Sheet metal-air battery, container, and container with cap

Abstract

To provide a metal air battery having flexibility.SOLUTION: A liquid-air shutoff layer 11 is formed of a synthetic resin material, and has moisture permeability of 45.0 (g / m2 24 h) or less and oxygen gas permeability of 19.2 (cm3 / m2 24 h atm) or less. An electrolyte layer 13 contains an aqueous solution containing an ion conductor, a gelatinizer or a thickener, and a conductive filler. A positive electrode layer 14 contains an olefin-based resin, and active carbon in an amount of 40 wt.% or more and 80 wt.% or less. A liquid shutoff layer 15 is formed of a synthetic resin material, and has moisture permeability of 45.0 (g / m2 24h) or less and oxygen gas permeability of 28.0 (cm3 / m2 24 h atm) or more. An air shutoff layer 16 is formed of a synthetic resin material, and has an oxygen gas permeability of 19.2 (cm3 / m2 24 h atm) or less. At least a part of the air shutoff layer is formed so that the part can be peeled from the liquid shutoff layer.SELECTED DRAWING: Figure 1

Description

[Technical Field]

[0001] The present invention relates to a sheet-type metal-air battery, a container, and a container with a cap. [Background technology]

[0002] Conventionally, metal-air batteries are known in which a metal negative electrode layer, an electrolyte layer, and a positive electrode layer are arranged in that order, as shown in, for example, Patent Document 1 below. In a metal-air battery, oxygen from the air taken in from the outside reacts with the electrolyte layer on the surface of the positive electrode layer, and the metal negative electrode layer also reacts with the electrolyte layer. As a result, the metal in the metal negative electrode layer releases electrons and becomes ionized, dissolving into the electrolyte layer. This causes a discharge, allowing current to flow between the metal negative electrode layer and the positive electrode layer. [Prior art documents] [Patent Documents]

[0003] [Patent Document 1] Japanese Patent Publication No. 2020-102399 [Overview of the project] [Problems that the invention aims to solve]

[0004] Conventional metal-air batteries often have a high rigidity in the positive electrode layer, which makes them difficult to apply to applications requiring a certain degree of flexibility, such as containers and labels.

[0005] The present invention provides a sheet-like metal-air battery, a container, and a container with a cap that can be made flexible. [Means for solving the problem]

[0006] A sheet-type metal-air battery according to one aspect of the present invention is configured with at least a gas-liquid barrier layer, a metal negative electrode layer, an electrolyte layer, a positive electrode layer, a liquid barrier layer, and a gas barrier layer provided in this order, wherein the gas-liquid barrier layer is formed of a synthetic resin material and has a moisture permeability of 45.0 g / m² at a thickness of 25 μm, measured in an atmosphere of 25°C and 90% relative humidity according to JIS Z 0208-1976. 2 The oxygen gas permeability at a thickness of 25 μm was measured at a temperature of 20°C and relative humidity of 65% in accordance with JIS K 7126 (isobaric method) and was 19.2 (cm 3 / m 2 The moisture permeability is 24h·atm or less, the electrolyte layer contains an aqueous solution containing an ion conductor, a gelling agent or thickener, and a conductive filler, the positive electrode layer contains an olefin resin and 40 wt% to 80 wt% activated carbon, and the liquid barrier layer is formed of a synthetic resin material, and the moisture permeability is 45.0 g / m³ 2 The oxygen gas permeability is less than 24 hours, and the oxygen gas permeability is 28.0 cm². 3 / m 2 The gas barrier layer is made of a synthetic resin material and the oxygen gas permeability is 19.2 (cm³). 3 / m 2 The temperature is set to be less than 24 hours atm, and at least a portion of the gas barrier layer is formed to be peelable from the liquid barrier layer.

