative electrode composite of the metal battery according to the present invention, the laminate film of the outer package that accommodates the metal negative electrode or the like follows the decrease in the thickness of the metal negative electrode. . As a result, even if the thickness of the metal negative electrode is reduced, high airtightness, water resistance, and solvent resistance of the joint portion are maintained. For this reason, the discharge capacity can be improved, and the damage can be prevented even if the discharge is performed for a long period of time, so that it is possible to withstand the deep discharge.

Furthermore, the negative electrode composite body of the metal-air battery according to the present invention is, in one embodiment thereof, the exterior body by thermally welding the edge portion of the laminate film provided so as to overlap in the stacking direction of the laminate body. And the metal layer of the outer package and the metal negative electrode are electrically energized.
In such a form, the metal layer of the outer package can be used as the negative electrode current collector, and the negative electrode current collector inside the negative electrode composite can be omitted, so the number of parts can be reduced and the negative electrode current collector can be produced. And the thickness of the negative electrode composite can be reduced. Moreover, in such a form, since the resin layer of the exterior body is on the surface opposite to the surface in contact with the metal negative electrode, the possibility that the negative electrode metal is deposited can be reduced, and the charge / discharge cycle characteristics can be improved.

Still further, the present invention is a metal-air battery according to another aspect, wherein the metal-air battery is configured such that the negative electrode composite and an air electrode including a positive electrode layer containing a conductive material are opposed to each other, and the negative electrode composite is provided. An aqueous electrolyte is provided between the body and the positive electrode layer, and the solid electrolyte of the negative electrode composite and the air electrode layer of the air electrode are in contact with the aqueous electrolyte.
If the negative electrode composite of the metal battery according to the present invention is adopted in such a metal-air battery, even if an aqueous electrolyte is used, moisture enters from the joint portion of the negative electrode composite exterior body and the solid electrolyte. Possibility can be reduced and stable long-term discharge can be enabled.

  ADVANTAGE OF THE INVENTION According to this invention, the negative electrode composite_body | complex of metal air battery and the metal air battery which enabled easy joining of a solid electrolyte and a laminate film, and were able to discharge stably for a long time are provided.

FIG. 1 is a cross-sectional view for explaining a first embodiment of a negative electrode composite of a metal-air battery according to the present invention. FIG. 2 is a conceptual diagram illustrating the first embodiment of the negative electrode composite body of the metal-air battery according to the present invention in a state where the exterior body 6 is unfolded. FIG. 3 is a cross-sectional view illustrating an embodiment in which a solid electrolyte is provided on both surfaces of a negative electrode composite in the first embodiment of the negative electrode composite of a metal-air battery according to the present invention. FIG. 4 is a cross-sectional view for explaining a second embodiment of the negative electrode composite of the metal-air battery according to the present invention. FIG. 5A is a conceptual plan view showing an exterior body plate 106 in the second embodiment of the negative electrode composite of the metal-air battery according to the present invention. FIG. 5B is a conceptual plan view showing the exterior body plate 107 in the second embodiment of the negative electrode composite of the metal-air battery according to the present invention. FIG. 6 is a cross-sectional view illustrating a third embodiment of the negative electrode composite of the metal-air battery according to the present invention. FIG. 7 is a graph showing the change in discharge voltage for Example 1 and Comparative Example 2 for Example 1 of the metal-air battery configured by the negative electrode composite according to the present invention. FIG. 8 is a graph showing a discharge / charge cycle for Example 2 of the metal-air battery constituted by the negative electrode composite according to the present invention. FIG. 9 is a graph showing a discharge / charge cycle for Comparative Example 3 with respect to Example 2 of the metal-air battery constructed of the negative electrode composite according to the present invention.

  Hereinafter, a negative electrode composite of a metal-air battery and a metal-air battery according to the present invention will be described with reference to embodiments shown in the accompanying drawings.

First Embodiment FIG. 1 shows a first embodiment of a negative electrode composite of a metal-air battery according to the present invention. The embodiment of FIG. 1 is a mode in which the solid electrolyte is provided on only one surface of the negative electrode composite to be produced in the first embodiment. Hereinafter, the “negative electrode composite of a metal-air battery” is also simply referred to as “negative electrode composite”. FIG. 1 shows a cross section of a negative electrode composite 1 according to the present embodiment. As a general form, the negative electrode composite body 1 is configured to extend in a flat plate shape in a direction perpendicular to the paper surface as in the conventionally known one.

  In the present embodiment, the negative electrode composite 1 includes a negative electrode current collector 2, a negative electrode layer 3 made of a negative electrode active material, a buffer layer 4 that can be seen up and down in a cross section, and an isolation layer 5. It is.

  The negative electrode current collector 2 has a linear shape or a plate shape. The material of the negative electrode current collector 2 may be present stably in the operating range of the metal-air battery, and may have any desired conductivity. Examples thereof include copper and nickel.

The negative electrode active material of the negative electrode layer 3 is not particularly limited as long as it is a material capable of occluding and releasing metal ions. The metal ion is preferably lithium ion.
As a negative electrode active material, metals, such as sodium, calcium, magnesium, aluminum, zinc, lithium, can be used, for example. Among these, an open circuit voltage is high and lithium is more preferable from a practical viewpoint. Further, the negative electrode active material is not limited to metallic lithium, and may be an alloy or compound containing lithium as a main component. The lithium-based alloy can include magnesium, calcium, aluminum, silicon, germanium, tin, lead, antimony, bismuth, silver, gold, zinc, and the like.

