JP6632815B2 - Water injection type battery, manufacturing method of water injection type battery - Google Patents

Description

  The present invention relates to a water injection type battery that starts power generation by water injection.

  In recent years, wearable terminals such as wristbands, wristwatches, and eyeglasses have become widespread.However, these terminals tend to be thinner, smaller, lighter, and more flexible. Are also expected to have similar characteristics. Further, since the wearable terminal is used in contact with the human body, it is also important to use a battery made of a material harmless to the human body.

  Various batteries mounted on the wearable terminal have been developed, and examples thereof include a liquid electrolyte secondary battery, an all-solid secondary battery, and a water battery. Patent Literature 1 discloses a water battery in which a substantially rectangular metal alloy thin plate is used for a positive electrode plate and a negative electrode plate as current collectors and water is used as an electrolyte. Patent Document 2 discloses a water battery in which a metal plate made of a magnesium material is used for a negative electrode and water is used as an electrolyte.

JP 2011-222236 A Utility Model Registration No. 3175210

  Lithium-ion batteries, which are the most common liquid electrolyte secondary batteries, have the advantage of high output because of their high energy density.However, since a flammable organic solvent is used as the electrolyte, the electrolyte must be outside the battery. There is a problem in terms of safety in consideration of the possibility of leakage into the vehicle. An all-solid secondary battery has a low risk of electrolyte leakage because the electrolyte is solid, but may not provide sufficient flexibility.

The water batteries shown in Patent Literatures 1 and 2 are those in which water is injected as an electrolyte before use of the battery, so that the battery life can be prolonged. Further, since the electrolyte is water, the water battery is compared with a lithium ion battery or the like. Not only is safety high, but also the cost required for manufacturing the electrolyte can be reduced. On the other hand, since a plate made of a metal material is used for the electrodes of these water batteries, the flexibility is not sufficient. If the electrode area is increased in order to further increase the power generation capacity, there is a concern that the whole battery will become larger and heavier. Thus, there is room for improvement in applying a water battery to a wearable terminal.
Therefore, an object of the present invention is to provide a water injection type battery having flexibility that can increase the capacity while ensuring safety for the human body.

  The water-filled battery of the present invention that has achieved the above object has a first base having flexibility, a positive electrode thin film member formed on one main surface of the first base, and a flexibility. A second base member, and a negative electrode thin film member formed on one main surface of the second base member, wherein the positive electrode thin film member and the negative electrode thin film member are arranged to face each other; And a liquid passage formed between the first electrode and the negative electrode thin film member. Since the first base material and the second base material have flexibility and the thin film member is used for the positive electrode and the negative electrode in the water injection type battery of the present invention, compared with the case of using a metal plate, The thickness is suppressed, and the flexibility of the battery can be increased. Further, since the water injection type battery of the present invention uses water as the electrolyte, the safety is higher than that of the lithium ion battery, and the cost required for manufacturing the electrolyte can be suppressed. Therefore, the water injection type battery of the present invention is suitable for mounting on a wearable terminal used in contact with the surface of a human body.

  The water supply type battery of the present invention preferably has a water supply port directly or indirectly connected to the liquid passage. As a result, water as an electrolyte can be injected from the water injection port into the liquid passage, so that the battery can be operated as a water injection type battery.

  In the water injection battery of the present invention, it is preferable that the positive electrode active material layer is provided on the main surface of the positive electrode thin film member and on the side opposite to the first substrate. By providing the positive electrode active material layer on the main surface of the positive electrode thin film member facing the negative electrode, the electrode reaction is efficiently activated. Further, if the positive electrode active material is provided separately from the positive electrode thin film member, a material suitable for the positive electrode thin film member and a material suitable for the positive electrode active material layer can be respectively selected.