[0007] On the surface of the positive electrode layer, oxygen from the air taken in from the gas barrier layer side reacts with the electrolyte layer, and the metal negative electrode layer also reacts with the electrolyte layer. As a result, the metal in the metal negative electrode layer releases electrons and becomes ionized, dissolving into the electrolyte layer. This generates a discharge, allowing current to flow between the metal negative electrode layer and the positive electrode layer. Since the positive electrode layer contains an olefin resin and activated carbon, it is possible to improve the flexibility of the positive electrode layer, and the sheet-shaped metal air battery can be applied to, for example, containers and labels, etc. which require a certain degree of flexibility. Since the positive electrode layer contains 40 wt% or more and 80 wt% or less of activated carbon, while ensuring the flexibility of the positive electrode layer, on the surface of the positive electrode layer, oxygen in the air taken in from the gas barrier layer side can be reliably reacted with the electrolyte layer. Since the moisture permeability of the gas-liquid barrier layer is 45.0 (g / m 2 ·24h) or less, it is possible to prevent moisture in the electrolyte layer that has passed through the metal negative electrode layer and moisture in an object such as the contents, etc. located on the opposite side of the metal negative electrode layer with respect to the gas-liquid barrier layer from passing through the gas-liquid barrier layer. Since the oxygen gas permeability of the gas-liquid barrier layer is 19.2 (cm 3 / m 2 ·24h·atm) or less, it is possible to prevent the air taken in from the gas barrier layer side from passing through the gas-liquid barrier layer, and oxygen in this air can be reliably reacted with the electrolyte layer on the surface of the positive electrode layer. Since the moisture permeability of the liquid barrier layer is 45.0 (g / m 2 ·24h) or less, it is possible to prevent moisture in the electrolyte layer that has passed through the positive electrode layer from passing through the liquid barrier layer. Since the oxygen gas permeability of the liquid barrier layer is 28.0 (cm 3 / m 2 ·24h·atm) or more, in the liquid barrier layer, it is possible to make it easier for air to enter from the part where the gas barrier layer is peeled off and exposed to the outside toward the inside of the sheet-shaped metal air battery, and oxygen in this air can be reliably reacted with the electrolyte layer on the surface of the positive electrode layer. Since the oxygen gas permeability of the gas barrier layer is 19.2 (cm 3 / m 2·Since it is below (24 h·atm), it becomes possible to prevent air from entering the inside of the sheet-shaped metal air battery from the opposite side of the liquid barrier layer with respect to the gas barrier layer, and at least a part of the gas barrier layer can be prevented from starting the above-described discharge and consuming the battery before being peeled off from the liquid barrier layer.

[0008] The gelling agent or the thickening agent may be a carboxylic acid-based thickening agent or an acrylic acid-based thickening agent.

[0009] Since the gelling agent or the thickening agent is a carboxylic acid-based thickening agent or an acrylic acid-based thickening agent, when air is taken in from the gas barrier layer side, the above-described discharge can be surely caused.

[0010] A container according to one aspect of the present invention is provided with a mouth part, a shoulder part, and a body part in this order from above downward, and the body part is formed by winding the sheet-shaped metal air battery of the present invention around the container axis so that the gas-liquid barrier layer constitutes the inner surface of the container and the gas barrier layer constitutes the outer surface of the container. The mouth part and the shoulder part include a negative electrode terminal layer extending upward from the metal negative electrode layer, a positive electrode terminal layer extending upward from the positive electrode layer, and an insulating layer provided between the negative electrode terminal layer and the positive electrode terminal layer. The negative electrode terminal layer and the positive electrode terminal layer contain an olefin-based resin and a conductive filler, and the insulating layer is formed of an olefin-based resin.

[0011] Since the body part is formed by the sheet-shaped metal air battery of the present invention, flexibility can be provided to the body part. Since the mouth part and the shoulder part include a negative electrode terminal layer, a positive electrode terminal layer, and an insulating layer and do not have an electrolyte layer, the container can be easily formed. Since the negative electrode terminal layer and the positive electrode terminal layer contain an olefin-based resin and a conductive filler, and the insulating layer is formed of an olefin-based resin, flexibility can be provided to the mouth part and the shoulder part, and the insulating layer can be firmly joined to the negative electrode terminal layer and the positive electrode terminal layer. Since the body is formed from the sheet-like metal-air battery of the present invention, and the mouth and shoulder portions are equipped with a negative electrode terminal layer, a positive electrode terminal layer, and an insulating layer, the battery forms part of the container and is built into the container, thus enabling space saving and cost reduction.

[0012] The negative electrode terminal layer is connected to the inner circumferential surface of the metal negative electrode layer, the positive electrode terminal layer is connected to the outer circumferential surface of the positive electrode layer, and the insulating layer may extend integrally upward from the upper opening edges of the metal negative electrode layer, the electrolyte layer, and the positive electrode layer, respectively.

[0013] Since the insulating layer extends integrally upward from the upper opening edges of the metal negative electrode layer, electrolyte layer, and positive electrode layer, it is possible to ensure sufficient thickness of the insulating layer, thereby reliably insulating the negative electrode terminal layer from the positive electrode terminal layer.

[0014] A capped container according to one aspect of the present invention has a cap that is detachably attached to the mouth of the container, and the inner surface of the cap is provided with an energizing portion that connects the negative electrode terminal layer and the positive electrode terminal layer.