The isolation layer 5 is located on the surface where the negative electrode composite 1 is in contact with the electrolytic medium portion described later, and is for protecting the negative electrode layer 3 from moisture. The material of the isolation layer 5 is not particularly limited as long as it has water resistance and metal ion conductivity. For example, a solid electrolyte such as glass ceramics can be used. When metallic lithium is used as the negative electrode active material, the lithium ion conductivity of the isolation layer 5 is desirably 10 ⁻⁵ S / cm or more. Examples of the material of the isolation layer 5 include a NASICON (Na Superconducting Conductor) type lithium ion conductor. Further, a part of the tetravalent cation M of the lithium ion conductor represented by the general formula LiM ₂ (PO ₄ ) ₃ (M is a tetravalent cation such as Zr, Ti, Ge) is trivalent such as In, Al. And a lithium ion conductor represented by the general formula Li _{1 + x} M _2−x M ′ _x (PO ₄ ) ₃ in which the lithium ion conductivity is improved by substitution with the cation M ′. Further, a part of the tetravalent cation M of the lithium ion conductor represented by the general formula LiM ₂ (PO ₄ ) ₃ (M is a tetravalent cation such as Zr, Ti, Ge) is converted to a pentavalent cation such as Ta. lithium ion conductor represented by "formula _{Li 1-x M 2-x} M with improved lithium ion conductivity by replacing" x _{(PO 4) 3} and the like M. P in these lithium ion conductors may be substituted with Si, and the lithium ion conductor represented by the general formula Li _{1 + x + y} Ti _2−x Al _x P _3−y Si _y O ₁₂ (LTAP) Desirable from the viewpoint of sex. In addition to these, a sulfide-based ceramic electrolyte having high lithium ion conductivity is also included.

The buffer layer 4 is for preventing contact between the negative electrode layer 3 and the isolation layer 5. When the negative electrode layer 3 and the isolation layer 5 come into contact with each other, the negative electrode active material such as lithium of the negative electrode layer 3 and the glass ceramics of the isolation layer 5 may react to deteriorate the isolation layer 5. Therefore, the buffer layer 4 is for preventing contact between the negative electrode layer 3 and the isolation layer 5.
The buffer layer 4 is a metal ion conductive polymer electrolyte or organic electrolyte. For example, an organic electrolyte solution soaked in a separator (a sheet made of porous polyethylene, polypropylene, cellulose, or the like) may be used. When metallic lithium is used as the negative electrode active material, it is desirable that the lithium ion conductivity (also referred to as lithium ion conductivity) of the buffer layer 4 is 10 ⁻⁵ S / cm or more. The organic electrolyte used is a mixture of ethylene carbonate mixed with diethyl carbonate or dimethyl carbonate and further added with a lithium salt. In addition, the buffer layer 4 may be a solid electrolyte in which a lithium salt is dispersed in a polymer, or may be a gel electrolyte in which an organic electrolyte solution in which a lithium salt is dissolved is swollen in a polymer. Examples of the lithium salt include LiPF ₆ , LiClO ₄ , LiBF ₄ , LiTFSI (Li (CF ₃ SO ₂ ) ₂ N), Li (C ₂ F ₄ SO ₂ ) ₂ N, LiBOB (lithium bisoxalatoborate), and the like. .

Examples of the polymer include PEO (polyethylene oxide) and PPO (polypropylene oxide). The polymer serving as a host for the gel electrolyte is PEO (polyethylene oxide), PVA (polyvinyl alcohol), PAN (polyacrylonitrile), PVP (polyvinylpyrrolidone), PEO-PMA (crosslinked product of polyethylene oxide-modified polymethacrylate), PVdF (polyfluoride). And vinylidene fluoride), PVA (polyvinyl alcohol), PAA (polyacrylic acid), PVdF-HFP (copolymer of polyvinylidene fluoride and hexafluoropropylene), and the like. In addition, when using especially desirable PEO as a polymer of the buffer layer 4, it is desirable that the molecular weight of PEO is 10 ⁴ to 10 ⁵ , and the molar ratio of PEO and lithium salt is 8 to 30: 1. It is desirable. Further, in order to improve the strength and electrochemical characteristics of the buffer layer 4, a ceramic filler, for example, BaTiO ₃ powder may be dispersed in the polymer. The mixing amount of the ceramic filler is desirably 1 to 20 parts by weight with respect to 100 parts by weight of the remaining components.

As shown in FIG. 1, the present embodiment has a configuration in which a laminated body of a negative electrode layer 3, a buffer layer 4, and an isolation layer 5 is surrounded by an exterior body 6.
The exterior body 6 is configured using a laminate film composed of a metal layer 6a having gas barrier properties and a resin layer 6b.

  As the metal layer 6a of the laminate film, it is preferable to use a metal having high electrical conductivity and physical properties that can withstand the organic electrolyte solution. For example, stainless steel, copper, aluminum, and the like are preferable.

  As the resin layer 6b of the laminate film, a resin having high heat durability and high strength is preferable, and a polyester-based resin, a nylon-based resin, or a thermoplastic polyolefin-based resin that can be thermally welded can be used. Examples of the polyester resin include polyethylene terephthalate, polybutylene terephthalate, polytrimethylene terephthalate, and polyethylene naphthalate. Examples of nylon resins include 6-nylon and 6,6-nylon. Examples of the polyolefin resin include polyethylene, polypropylene, and polybutylene.

  For example, when a thermoplastic polyolefin resin that can be thermally welded to the resin layer 6b of the outer package 6 is used, the end of the laminate film (end) is obtained by bending the ends inward and thermally welding the polyolefin resins together. The overlapping part) can be heat welded. When a polyester-based or nylon-based resin is used for the resin layer 6b of the outer package 6, a thermoplastic polyolefin-based resin film that can be heat-welded as an innermost layer may be provided at the end of heat-welding and heat-welded. .