  In the water injection battery of the present invention, it is preferable that the positive electrode thin film member contains a positive electrode active material or is made of a material capable of collecting the positive electrode active material. Thus, the positive electrode active material that directly contributes to the reaction at the positive electrode can be supplied to the positive electrode thin film member, so that it is not necessary to provide a positive electrode active material layer separately from the positive electrode thin film member.

  In the water injection battery of the present invention, it is preferable that a negative electrode active material layer is provided on the main surface of the negative electrode thin film member and on the side opposite to the second base material. By providing the negative electrode active material layer on the main surface of the negative electrode thin film member facing the positive electrode, the electrode reaction is efficiently activated. If a negative electrode active material layer is provided separately from the negative electrode thin film member, a material suitable for the negative electrode thin film member and a material suitable for the negative electrode active material layer can be selected.

  In the water injection type battery of the present invention, it is preferable that the negative electrode thin film member is made of a material containing a negative electrode active material. Thus, the negative electrode active material that directly contributes to the reaction at the negative electrode can be supplied to the negative electrode thin film member, so that it is not necessary to provide a negative electrode active material layer separately from the negative electrode thin film member.

  In the water injection type battery of the present invention, a separator is suitably provided between the positive electrode thin film member and the negative electrode thin film member. By providing the separator, a short circuit between the positive electrode thin film member and the negative electrode thin film member is suppressed.

  The separator is preferably an insulating film layer formed on at least one of the main surfaces of the positive electrode thin film member and the negative electrode thin film member. By forming the separator with the insulating film layer, an increase in the thickness of the separator can be suppressed. Preferably, a pattern is formed on the insulating film layer. Thus, a liquid passage through which the electrolytic solution passes is formed in a portion where the insulating film layer does not exist.

  The water injection type battery of the present invention is preferably provided with an outer package containing the positive electrode thin film member, the negative electrode thin film member, and the electrolyte. Thus, the electrolyte required for the electrode reaction can be held in the battery.

  In the water-filled battery of the present invention, it is preferable that an end portion of the first base member and an end portion of the second base member are joined to each other to form an electrolyte solution accommodating portion. Accordingly, it is not necessary to newly provide a member for accommodating the electrolytic solution, so that an increase in the thickness and size of the battery can be suppressed as compared with the case where the exterior body is provided.

  In the water injection type battery of the present invention, it is preferable that the first base material and the second base material are formed continuously through the bent portion. Thereby, the number of members constituting the battery can be reduced as compared with the case where the first base material and the second base material are formed of different base materials.

  The present invention also includes a water injection type cylindrical battery in which the above water injection type battery is wound in a roll shape. The water-filled battery of the present invention has high flexibility and can be easily wound, so that it is suitable for processing into a general cylindrical battery.

  The method of manufacturing a water-injection battery according to the present invention, which has achieved the above object, includes a step of forming a positive electrode thin film member on one principal surface of a flexible first base material; Forming a positive electrode active material layer on at least one of the positive electrode thin film members, forming a negative electrode thin film member on one main surface of a flexible second base material, And a step of forming a liquid passage between the positive electrode thin film member and the negative electrode thin film member by disposing the negative electrode thin film member and the negative electrode thin film member so as to face each other. In the method for manufacturing a water-injection battery according to the present invention, since the thin film members are formed as the positive electrode and the negative electrode, the thickness of the electrode is suppressed as compared with the case where a metal plate is used, and a highly flexible battery is obtained.

  In the method for manufacturing a water injection type battery according to the present invention, it is preferable that the negative electrode thin film member is formed of a material containing a negative electrode active material. Since such a negative electrode thin film member can not only function as a current collector but also serve as a negative electrode active material layer, it is not necessary to provide a negative electrode active material layer separately from the negative electrode thin film member.

  It is preferable to use a sputtering method or a coating method in the step of forming the positive electrode thin film member and the step of forming the negative electrode thin film member. When the sputtering method or the coating method is used, the thickness of the positive electrode thin film member and the negative electrode thin film member can be reduced, so that the flexibility of the battery can be further improved.