[0015] Since the inner surface of the cap is provided with an energizing section, when at least a portion of the gas barrier layer is separated from the liquid barrier layer and the aforementioned discharge is initiated, current flows through the negative electrode terminal layer, the energizing section of the cap, and the positive electrode terminal layer, causing current to flow between the metal negative electrode layer and the positive electrode layer. Therefore, there is no need to prepare a separate component with an energizing section, which improves operability. Since the cap is detachably attached to the mouth of the container, even after the aforementioned discharge has started, it is possible to switch between energized and de-energized states between the negative electrode terminal layer and the metal negative electrode layer and positive electrode layer through the positive electrode terminal layer by attaching and detaching the cap to the mouth, thereby ensuring the battery's lifespan. [Effects of the Invention]

[0016] According to one aspect of the present invention, flexibility can be provided. [Brief explanation of the drawing]

[0017] [Figure 1] This is a cross-sectional view of a sheet-shaped metal-air battery, a container, and a container with a cap, as shown in one embodiment. [Modes for carrying out the invention]

[0018] A sheet-type metal-air battery 1 according to one embodiment of the present invention will be described below with reference to the drawings.

[0019] As shown in Figure 1, the sheet-type metal-air battery 1 is configured with at least a gas-liquid barrier layer 11, a metal negative electrode layer 12, an electrolyte layer 13, a positive electrode layer 14, a liquid barrier layer 15, and a gas barrier layer 16, arranged in this order. The sheet-type metal-air battery 1 is a primary battery.

[0020] The gas-liquid barrier layer 11 is formed of a synthetic resin material such as polyethylene terephthalate, polyethylene, polypropylene, or ethylene-vinyl alcohol copolymer. In the gas-liquid barrier layer 11, the moisture permeability at a thickness of 25 μm was measured at a temperature of 25°C and a relative humidity of 90% in an atmosphere based on JIS Z 0208-1976, and was 45.0 g / m². 2 (24h) or less, preferably 10.0 (g / m²) 2 The value is less than 24 hours. In the gas-liquid barrier layer 11, the oxygen gas permeability at a thickness of 25 μm was measured at a temperature of 20°C and a relative humidity of 65% based on JIS K 7126 (isobaric method), and was 19.2 cm². 3 / m 2 (24 hours atm) or less, preferably 13.0 cm 3 / m 2 (24-hour ATM) or less.

[0021] Hereinafter, "water permeability" and "oxygen gas permeability" will represent values ​​measured under the same conditions as those for the gas-liquid barrier layer 11.

[0022] The metal anode layer 12 is formed from, for example, aluminum, magnesium, calcium, lithium, iron, or zinc. The metal anode layer 12 is composed of a single metal material, such as aluminum foil.

[0023] The electrolyte layer 13 contains an aqueous solution containing an ion conductor (for example, an aqueous solution of sodium chloride), a gelling agent or thickening agent (for example, sodium polyacrylate), and a conductive filler (for example, carbon). The electrolyte layer 13 insulates the metal negative electrode layer 12 and the positive electrode layer 14. By using an aqueous sodium chloride solution as the aqueous solution in the electrolyte layer 13 and sodium polyacrylate as the thickener, the electrolyte layer 13 can be firmly bonded to the metal negative electrode layer 12 and the positive electrode layer 14.

[0024] Examples of ion conductors include one or more selected from chlorides such as sodium chloride and potassium chloride, acetates, carbonates, citrates, phosphates, pyrophosphates, and metaphosphates. The gelling agent or thickening agent is a carboxylic acid-based thickening agent or an acrylic acid-based thickening agent. Examples of gelling agents or thickening agents include one or a mixture of several selected from sodium polyacrylate, agarose, gelatin, cellulose-based (methylcellulose, hydroxypropyl methylcellulose, hydroxyethylcellulose, sodium carboxymethylcellulose, etc.), carboxyvinyl polymer, starch, glycogen, pectin, carrageenan, and xanthan gum. The content of the gelling agent or thickening agent is 1 to 30% by weight relative to the aqueous solution, preferably about 5 to 10%. Examples of conductive fillers include metals such as nickel, aluminum, stainless steel, silver, copper, and titanium, carbon such as graphite and carbon black, and mixtures thereof. The content of the conductive filler is 1 to 30% by weight relative to the aqueous solution, preferably about 5 to 10%.