When a laminate film composed of the metal layer 6a and the resin layer 6b is used as the exterior body 6, the metal layer 6a and the isolation layer 5 are bonded. If the isolation layer 5 is ceramic, it can be joined by various methods such as brazing, pressure welding, solid phase welding, and fusion welding. Among them, bonding by adhesion is preferable, and adhesives used for adhesive bonding are epoxy adhesives, olefin adhesives, cyanoacrylic adhesives, synthetic rubber adhesives such as styrene butanediene rubber adhesives, etc. Can be used. However, the adhesive is not particularly limited as long as the metal layer 6a and the isolation layer 5 can be bonded to each other, and has low moisture permeability and gas permeability, and is resistant to non-aqueous electrolytes and aqueous electrolytes. Things are good.
In the negative electrode composite body 1 according to the first embodiment, the metal layer 6a and the isolation layer 5 can be easily joined in this way, and workability can be improved. In addition, since it is possible to obtain a joint having high airtightness, water resistance, and solvent resistance, the possibility of moisture entering from the joint portion between the metal layer 6a and the isolation layer 5 can be reduced, and stable long-term discharge can be achieved. Can be possible.
In addition, the negative electrode composite 1 according to the first embodiment includes a stack in the stacking direction including a negative electrode layer 3 (metal negative electrode), a negative electrode current collector 2, and a separation layer 5 (solid electrolyte). The thickness can be 200 μm or more.
If the length (thickness) in the stacking direction of the laminate is 200 μm or more, the energy density can be improved and the discharge capacity can be increased. Here, even when the thickness of the metal negative electrode is reduced, according to the negative electrode composite of the metal battery according to the present invention, the laminate film of the outer package 6 that accommodates the metal negative electrode or the like follows the decrease in the thickness of the metal negative electrode. To do. As a result, even if the thickness of the metal negative electrode is reduced, high airtightness, water resistance, and solvent resistance of the joint portion are maintained. For this reason, the discharge capacity can be improved, and the damage can be prevented even if the discharge is performed for a long period of time, so that it is possible to withstand the deep discharge. In addition, since the metal layer 6a and the isolation layer 5 are joined, the range of selection of the adhesive to be used for joining is widened, and it becomes possible to use an adhesive having high gas barrier properties and solvent resistance.

Next, with reference to FIG. 2 in addition to FIG. 1, an embodiment of a method for producing the negative electrode composite according to the first embodiment will be described.
Procedure 1: Production of Exterior Body of Negative Electrode Composite 1 FIG. 2 shows an unfolded state of one embodiment of the exterior body 6. In FIG. 2, the metal layer 6a side of the outer package 6 is visible.
A part of the outer package 6 made of a laminate film of the metal layer 6a and the resin layer 6b is cut into a window shape as the solid electrolyte opening 7. An adhesive is applied to the solid electrolyte bonding portion 8 around the solid electrolyte opening 7, and a solid electrolyte such as ceramic is bonded to the metal layer 6 a side of the solid electrolyte opening 7. In addition, the joining method of the metal layer 6a and the isolation layer 5 of a solid electrolyte is not limited to the method using such an adhesive agent.
Next, the end portions 9 and 9 of the laminate film were folded to the metal layer 6a side, folded at the bent portion 10, and the upper and lower resin layers 6b and 6b surfaces of the end portions 9 and 9 were overlapped. Next, the mating surfaces of the end portions 9 and 9 are joined together by thermoplastic welding between thermoplastic polyolefin resins.
In FIG. 1, the isolation layer 5 of a solid electrolyte, the adhesion layers 11 and 11 with the metal layer 6a, and the heat welding part 12 of one resin layer 6b of the edge parts 9 and 9 are shown. FIG. 1 is a cross-sectional view, and a cross-section in a state where the bent portion 10 is bent should appear on the left side. However, FIG. 1 shows a cross-sectional structure of the heat-welded portion 12 between the resin layers 6b of the end portions 9 and 9 for convenience.

Procedure 2: Production of Negative Electrode Composite The outer package 6 of the negative electrode complex 1 is moved to an inert atmosphere of argon gas, and the negative electrode current collector 2 having the negative electrode layer 3 on one side is placed in the outer package 6. In addition, the two end portions facing in parallel with the folded portion 10 of the folded exterior body 6 constitute the heat-welded joint portions 13 and 13 made of an acid-modified polyolefin-based heat-welded sheet, The negative electrode current collector 2 is inserted through the gap formed by 13. At this time, the negative electrode layer 3 is wrapped with a polyolefin-based separator or a cellulose separator. The separator constitutes the buffer layer 4 after the negative electrode composite 1 is completed.
A part of the negative electrode current collector 2 is used as a terminal 14 so as to extend outward from the heat-welded joint portions 13 and 13 of the outer package 6.
Then, an electrolytic solution such as a non-aqueous electrolytic solution or a polymer electrolyte is injected into the negative electrode composite 1 through the gap formed by the heat welding joint portions 13 and 13.
An acid-modified polyolefin-based heat-welded sheet is sandwiched between both sides of the heat-welded joint portions 13 and 13 of the facing exterior body 6 and sealed by heat-weld joint, thereby producing the negative electrode composite 1 having the cross-sectional structure of FIG. Can be completed.

The negative electrode composite 1 can form a metal-air battery by combining with the positive electrode part with the electrolytic medium part interposed therebetween.
The positive electrode part can be configured as a positive electrode structure. Such a positive electrode structure is composed of a material having conductivity and gas diffusibility, a material in which fine particles of noble metal such as platinum and gold are supported on conductive carbon black, and a material having catalytic activity such as MnO _2. A positive electrode layer configured to be supported, a positive electrode current collector electrically connected to the positive electrode layer, and a positive electrode exterior body partially covering the positive electrode layer can be provided.

  As a material having conductivity and gas diffusivity used for the positive electrode layer, a conductive material having a porous structure may be used. Examples of the porous structure include a mesh structure in which constituent fibers are regularly arranged, a nonwoven fabric structure in which the fibers are randomly arranged, and a three-dimensional network structure. More specifically, there are carbon fiber materials such as carbon paper, carbon cloth, and carbon nonwoven fabric. The carbon cloth is in the form of a sheet in which carbon fibers are regularly knitted, and the carbon non-woven fabric is in the form of a sheet in which carbon fibers are randomly entangled. In addition, as long as it has a porous structure, for example, a metal material such as stainless steel, nickel, aluminum, or iron may be used. Among these, carbon fiber is more preferable from the viewpoint of weight reduction of the positive electrode and high corrosion resistance against the electrolytic solution.