  A mask layer is formed on one of the first base material and the second base material, and the mask layer is brought into contact with an etchant to remove a part of the region, thereby forming the first base material, the positive electrode thin film member, and the positive electrode active material. It is preferable to include a step of forming an opening in the material layer and the separator, or in the second base material, the negative electrode thin film member, and the separator. The opening thus formed serves as a liquid passage through which the electrolytic solution passes. Then, when the electrolytic solution is supplied from the side surface on which the pattern is formed, the electrolytic solution easily spreads over the entire electrode thin film member through the liquid passage.

The water-filled battery of the present invention has high flexibility because the first base material and the second base material have flexibility and the thickness of the electrode is suppressed. Further, since water is used as the electrolyte, the safety is higher than that of the lithium ion battery, and the cost required for manufacturing the electrolyte can be suppressed. For this reason, a battery suitable for mounting on a wearable terminal used in contact with the surface of a human body is obtained.
In addition, according to the method for manufacturing a water-injected battery of the present invention, since the thin film members are formed as a positive electrode and a negative electrode on a flexible base material, the thickness of the electrode is smaller than when a metal plate is used. And a highly flexible battery can be obtained.

FIG. 1 is a cross-sectional view of the water injection battery according to Embodiment 1 of the present invention. FIG. 2 is a cross-sectional view of the water injection type battery according to Embodiment 1 of the present invention. FIG. 3 is a cross-sectional view of the water injection type battery according to Embodiment 1 of the present invention. FIG. 4 is a cross-sectional view of the water injection type battery according to Embodiment 1 of the present invention. 5A and 5B are plan views of the insulating film layer according to the first embodiment of the present invention. FIG. 5A shows a dot shape, FIG. 5B shows a stripe shape, and FIGS. 5C and 5D. 5) is a plan view of a leaf-shaped insulating film layer, and FIG. FIG. 6 is a perspective view showing a configuration example in which the exterior body is provided in the water-injection type battery according to Embodiment 1 of the present invention. FIG. 7 is a view of the water injection type battery of FIG. FIG. 8 is a perspective view showing a configuration example in which an electrolyte container is formed in the water injection type battery according to Embodiment 1 of the present invention. FIG. 9 is a cross-sectional view of the water injection type battery of FIG. 8 in the XZ plane direction. FIG. 10 is a cross-sectional view of a water injection type battery according to Embodiment 2 of the present invention. FIG. 11 is a developed view showing another configuration example of the water-injection battery according to Embodiment 2 of the present invention. FIG. 12 is a cross-sectional view showing another configuration example of the water injection type battery according to Embodiment 2 of the present invention. FIG. 13 is a developed view of a water-injection battery according to Embodiment 3 of the present invention. FIG. 14 is a cross-sectional view of the water injection type battery according to Embodiment 3 of the present invention. FIG. 15 is a plan view of a water injection type battery according to Embodiment 4 of the present invention. FIG. 16 is a sectional view taken along line XVI-XVI in FIG. FIG. 17 is a perspective view illustrating a method for manufacturing a water-injection cylindrical battery according to Embodiment 5 of the present invention. FIG. 18 is a cross-sectional view illustrating the method for manufacturing the water-injection battery of the present invention. FIG. 19 is a cross-sectional view illustrating the method for manufacturing the water-injection battery of the present invention. FIG. 20 is a cross-sectional view illustrating a method for manufacturing a water injection type battery of the present invention. FIG. 21 is a cross-sectional view illustrating the method for manufacturing the water-injection battery of the present invention.

  Hereinafter, the water-injection battery according to the present invention will be specifically described with reference to the drawings, but the present invention is not limited to the illustrated examples, and may be appropriately applied within a range that can conform to the purpose described above and below. Modifications may be made and all of them are included in the technical scope of the present invention.