[0025] If the electrolyte layer 13 is thin, a separator (not shown) may be provided in the electrolyte layer 13 to prevent a short circuit between the metal negative electrode layer 12 and the positive electrode layer 14. Examples of separators include porous films made of polyethylene or polypropylene, laminates of these porous films, and nonwoven fabrics made of synthetic fibers such as polyester fibers and aramid fibers, or glass fibers. Ceramic fine particles such as silica, alumina, and titania may be attached to the surfaces of these porous films, laminates, and nonwoven fabrics.

[0026] The positive electrode layer 14 contains an olefin resin and 40 wt% to 80 wt%, preferably 50 wt% to 70 wt%, of activated carbon. On the surface of the positive electrode layer 14, oxygen from the air taken in from the gas barrier layer 16 side reacts with the electrolyte layer 13 to reduce the oxygen. Examples of olefin resins include polyethylene or polypropylene. By mixing activated carbon with the olefin resin, it is possible to suppress the shedding of powdered activated carbon from the positive electrode layer 14 and ensure the flexibility of the positive electrode layer 14.

[0027] The liquid barrier layer 15 is formed of a synthetic resin material such as polytetrafluoroethylene (PTFE). The moisture permeability of the liquid barrier layer 15 is 45.0 g / m³. 2 (24h) or less, preferably 10.0 (g / m²) 2 The oxygen gas permeability of the liquid barrier layer 15 is less than 28.0 (cm²). 3 / m 2 It is 24 hours (ATM) or longer. Since PTFE generally has high water repellency, the moisture permeability can be easily reduced, and when it is made porous by stretching or other means, the oxygen gas permeability can be increased while maintaining low moisture permeability.

[0028] The gas barrier layer 16 is formed of a synthetic resin material such as polyethylene terephthalate, polyethylene, polypropylene, or ethylene-vinyl alcohol copolymer. The synthetic resin material forming the gas barrier layer 16 may be the same as the synthetic resin material forming the gas-liquid barrier layer 11. The oxygen gas permeability of the gas barrier layer 16 is 19.2 cm². 3 / m 2 (24 hours atm) or less, preferably 13.0 cm 3 / m 2 The temperature is less than or equal to 24 hours atm. At least a portion of the gas barrier layer 16 is formed to be peelable from the liquid barrier layer 15. A weakening line may be provided on the outer surface of the gas barrier layer 16 opposite to the liquid barrier layer 15, so that a portion of the gas barrier layer 16 can be easily peeled from the liquid barrier layer 15.

[0029] As described above, in the sheet-type metal-air battery 1 according to this embodiment, oxygen in the air taken in from the gas barrier layer 16 side reacts with the electrolyte layer 13 on the surface of the positive electrode layer 14, and the metal negative electrode layer 12 also reacts with the electrolyte layer 13. As a result, the metal of the metal negative electrode layer 12 releases electrons and becomes ionized, dissolving into the electrolyte layer 13. This causes a discharge, and the metal negative electrode layer 12 and the positive electrode layer 14 become electrically conductive.

[0030] Since the positive electrode layer 14 contains an olefin resin and activated carbon, it is possible to improve the flexibility of the positive electrode layer 14, and the sheet-type metal-air battery 1 can be applied to containers and labels, etc., where a certain degree of flexibility is required. Since the positive electrode layer 14 contains 40 wt% to 80 wt% activated carbon, the flexibility of the positive electrode layer 14 can be ensured, while reliably reacting the oxygen in the air taken in from the gas barrier layer 16 side with the electrolyte layer 13 on the surface of the positive electrode layer 14.

[0031] The moisture permeability of the gas-liquid barrier layer 11 is 45.0 g / m³. 2Since the interval is less than 24 hours, it is possible to prevent moisture in the electrolyte layer 13 that has passed through the metal negative electrode layer 12, and moisture in an object located on the opposite side of the metal negative electrode layer 12 from the gas-liquid barrier layer 11, such as the contents, from passing through the gas-liquid barrier layer 11. The oxygen gas permeability of the gas-liquid barrier layer 11 is 19.2 cm 3 / m 2 Since the temperature is below 24h·atm, it is possible to prevent air taken in from the gas barrier layer 16 side from passing through the gas-liquid barrier layer 11, and the oxygen in this air and the electrolyte layer 13 can be reliably reacted on the surface of the positive electrode layer 14.