  The positive electrode layer has a thin plate shape. Although the positive electrode layer is surrounded by the positive electrode outer package, the positive electrode outer package is arranged so that one surface of the positive electrode layer faces at least one surface of the negative electrode composite 1 (that is, the surface of the isolation layer 5). Is provided with an opening. In addition, another opening is provided in the positive electrode exterior body so that air as the positive electrode active material is introduced into the positive electrode layer. Furthermore, the positive electrode exterior body is provided with an opening for drawing out the positive electrode current collector to the outside of the outer shell.

  The surface of the positive electrode layer includes a catalyst such as a noble metal or a metal oxide that promotes the oxidation-reduction reaction, and a conductive material or a binder that binds these as necessary. Examples of a preferable material as the conductive material include high specific surface area carbon such as carbon black and activated carbon.

  The positive electrode current collector may be present stably in the operating range of the metal-air battery and may have a desired conductivity. Examples of the material for the positive electrode current collector include metal materials such as stainless steel, nickel, aluminum, gold, and platinum, and carbon fiber materials such as carbon cloth and carbon nonwoven fabric.

  The electrolytic medium portion interposed between the negative electrode composite and the positive electrode structure can be constituted by an electrolytic medium and an electrolytic medium exterior body that houses the electrolytic medium. The electrolytic medium can also include an electrolytic solution containing a catalyst. The catalyst has a catalytic activity that promotes at least the oxygen reduction reaction performed in the positive electrode layer during the discharge of the metal-air battery. At the same time, the catalyst preferably has a catalytic activity that promotes the oxygen generation reaction performed in the positive electrode layer when the metal-air battery is charged.

  As such a catalyst, a noble metal or other transition metals can be used. Examples of the noble metal include Au, Ag, Pt, Pd, Rh, Ru, Ir, and oxides thereof. Examples of other transition metals include V, Mn, Fe, Co, Ni, Cu, Zn, La, Ce, and oxides thereof.

The electrolytic solution may be an aqueous electrolytic solution or a non-aqueous electrolytic solution.
The aqueous electrolyte solution only needs to have electrical conductivity, and an aqueous electrolyte in which a lithium salt is dissolved in water is preferable. Examples of the lithium salt dissolved in water include LiCl (lithium chloride), LiOH (lithium hydroxide), LiNO ₃ (lithium nitrate), and CH ₃ COOLi (lithium acetate).
Note that, in the negative electrode composite according to the first embodiment, even if an aqueous electrolyte is used, there is a possibility that moisture may enter from the joint between the exterior body 6 of the negative electrode composite 1 and the isolation layer 5 (solid electrolyte). It can be reduced and stable long-term discharge can be realized.

As the non-aqueous electrolyte, a cyclic carbonate such as propylene carbonate (PC) or ethylene carbonate (EC), a chain carbonate such as dimethyl carbonate (DMC) or ethyl methyl carbonate (EMC), or a mixed solution thereof may be used. In order to provide conductivity, LiPF ₆ (lithium hexafluorophosphate), LiClO ₄ (lithium perchlorate), LiBF ₄ , (lithium tetrafluoroborate), LiN (SO ₂ CF ₃ ) ₂ (lithium An electrolyte such as bis (trifluoromethanesulfonyl) imide) may be added.

  Moreover, you may use the electrolytic medium which impregnated the electrolyte solution with the porous body. As the porous body, in addition to a porous film such as polyethylene or polypropylene, a nonwoven fabric such as cellulose, a resin nonwoven fabric or a glass fiber nonwoven fabric, hydrogel, or the like may be used.

  The electrolytic medium is accommodated in the electrolytic medium outer package, and is disposed so that the electrolytic medium is in contact with both the isolation layer 5 and the positive electrode layer of the negative electrode composite 1.

  In the first embodiment described with reference to FIGS. 1 and 2, the solid electrolyte 5 is provided only on one surface of the negative electrode composite 1. FIG. 3 shows an embodiment in which solid electrolytes 5 and 5 are provided on both surfaces of the negative electrode composite 1 in the first embodiment.

In the embodiment shown in cross section in FIG. 1 in which the isolation layer 5 is provided only on one side, the end portions 9 and 9 of the laminate film are folded to the metal layer 6a side, and folded at the folded portion 10 (FIG. 2). The upper and lower resin layers 6b and 6b surfaces of the portions 9 and 9 were overlapped. Next, the mating surfaces of the end portions 9 and 9 were joined by heat welding.
The negative electrode composite body 1 in FIG. 3 does not have the bent portion 10 and uses two laminate films, and the peripheral portion corresponding to the bent portion 10 has the same configuration as the end portions 9 and 9 in FIG. That is, the end portions of the four sides of the laminate film are folded to the metal layer 6a side like the end portions 9 and 9, and the upper and lower resin layers 6b and 6b are overlapped. Next, the mating surfaces at the ends are joined by heat welding to form the welded portion 12.

  A further difference from the embodiment in which the cross section is shown in FIG. 1 is that a part of both laminate films is cut into a window shape as a solid electrolyte opening. Furthermore, the negative electrode current collector 2 having the negative electrode layer 3 on both sides instead of one side is placed in the outer package 6. In addition, about the part 15 which pinches | interposes the terminal 14, the lamination film 6 and the negative electrode collector 15 are heat-welded and joined by interposing an acid-modified polyolefin-type heat welding sheet.

Otherwise, the negative electrode composite 1 shown in FIG. 3 can be obtained in the same manner as in Procedure 1 and Procedure 2 described above. In FIG. 3, the fabricated negative electrode composite 1 is made of the same material as in FIG. 1, and elements having the same functions are denoted by the same reference numerals.
In the embodiment of FIG. 3, the same effect as that of the first embodiment described above can be expected, and in addition, the entire volume of the negative electrode composite 1 can be reduced.