[0032] The moisture permeability of the liquid barrier layer 15 is 45.0 (g / m²). 2 Since the interval is less than 24 hours, it is possible to prevent the moisture in the electrolyte layer 13 that has passed through the positive electrode layer 14 from passing through the liquid barrier layer 15. The oxygen gas permeability of the liquid barrier layer 15 is 28.0 cm 3 / m 2 Since the temperature is above 24 hours atm, the liquid barrier layer 15 allows air to easily enter the inside of the sheet-like metal-air battery 1 from the portion of the liquid barrier layer 15 that has been peeled off and exposed to the outside, and this allows the oxygen in the air and the electrolyte layer 13 to react reliably on the surface of the positive electrode layer 14.

[0033] The oxygen gas permeability of the gas barrier layer 16 is 19.2 cm 3 / m 2 Since the pressure is less than 24 hours atm, it is possible to prevent air from entering the inside of the sheet-shaped metal-air battery 1 from the opposite side of the liquid barrier layer 15 relative to the gas barrier layer 16, and it is possible to prevent the aforementioned discharge from starting and the battery from being consumed before at least a portion of the gas barrier layer 16 peels off from the liquid barrier layer 15.

[0034] Since the gelling agent or thickening agent contained in the electrolyte layer 13 is a carboxylic acid-based thickening agent or an acrylic acid-based thickening agent, the aforementioned discharge can be reliably generated when air is drawn in from the gas barrier layer 16 side.

[0035] Next, a capped container 2 according to one embodiment of the present invention will be described. The container with a cap 2 comprises a container 3 and a cap 4.

[0036] Container 3 is constructed with a mouth portion 31, a shoulder portion 32, a body portion 33, and a bottom portion (not shown), arranged in this order from top to bottom. The bottom portion closes the lower end opening of the body portion 33. The mouth portion 31, shoulder portion 32, and body portion 33 are arranged in this order with their respective central axes positioned on a common axis.

[0037] Hereinafter, the common axis will be referred to as the container axis O, the side of the opening 31 along the container axis O will be referred to as the upper side, the opposite side as the lower side, and the direction along the container axis O will be referred to as the vertical direction. The direction that intersects the container axis O when viewed from the vertical direction will be referred to as the radial direction, and the direction that circles around the container axis O when viewed from the vertical direction will be referred to as the circumferential direction.

[0038] The body portion 33 is constructed by rolling a sheet-shaped metal-air battery 1 around the container axis O such that the gas-liquid barrier layer 11 constitutes the inner surface i of the container and the gas barrier layer 16 constitutes the outer surface o of the container. If the weakening line is provided in the gas barrier layer 16, the weakening line is located on the outer surface o of the container. The body portion 33 is formed by joining the circumferential edges of the sheet-shaped metal-air battery 1 together. As a result, the body portion 33 is constructed by stacking the gas-liquid barrier layer 11, the metal negative electrode layer 12, the electrolyte layer 13, the positive electrode layer 14, the liquid barrier layer 15, and the gas barrier layer 16 in this order from the radial inside to the outside, regardless of their circumferential position.

[0039] The bottom portion is formed when the lower end of the sheet-like metal-air battery 1, which is rolled up around the container axis O, is crushed in one radial direction. In other words, the container 3 is a tube container.

[0040] The upper ends of the metal negative electrode layer 12, the electrolyte layer 13, and the positive electrode layer 14 are located above the upper opening edges of the gas-liquid barrier layer 11, the liquid barrier layer 15, and the gas barrier layer 16. The upper ends of the metal negative electrode layer 12, the electrolyte layer 13, and the positive electrode layer 14 extend straight in the vertical direction and are located at the lower end of the shoulder portion 32.

[0041] The mouth portion 31 and the shoulder portion 32 include a negative electrode terminal layer 34 extending upward from the metal negative electrode layer 12, a positive electrode terminal layer 35 extending upward from the positive electrode layer 14, and an insulating layer 36 provided between the negative electrode terminal layer 34 and the positive electrode terminal layer 35.

[0042] The negative terminal layer 34 and the positive terminal layer 35 contain an olefin resin and a conductive filler. The insulating layer 36 is formed of an olefin resin. In these layers 34-36, examples of olefin resins include polyethylene or polypropylene, and examples of conductive fillers include metals such as nickel, aluminum, stainless steel, silver, copper, and titanium, carbon such as graphite and carbon black, and mixtures thereof. Each of the negative electrode terminal layer 34 and the positive electrode terminal layer 35 contains 15 wt% or more of olefin resin. Because the negative electrode terminal layer 34 and the positive electrode terminal layer 35 contain olefin resin and conductive filler, rather than being made solely of metal material, the mouth portion 31 and shoulder portion 32 can be given flexibility and good moldability.

[0043] If oxygen from the air enters the positive electrode terminal layer 35 from the outer surface and reaches the positive electrode layer 14, it is preferable to cover the entire outer surface of the positive electrode terminal layer 35 with a coating layer made of a synthetic resin material such as polyethylene terephthalate, polyethylene, polypropylene, or ethylene-vinyl alcohol copolymer to prevent such air from entering. The inner circumferential surface of the negative electrode terminal layer 34 may be covered over its entire surface with a coating layer made of a synthetic resin material such as polyethylene terephthalate, polyethylene, polypropylene, or ethylene-vinyl alcohol copolymer, thereby preventing the conductive filler from falling off the inner circumferential surface of the negative electrode terminal layer 34 and preventing the contents from coming into contact with the negative electrode terminal layer 34.

[0044] The negative electrode terminal layer 34 is connected to the inner circumferential surface of the metal negative electrode layer 12. In the illustrated example, the negative electrode terminal layer 34 extends integrally upward from the inner circumferential surface of the upper end of the metal negative electrode layer 12 and from the upper opening edge of the gas-liquid barrier layer 11. The inner circumferential surface of the negative electrode terminal layer 34 is connected vertically to the inner circumferential surface of the gas-liquid barrier layer 11 without any steps. The negative electrode terminal layer 34 may also cover the inner circumferential surface of the upper end of the gas-liquid barrier layer 11. The positive electrode terminal layer 35 is connected to the outer circumferential surface of the positive electrode layer 14. In the illustrated example, the positive electrode terminal layer 35 extends integrally upward from the outer circumferential surface of the upper end of the positive electrode layer 14, and from the upper opening edges of the liquid barrier layer 15 and the gas barrier layer 16. The outer circumferential surface of the positive electrode terminal layer 35 is connected vertically to the outer circumferential surface of the gas barrier layer 16 without any steps. The positive electrode terminal layer 35 may also cover the outer circumferential surface of the upper end of the gas barrier layer 16. The insulating layer 36 extends integrally upward from the upper opening edges of the metal negative electrode layer 12, the electrolyte layer 13, and the positive electrode layer 14. The inner circumferential surface of the insulating layer 36 is joined to the outer circumferential surface of the negative electrode terminal layer 34, and the outer circumferential surface of the insulating layer 36 is joined to the inner circumferential surface of the positive electrode terminal layer 35.

[0045] The cap 4 is detachably attached to the mouth 31 of the container 3. An energizing portion 41 is provided on the inner surface of the cap 4, which connects the negative terminal layer 34 and the positive terminal layer 35.

[0046] In the illustrated example, the cap 4 is made of an olefin resin such as polyethylene or polypropylene. The cap 4 is formed in a top-tube shape and is detachably screwed onto the outside of the mouth 31. A seal tube 4a is formed on the top wall of the cap 4, projecting downward and fitted inside the mouth 31.

[0047] The energizing portion 41 is formed in an annular shape and is arranged coaxially with the container axis O. The energizing portion 41 is provided on the lower surface of the top wall of the cap 4. The energizing portion 41 is provided between the outer circumferential surface of the seal cylinder 4a and the inner circumferential surface of the peripheral wall of the cap 4. The energizing portion 41 is made of, for example, copper.

[0048] Furthermore, a light or electrical circuit may be provided on the top wall of the cap 4, and these may be electrically connected to the energizing part 41. If a light or electrical circuit is provided on the upper surface of the top wall of the cap 4, an outer cap may be provided to cover the upper surface of the top wall of the cap 4. Examples of the light include decorative LED lights or UV lights for sterilizing the mouth 31 of the container 3.

[0049] As described above, in the container 3 of this embodiment, since the body portion 33 is formed from a sheet-shaped metal-air battery 1, the body portion 33 can be made flexible. Since the mouth portion 31 and shoulder portion 32 are equipped with a negative electrode terminal layer 34, a positive electrode terminal layer 35, and an insulating layer 36, and do not have an electrolyte layer 13, the container 3 can be easily formed. Since the negative terminal layer 34 and the positive terminal layer 35 contain olefin resin and conductive filler, and the insulating layer 36 is formed of olefin resin, flexibility can be provided to the mouth portion 31 and shoulder portion 32, and the insulating layer 36 can be firmly bonded to the negative terminal layer 34 and the positive terminal layer 35. Since the body portion 33 is formed from a sheet-shaped metal-air battery 1, and the mouth portion 31 and shoulder portion 32 are equipped with a negative electrode terminal layer 34, a positive electrode terminal layer 35, and an insulating layer 36, the battery forms part of the container 3 and is built into the container 3, thereby saving space and reducing costs.