Second Embodiment The negative electrode composite according to the second embodiment is used as a material constituting an exterior body by a three-layer laminate film.
FIG. 4 shows an embodiment of a negative electrode composite 101 according to the present invention. The negative electrode composite 101 includes a negative electrode current collector 102, a negative electrode layer 103 composed of a negative electrode active material, a buffer layer 104, and an isolation layer. 105 are laminated.
The negative electrode current collector 102, the negative electrode layer 103, the buffer layer 104, and the isolation layer 105 are made of the same material as the negative electrode current collector 2, the negative electrode layer 3, the buffer layer 4, and the isolation layer 5 described with reference to FIG. Can do.
As shown in FIG. 4, in this embodiment mode, a laminate of the negative electrode layer 103, the buffer layer 104, and the isolation layer 105 is sandwiched between the exterior body plate 106 and the exterior body plate 107. The exterior body plate 106 and the exterior body plate 107 are configured to have a size that can be overlapped, and the exterior body 108 is configured by overlapping these.
The exterior body plates 106 and 107 are configured by using laminated films composed of metal layers 106a and 107a having gas barrier properties, outer resin layers 106b and 107b, and inner resin layers 106c and 107c, respectively.

  The metal layers 106a and 107a can be made of the same material as the metal layer 6a. The outer resin layers 106b and 107b and the inner resin layers 106c and 107c can be made of the same material as the resin layer 6b.

  When such an exterior body plate 106 is used, a portion where the inner resin layer 106c is not provided is provided, and the metal layer 106a and the isolation layer 105 are joined. This will be described later. The bonding method is the same as the method of bonding the metal layer 6a and the isolation layer 5.

Next, in addition to FIG. 4, an embodiment of a method for producing the negative electrode composite 101 according to the second embodiment will be described with reference to FIGS. 5 (a) and 5 (b).
FIG. 5A shows an embodiment of the exterior body plate 106, and FIG. 5B shows an embodiment of the exterior body plate 107. 5A and 5B, the inner resin layers 106c and 107c of the exterior plates 106 and 107 are visible.
As shown in FIG. 5 (a), the inner resin layer 106 c of the exterior body plate 106 is punched into a quadrangular shape at the solid electrolyte bonding portion 109. A part of the solid electrolyte bonding portion 109 is cut as a solid electrolyte opening 110 in a window shape. And an adhesive agent is apply | coated to the metal layer 106a which appears in the solid electrolyte adhesion part 109 which exists around the solid electrolyte opening part 110, and solid electrolytes, such as ceramics, are adhere | attached on the metal layer 106a.
The exterior body plate 106 having the solid electrolyte bonding portion 109 is bonded to the outer resin layer 106b by diluting and applying an adhesive to an appropriate viscosity with an organic solvent, drying, and pressing and bonding to the metal layer 106a by a dry laminating method. Then, the inner resin layer 106c obtained by cutting the solid electrolyte bonding portion 109 can be produced by applying heat to the metal layer 106a by a heat laminating method and bonding them together.

  Under an inert atmosphere, the negative electrode current collector 102 to which the negative electrode layer 103 is bonded is placed on the exterior body plate 107 shown in FIG. Note that an acid-modified polyolefin-based heat welding sheet 112 is attached to the exterior body plate 107 corresponding to a portion where the terminal portion 111 of the negative electrode current collector 102 extends. On the other hand, a heat welding sheet 113 is attached to the exterior body plate 106 at a position corresponding to the heat welding sheet 112.

The terminal portions 111 are stacked so as to be sandwiched between the heat welding sheets 112 and 113. The side where the thermal welding sheets 112 and 113 are located and the three sides are joined by thermal welding. In FIG. 4, reference numerals 114 and 115 denote heat welding portions, and the heat welding portion 115 constitutes a heat welding portion between the heat welding sheets and / or a welding portion between the laminate films. In FIG. 4, reference numeral 116 denotes an adhesive layer made of an adhesive.
Next, a buffer layer 104 such as a separator is placed on the negative electrode layer 103.
Then, an electrolyte such as a non-aqueous electrolyte is injected from the gap between the sides not welded in the negative electrode composite 101.
Finally, the end of the remaining one side can be joined by heat welding using a heat sealer or the like to complete the negative electrode composite 101.

Similar to the first embodiment, the negative electrode composite 101 can be combined with the positive electrode portion with the electric field medium portion interposed therebetween to constitute a metal-air battery. The description relating to the first embodiment for each of the positive electrode part and the electric field medium part also applies to the negative electrode composite body 101 according to the second embodiment as it is.
The effects that can be expected from the negative electrode composite 101 according to the first embodiment can also be expected from the negative electrode composite 101 according to the second embodiment. In addition, in the negative electrode composite 101 according to the second embodiment, the cycle characteristics can be further improved as compared with the negative electrode composite 1 according to the first embodiment. Furthermore, as is clear from FIG. 4, both ends have a laminate structure, which is flexible and can be expanded and contracted, so that it is possible to cope with a change in internal pressure accompanying discharge.
Note that, similarly to the negative electrode composite 1 according to the first embodiment, the negative electrode composite 101 according to the second embodiment is also implemented as a mode in which the isolation layers 105 are provided on both sides as shown in FIG. be able to. Further, not only a three-layer laminate film such as the negative electrode composite 101 according to the second embodiment, but also a four-layer or more metal foil laminate in which one or more resin films such as a nylon film are interposed therebetween is used. It is also possible to do.

Third Embodiment The negative electrode composite according to the third embodiment is an embodiment in which a two-layer laminate film is used as a material constituting an exterior body, and the negative electrode current collector is also used as a metal layer of the laminate film. It is a form.
FIG. 6 shows a third embodiment of the negative electrode composite 201. The negative electrode composite 201 includes a negative electrode current collector 202, a negative electrode layer 203 composed of a negative electrode active material, a buffer layer 204, an isolation layer 205, Are provided.
The negative electrode current collector 202, the negative electrode layer 203, the buffer layer 204, and the isolation layer 205 may be made of the same material as the negative electrode current collector 2, the negative electrode layer 3, the buffer layer 4, and the isolation layer 5 described with reference to FIG. it can.
As shown in FIG. 6, in this embodiment mode, a laminate of the negative electrode layer 203, the buffer layer 204, and the isolation layer 205 is sandwiched between the exterior body plate 206 and the exterior body plate 207. The exterior body plate 206 and the exterior body plate 207 are configured to have a size that can be overlapped, and the exterior body is configured by overlapping these.
The exterior body plates 206 and 207 are configured using a laminate film composed of metal layers 206a and 207a having gas barrier properties and resin layers 206b and 207b, respectively.