[0050] Since the insulating layer 36 extends integrally upward from the upper opening edges of the metal negative electrode layer 12, the electrolyte layer 13, and the positive electrode layer 14, it is possible to ensure the thickness of the insulating layer 36, thereby reliably insulating the negative electrode terminal layer 34 and the positive electrode terminal layer 35 electrically.

[0051] In the capped container 2 of this embodiment, since the inner surface of the cap 4 is provided with an energizing portion 41, when at least a portion of the gas barrier layer 16 is peeled off from the liquid barrier layer 15 and the aforementioned discharge is initiated, current flows through the negative electrode terminal layer 34, the energizing portion 41, and the positive electrode terminal layer 35, causing the metal negative electrode layer 12 and the positive electrode layer 14 to conduct electricity. Therefore, there is no need to separately prepare a component having the energizing portion 41, and operability can be improved. Since the cap 4 is detachably attached to the opening 31 of the container 3, even after the aforementioned discharge has started, the state of energization and de-energization between the metal negative electrode layer 12 and the positive electrode layer 14 through the negative electrode terminal layer 34 and the positive electrode terminal layer 35 can be switched by attaching or detaching the cap 4 to the opening 31, thereby ensuring the battery's lifespan.

[0052] Furthermore, the technical scope of the present invention is not limited to the embodiments described above, and various modifications can be made without departing from the spirit of the invention.

[0053] In order to increase the electromotive force of the sheet-type metal-air battery 1, a plurality of battery layers consisting of a metal negative electrode layer 12, an electrolyte layer 13, and a positive electrode layer 14 may be arranged in series in the thickness direction between the gas-liquid barrier layer 11 and the liquid barrier layer 15. The sheet-type metal-air battery 1 is not limited to a tube container such as container 3, but may also be used in a pouch container formed by bonding two sheets together, or in a label, for example. In the latter case, an adhesive layer may be provided on the surface of the gas-liquid barrier layer 11 opposite to the metal negative electrode layer 12, and the gas-liquid barrier layer 11 may be bonded to the surface via the adhesive layer.

[0054] The cap 4 may be mounted on the opening 31 to seal the inside of the container 3, and may be provided so as to be movable in the vertical direction between an energized position in which the energized portion 41 is in contact with the negative terminal layer 34 and the positive terminal layer 35, and a non-energetic position located above the energized position in which the energized portion 41 is separated upward from the negative terminal layer 34 and the positive terminal layer 35. In this case, the cap 4 moves vertically between the energized position and the de-energized position while sealing the inside of the container 3, thus preventing deterioration of the contents inside the container 3 and ensuring the battery's lifespan.

[0055] Furthermore, without departing from the spirit of the present invention, the components in the above embodiments may be replaced with well-known components as appropriate, and the above embodiments and modifications may be combined as appropriate.

[0056] Examples of the present invention are as follows: <1> At least a gas-liquid barrier layer, a metal negative electrode layer, an electrolyte layer, a positive electrode layer, a liquid barrier layer, and a gas barrier layer are provided in this order. The aforementioned gas-liquid barrier layer is formed of a synthetic resin material, and its moisture permeability at a thickness of 25 μm was measured at a temperature of 25°C and a relative humidity of 90% in accordance with JIS Z 0208-1976, and was 45.0 g / m². 2 The oxygen gas permeability at a thickness of 25 μm was measured at a temperature of 20°C and relative humidity of 65% in accordance with JIS K 7126 (isobaric method) and was 19.2 (cm 3 / m 2 (24 hours / atm) or less. The electrolyte layer contains an aqueous solution containing an ion conductor, a gelling agent or thickening agent, and a conductive filler. The positive electrode layer contains an olefin resin and 40 wt% to 80 wt% activated carbon. The liquid barrier layer is formed of a synthetic resin material, and the moisture permeability is 45.0 g / m². 2 The oxygen gas permeability is less than 24 hours, and the oxygen gas permeability is 28.0 cm². 3 / m 2(24 hours / atm) or longer. The gas barrier layer is formed of a synthetic resin material, and the oxygen gas permeability is 19.2 cm². 3 / m 2 (24 hours / atm) or less. A sheet-type metal-air battery, wherein at least a portion of the gas barrier layer is formed to be detachable from the liquid barrier layer. <2> The gelling agent or the thickening agent is a carboxylic acid-based thickening agent or an acrylic acid-based thickening agent. <1> A sheet-type metal-air battery as described above. <3> The mouth, shoulders, and torso are arranged in this order from top to bottom. The body portion is such that the gas-liquid barrier layer constitutes the inner surface of the container and the gas barrier layer constitutes the outer surface of the container. <1> or <2> The sheet-shaped metal-air battery described above is formed by rolling it up around the axis of the container. The mouth portion and the shoulder portion are, A negative electrode terminal layer extending upward from the aforementioned metal negative electrode layer, A positive electrode terminal layer extending upward from the positive electrode layer, The system comprises an insulating layer provided between the negative terminal layer and the positive terminal layer, The negative electrode terminal layer and the positive electrode terminal layer contain an olefin resin and a conductive filler. The container is formed of an olefin resin as the insulating layer. <4> The negative electrode terminal layer is connected to the inner circumferential surface of the metal negative electrode layer, The positive electrode terminal layer is connected to the outer circumferential surface of the positive electrode layer, The insulating layer extends integrally upward from the upper opening edge of the metal negative electrode layer, the electrolyte layer, and the positive electrode layer, <3> The container described. <5> The aforementioned <3> or <4> A cap is detachably attached to the opening of the container described above. A container with a cap, wherein the inner surface of the cap is provided with an energizing portion for connecting the negative terminal layer and the positive terminal layer. [Explanation of symbols]

[0057] 1. Sheet-type metal-air battery 2 containers with caps 3 containers 4 caps 11. Gas-liquid barrier layer 12 Metal negative electrode layer 13 Electrolyte layer 14. Positive electrode layer 15. Liquid barrier layer 16. Gas barrier layer 31 Mouth 32 Shoulder 33 Torso 34 Negative terminal layer 35 Positive terminal layer 36 Insulating layer 41 Power supply section i Inside of the container o Container exterior O Container axis

Claims

1. At least a gas-liquid barrier layer, a metal negative electrode layer, an electrolyte layer, a positive electrode layer, a liquid barrier layer, and a gas barrier layer are provided in this order. The aforementioned gas-liquid barrier layer is formed of a synthetic resin material, and its moisture permeability at a thickness of 25 μm was measured at a temperature of 25°C and a relative humidity of 90% in accordance with JIS Z 0208-1976, which is 45.0 g / m². ２ - The oxygen gas permeability at a thickness of 25 μm was measured at a temperature of 20°C and a relative humidity of 65% in accordance with JIS K 7126 (isobaric method) and was less than 24 h. ３ / m ２ (24 hours / atm) or less, The electrolyte layer contains an aqueous solution containing an ion conductor, a gelling agent or thickening agent, and a conductive filler. The positive electrode layer contains an olefin resin and 40 wt% to 80 wt% activated carbon. The liquid barrier layer is formed of a synthetic resin material, and the moisture permeability is 45.0 g / m³. ２ - The oxygen gas permeability is less than or equal to 24 hours, and the oxygen gas permeability is 28.0 cm². ３ / m ２ (24 hours at) or more, The gas barrier layer is formed of a synthetic resin material, and the oxygen gas permeability is 19.2 cm. ３ / m ２ (24 hours / atm) or less, A sheet-type metal-air battery, wherein at least a portion of the gas barrier layer is formed to be detachable from the liquid barrier layer.

2. The sheet-type metal-air battery according to claim 1, wherein the gelling agent or the thickening agent is a carboxylic acid-based thickening agent or an acrylic acid-based thickening agent.

3. The mouth, shoulders, and torso are arranged in this order from top to bottom. The body portion is constructed by rolling up a sheet-like metal-air battery according to claim 1 or 2 around the container axis such that the gas-liquid barrier layer constitutes the inner surface of the container and the gas barrier layer constitutes the outer surface of the container. The mouth portion and the shoulder portion are, A negative electrode terminal layer extending upward from the aforementioned metal negative electrode layer, A positive electrode terminal layer extending upward from the positive electrode layer, The system comprises an insulating layer provided between the negative terminal layer and the positive terminal layer, The negative electrode terminal layer and the positive electrode terminal layer contain an olefin resin and a conductive filler. The container is formed of an olefin resin as the insulating layer.

4. The negative electrode terminal layer is connected to the inner circumferential surface of the metal negative electrode layer, The positive electrode terminal layer is connected to the outer circumferential surface of the positive electrode layer, The container according to claim 3, wherein the insulating layer extends integrally upward from the upper opening edge of the metal negative electrode layer, the electrolyte layer, and the positive electrode layer, respectively.

5. A cap is detachably attached to the mouth of the container according to claim 3. A container with a cap, wherein the inner surface of the cap is provided with an energizing portion for connecting the negative terminal layer and the positive terminal layer.

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