The metal layer 206a can be made of the same material as that of the metal layer 6a employed in the first embodiment. The metal layer 207a is made of a material that can form a negative electrode current collector such as a copper foil. That is, the metal layer 207a also serves as the negative electrode current collector 202, and is provided integrally with the negative electrode terminal portion 209 extended.
The resin layers 206b and 207b can be made of the same material as that of the resin layer 6b employed in the first embodiment. The most preferable material is a polyester resin film such as PET resin having high heat resistance.
For the negative electrode composite 201 according to the third embodiment, the same effect as that of the negative electrode composite 1 according to the first embodiment can be expected. In addition, the metal layer 202 of the outer package can be used as a negative electrode current collector, and the negative electrode current collector inside the negative electrode composite 201 can be omitted, so the number of parts can be reduced and the negative electrode current collector can be easily manufactured. In addition, the negative electrode composite 201 can be made thin and light. Moreover, in such a form, since the resin layer 207b of the exterior body is on the surface opposite to the surface in contact with the negative electrode layer 203 (metal negative electrode), the possibility that the negative electrode metal is deposited can be reduced, and the charge / discharge cycle The characteristics can be improved.

Next, an embodiment of a method for producing the negative electrode composite 201 according to the third embodiment will be described.
The following operations are performed under an inert atmosphere such as argon gas.
The solid electrolyte opening 210 of the outer body plate 206 is cut into a square shape. The periphery of the solid electrolyte opening 210 is defined as a solid electrolyte adhesion portion 211. Then, an adhesive 212 is applied to the solid electrolyte bonding portion 211, and a solid electrolyte such as ceramics constituting the isolation layer 205 is bonded to the metal layer 206a.

  The negative electrode layer 203 is bonded on the metal layer 207 a of the exterior body plate 207. Further, the four sides around the negative electrode layer 203 are continuously covered with an acid-modified polyolefin-based heat welding sheet 213.

The outer body plates 206 and 207 are overlapped. Three sides other than the side where the negative electrode terminal portion 209 is provided are joined by thermal welding. Next, a buffer layer 204 such as a separator is placed on the negative electrode layer 203.
Then, an electrolytic solution such as a non-aqueous electrolytic solution is injected into the negative electrode composite 201 from the gap between the sides that are not thermally welded.
Finally, the end of the remaining one side can be joined with a heat sealer or the like to complete the negative electrode composite 201.

  Similar to the first embodiment, the negative electrode composite 201 can be combined with the positive electrode portion with the electric field medium portion interposed therebetween to constitute a metal-air battery. The description relating to the first embodiment with respect to each of the positive electrode part and the electric field medium part is directly applicable to the negative electrode composite body 201 according to the third embodiment.

  Hereinafter, the negative electrode composite of the metal-air battery and the metal-air battery according to the present invention will be described in more detail with respect to examples thereof. The technical scope of the present invention is not limited by the following examples.

Examples and comparative examples according to the first embodiment
Example 1
1. Production of Negative Electrode Composite Exterior Body A metal foil laminate film of stainless steel foil (SUS316L) / PP (polypropylene) resin was cut in the shape shown in FIG. A two-component room temperature curing type epoxy adhesive was applied to the solid electrolyte bonding portion 8, and a rectangular solid electrolyte was bonded to the stainless steel foil side 6 a of the solid electrolyte opening 7. The end portions 9 and 9 of the laminate film were folded on the stainless steel foil side 6a, folded at the bent portion 10, and the upper and lower PP resin surfaces 6b of the end portions 9 and 9 were overlapped. Thereafter, the two overlapped mating surfaces were joined together by heat welding with an up-and-down heating compatible impulse heat sealer to obtain an exterior body 6 of the negative electrode composite 1 in FIG.

2. Production of Negative Electrode Composite The outer package 6 of the negative electrode composite 1 was transferred into a glove box under an argon atmosphere, the metal Li portion of the copper foil current collector 2 with single-sided metal lithium was wrapped with a cellulose separator, and the outer package of the negative electrode composite 1 was obtained. I put it in the body 6. The negative electrode current collector 2 portion is used as a terminal to be taken out from the joint portions 13 and 13 of the outer package 6, and a non-aqueous electrolyte (1 M LiPF ₆ / EC (ethyl carbonate): EMC (ethyl methyl carbonate) = 1: 1) is used as the negative electrode composite 1 was injected. Finally, both sides of the joint portions 13 and 13 of the outer package 6 facing each other were joined and sealed with a heat sealer via an acid-modified polyolefin-based heat welding sheet, and the negative electrode composite 1 of FIG. 1 was produced.

LTAP was used for the solid electrolyte. Although this LTAP has water resistance, it cannot be directly contacted because it does not have lithium metal resistance. In order to prevent direct contact and to carry lithium ion conduction between the solid electrolyte and the lithium metal, a protective layer is formed by impregnating a cellulose separator with a non-aqueous electrolyte (1MLiPF ₆ / EC: EMC = 1: 1). .

3. Production of positive electrode A positive electrode was produced by the following procedure.
(1) Weigh 80 mg of platinum-supported carbon (Pt: 47.2%) as a positive electrode catalyst and 20 mg of polyvinylidene fluoride (PVdF) as a binder (binder), and 2 ml of N-methylpyrrolidone (NMP). A mixed solvent was prepared by addition.
(2) The mixed solvent was applied to the end of the carbon cloth with a stirrer (AR-100, manufactured by Shinki Co., Ltd.) for 6 minutes and with ultrasonic waves for 30 minutes, using a coating machine (K202 control coater manufactured by Matsuo Sangyo Co., Ltd.). Then, it put on the hotplate and heat-dried at 110 degreeC for 1 hour, and produced the positive electrode of platinum carrying amount about 0.5 mg / cm < ² >.

4). Preparation of Air Battery A 2M (mol / L) LiCl aqueous solution was prepared. In order to hold the LiCl aqueous solution, the solution was dropped on the cellulose sheet and disposed between the positive electrode structure and the negative electrode composite 1.

Comparative Examples 1 and 2
For Comparative Examples 1 and 2, a method for producing a negative electrode composite using a conventional aluminum laminate film will be described.
1. Preparation of negative electrode composite exterior body A window material portion of an aluminum laminate film of PET resin / aluminum foil / PE resin was cut. In Comparative Example 1, a two-component room temperature curing type epoxy adhesive was applied to the solid electrolyte adhesive portion, and in the Comparative Example 2, an SBR adhesive was applied, and the rectangular solid electrolyte was adhered to the PE resin side of the solid electrolyte opening. . Folded at the folded part of the laminate film, the PE resin surface above the end part (window material part side) was superposed and joined by heat welding with a heat sealer to obtain an exterior body of the negative electrode composite.

2. Preparation of negative electrode composite The outer body of the negative electrode composite was transferred into a glove box under an argon atmosphere, the metal Li portion of the copper foil current collector with metal lithium on one side was wrapped with a cellulose separator, and the outer body of the negative electrode composite was I put it in. The negative electrode current collector part was taken out from the adhesion part of the outer package as a terminal, and a non-aqueous electrolyte (1 M LiPF ₆ / EC: EMC = 1: 1) was injected into the negative electrode composite. Finally, a two-component room-temperature curing type epoxy adhesive was applied to both sides of the adhesive portion of the outer packaging facing each other, and an SBR adhesive was applied and bonded in Comparative Example 2 to form a negative electrode composite. .

3. Production of positive electrode / Production of air battery It was produced in the same manner as in Example 1.

Discharge test of Example 1 and Comparative Examples 1 and 2 In the cell corresponding to the theoretical capacity of 84 mAh of Example 1, the change in discharge voltage when discharged at a current density of 4 mA / cm ² corresponding to 0.1 C with respect to the theoretical capacity is 25. Table 1 shows the results of measurement with HJ1001SD8 manufactured by Hokuto Denko Corporation at a temperature of ° C.
As a result, the cell of Comparative Example 1 did not discharge and the cell of Comparative Example 2 had a discharge depth of 15%, whereas the cell of Example 1 had a discharge depth of 72%. The depth of discharge is the ratio of the discharge amount to the discharge capacity.

Examples and comparative examples according to the second embodiment
Example 2
1. Production of negative electrode composite In a glove box under an argon atmosphere, a PP resin 106c / metal foil 106a (stainless steel foil SUS316L in Example 2) / PET resin 106b PP resin partially punched laminate film (exterior body) 5 (a), the portion of the solid electrolyte opening 110 that is not covered with the PP resin was cut off with the solid electrolyte adhesion portion 109 remaining. A two-component room temperature curing type epoxy adhesive was applied to the solid electrolyte bonding portion 109 on the surface of the SUS foil not coated with PP resin, and a rectangular solid electrolyte was bonded. An outer body lower laminate film (outer body plate 107), a negative electrode 103 in which metal Li is bonded to one side of a copper foil, and a copper terminal portion 111 are sandwiched between acid-modified polyolefin-based heat welding sheets 112 and 113, and the aforementioned solid electrolyte side The laminate film (exterior body plate 106) was overlapped, and the ends of the three sides were joined by heat welding with a heat sealer. A cellulose separator was placed on the metal Li, and a non-aqueous electrolyte (1M LiPF ₆ / EC: EMC = 1: 1) was injected into the negative electrode composite 101. Finally, the end portion of the remaining one side was joined and sealed with a heat sealer to produce the negative electrode composite 101 of FIG.

LTAP was used for the solid electrolyte. Further, in order to prevent direct contact between LTAP and the negative electrode composite, a buffer separator was impregnated with a non-aqueous electrolyte solution (this example, 1MLiPF ₆ / EC: EMC = 1: 1) in a cellulose separator. .

2. Preparation of positive electrode The positive electrode was prepared in the same manner as in Example 1.

3. Preparation of air battery It was manufactured in the same manner as in Example 1.

Comparative Example 3
1. Production of Negative Electrode Composite In a glove box under an argon atmosphere, a solid electrolyte opening was cut from a metal foil of a solid electrolyte side laminate film (stainless steel foil SUS316L in Comparative Example 3) / PET resin two-layer metal foil laminate film. A two-component room temperature curing type epoxy-based adhesive was applied to the solid electrolyte adhesion portion, and a rectangular solid electrolyte was adhered to the SUS foil surface. A negative electrode in which an acid-modified polyolefin-based heat welding sheet is placed on the PP resin / metal foil (stainless steel foil in the comparative example) / PET resin laminate film of the lower laminate film of the outer package, and the metal Li is bonded to one side of the copper foil, The welding sheet and the above-mentioned solid electrolyte side laminate film were overlapped, and the ends of the three sides were joined by heat welding with a heat sealer. A cellulose separator was placed on the metal Li, and a nonaqueous electrolytic solution (1M LiPF ₆ / EC: EMC = 1: 1) was injected into the negative electrode composite. Finally, the end of the remaining one side was sealed with a heat sealer to produce a negative electrode composite.
The negative electrode composite according to Comparative Example 3 has the same form as Example 1 except that separate upper and lower exterior body plates are used.

2. Production of positive electrode / Production of air battery It was produced in the same manner as in Example 1.

Discharge / Charge Test In the cell corresponding to the theoretical capacity of 84 mAh in Example 2, when discharging and charging (upper limit voltage 4.2 V) for 1 hour at a current density of ² mA / cm ² equivalent to 0.05 C with respect to the theoretical capacity were repeated. FIG. 8 (Example 2) and FIG. 9 (Comparative Example 3) show the results of measuring the voltage transition using a HJ1001SD8 manufactured by Hokuto Denko at a temperature of 25 ° C.
As a result, Example 2 continued for 14 cycles or more, and stability during discharging and charging was improved. In Comparative Example 3, the discharge voltage was maintained until the 11th cycle. That is, these results show that the stability during discharging and charging is further improved in Example 2.

Examples and comparative examples according to the third embodiment
Example 3
1. Production of negative electrode composite In a glove box under an argon atmosphere, the metal electrolyte (copper foil in the example) of the solid electrolyte side laminate film (exterior body plate 206) / the solid electrolyte opening of the metal foil laminate film of PET resin is cut. did. A two-component room temperature curing type epoxy adhesive 212 was applied to the solid electrolyte bonding portion 211, and a rectangular solid electrolyte was bonded to the copper foil surface 206a. A metal Li is bonded to the copper foil / PET resin copper foil portion 207a of the metal Li negative electrode side laminate film (exterior body plate 207), and the acid-modified polyolefin-based heat welding sheet 213 obtained by cutting the metal Li portion is used as the metal Li. The solid electrolyte side laminate film (exterior body plate 206) was placed on the negative electrode side laminate film (exterior body plate 207), and the ends of the three sides were joined by heat welding with a heat sealer.

A cellulose separator was placed on the metal Li, and a nonaqueous electrolytic solution (1M LiPF ₆ / EC: EMC = 1: 1) was injected into the negative electrode composite 201. Finally, the end of the remaining one side was joined and sealed with a heat sealer, and the negative electrode composite 201 in FIG. 6 was produced.

LTAP was used for the solid electrolyte. Further, in order to prevent direct contact between the LTAP and the solid electrolyte and to carry lithium ion conduction between the solid electrolyte and the lithium metal, a non-aqueous electrolyte solution (in this embodiment, 1 M LiPF ₆ / EC: EMC = 1: The buffer layer was soaked with 1).

2. Production of positive electrode It was produced in the same manner as in Example 1.

3. Production of air battery It was produced by the same method as in Example 1.

Comparative Example 4
1. Production of Negative Electrode Composite In a glove box under an argon atmosphere, the solid electrolyte side laminate film metal foil (copper foil in the comparative example) / PET resin metal foil laminate film opening was cut. A two-component room-temperature curing type epoxy adhesive was applied to the solid electrolyte bonding portion, and a rectangular solid electrolyte was bonded to the copper foil surface. An acid-modified polyolefin-based heat-welded sheet with the metal Li portion cut out is placed on the PP resin / metal foil (copper foil in the comparative example) / PET resin laminate film of the lower laminate film of the exterior material, and the metal Li is applied to the copper foil. The joined negative electrode and the copper foil portion of the above-mentioned solid electrolyte side laminate film were overlapped, and the ends of the three sides were joined by heat welding with a heat sealer. A cellulose separator was placed on the metal Li, and a non-aqueous electrolyte (LiPF ₆ / EC: EMC = 1: 1) was injected into the negative electrode composite. Finally, the end portion of the remaining one side was joined with a heat sealer and sealed to prepare a negative electrode composite of Comparative Example 4.

2. Production of positive electrode / air battery It was produced in the same manner as in Example 3.

Discharge and charge test In the cell equivalent to the theoretical capacity of 1.71 Ah in the example, the transition of the discharge voltage when discharging at a current density of ² mA / cm ² equivalent to 0.05 C with respect to the theoretical capacity was performed at a temperature of 25 ° C. Measurement was carried out with HJ1001SD8 manufactured by the company.
As a result, in Example 3 and Comparative Example 4, the average voltage was good for both discharging and charging. That is, both were excellent in such characteristics. However, Example 3 was 0.01 mm thinner and was about 5% lighter than Comparative Example 4.

1, 101, 201 Negative electrode composite 2, 102, 202 Negative electrode current collector 3, 103, 203 Negative electrode layer 4, 104, 204 Buffer layer 5, 105, 205 Isolation layer 6 Exterior body 6a, 106a, 107a, 206a, 207a Metal layer 6b, 206b, 207b Resin layer 7, 110, 210 Solid electrolyte opening 8, 109, 211 Solid electrolyte adhesion part 9 End part 10 Bending part 11 Adhesive layer 12, 114, 115 Thermal welding part 13 Thermal welding joint part 14 Terminals 106 and 206 Exterior body plates 107 and 207 Exterior body plates 106b and 107b Outer resin layers 106c and 107c Inner resin layers 111 Terminal portions 112 and 113 Thermal welding sheets 116 Adhesive layers 209 Negative electrode terminal portions 212 Adhesives

Claims (5)

A laminate comprising a metal negative electrode, a negative electrode current collector electrically connected to the metal negative electrode, and a metal ion conductive solid electrolyte;
An exterior body that houses the laminate and has an opening that exposes a portion of the laminate to the surface;
The outer package includes a laminate film having at least an outer resin layer and a metal layer inside the resin layer, and is provided so that the opening and the solid electrolyte overlap with each other, and the metal layer of the laminate film And a negative electrode composite of a metal-air battery, wherein the solid electrolyte is joined.   2. The negative electrode composite for a metal-air battery according to claim 1, wherein the metal negative electrode is made of metal lithium, an alloy containing lithium as a main component, or a compound containing lithium as a main component.   The negative electrode composite body of the metal air battery of Claim 1 or 2 whose length of the lamination direction of the said laminated body of the said metal negative electrode is 200 micrometers or more.   An exterior body is formed by thermally welding the edge of a laminate film provided so as to overlap in the stacking direction of the laminate, and the metal layer of the exterior body and the metal negative electrode are electrically energized. The metal negative electrode composite for an air battery according to any one of claims 1 to 3, wherein the metal negative electrode composite is configured.   The negative electrode composite according to any one of claims 1 to 4 and an air electrode including a positive electrode layer containing a conductive material are opposed to each other, and an aqueous system is provided between the negative electrode composite and the positive electrode layer. A metal-air battery in which an electrolyte is provided and a solid electrolyte of the negative electrode composite and an air electrode layer of the air electrode are in contact with the aqueous electrolyte.

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