1. Water injection type battery The water injection type battery of the present invention has a first base material having flexibility, a positive electrode thin film member formed on one main surface of the first base material, and a second base material having flexibility. And a negative electrode thin film member formed on one main surface of the second base material, wherein the positive electrode thin film member and the negative electrode thin film member are arranged to face each other, and the positive electrode thin film member and the negative electrode thin film A liquid passage is formed between the members. Since the first base material and the second base material have flexibility and the thin film member is used for the positive electrode and the negative electrode in the water injection type battery of the present invention, compared with the case of using a metal plate, The thickness is suppressed, and the flexibility of the battery can be increased. Further, since the water injection type battery of the present invention uses water as the electrolyte, the safety is higher than that of the lithium ion battery, and the cost required for manufacturing the electrolyte can be suppressed. Therefore, the water-filled battery of the present invention is suitable for mounting on a wearable terminal used in contact with the surface of a human body.

  In the present invention, the injection type battery has a thickness direction and a plane direction. The thickness direction of the water injection battery is a direction in which the first base material, the positive electrode thin film member, the second base material, and the negative electrode thin film member are stacked, and corresponds to the Z direction in the drawings of the present invention. The surface direction of the water-filled battery is a direction XY orthogonal to the thickness direction Z, and has a horizontal direction X and a vertical direction Y.

  The injection type battery handled in the present invention is one in which water is poured as an electrolyte before using the battery. Therefore, so-called water batteries, air batteries, and oxygen batteries in which water is used as the electrolyte are included in the scope of the present invention. The type of the electrolyte is not particularly limited as long as it contains water, and examples thereof include tap water, seawater, muddy water, sugar water, saline, rainwater, urine, and the like.

(Embodiment 1)
The water injection type battery according to Embodiment 1 of the present invention will be described with reference to FIGS. FIG. 1 is a cross-sectional view of a water injection type battery 10 according to Embodiment 1 of the present invention. The water-filled battery 10 (10A) includes a first base member 20, a positive electrode thin film member 30, a second base member 21, and a negative electrode thin film member 40.

  The first base member 20 is provided to support the positive electrode thin film member 30, and has one main surface 20a and the other main surface 20b. The first base material 20 has flexibility and is formed of, for example, a polymer film such as polyethylene naphthalate (PEN), polyethylene terephthalate (PET), polyimide (PI), and polyurethane having elasticity. Is preferred. Thereby, a highly flexible water injection type battery can be obtained.

  The first base material 20 preferably has liquid permeability. As a result, the electrolytic solution also reaches the other main surface 20b side of the first base material 20 where the positive electrode thin film member 30 is not formed, and the electrolytic solution also contacts the surface of the positive electrode thin film member 30 on the first base material 20 side. As a result, the number of electrons transferred per unit time can be increased, so that the battery capacity can be increased.

  If the thickness of the first base material 20 (thickness in the thickness direction Z) is too large, the thickness of the entire battery increases, so the thickness of the first base material is preferably 1,000 μm or less, and more preferably 500 μm or less. More preferably, it is even more preferably 100 μm or less. On the other hand, if the film thickness of the first base material 20 is too small, the base material may be broken or broken during the manufacture of the battery, making it difficult to handle. Therefore, the thickness of the first base material is preferably 10 μm or more, preferably 20 μm. It is more preferably at least 30 μm.

  The positive electrode thin film member 30 is a thin film formed on one main surface 20a of the first base member 20, and functions as a current collector. The positive electrode thin film member 30 only needs to include a conductive material having a low ionization tendency with respect to a negative electrode active material described later, for example, a metal material such as copper, silver, and nickel, and can collect oxygen in air. Activated carbon, carbon materials such as carbon nanotubes (CNT) and graphene, oxides such as manganese dioxide, iron oxide and silver oxide, chlorides such as copper chloride, lead chloride and silver chloride, copper iodide, potassium persulfate and the like Combinations can be used.

  In the positive electrode including the first base member 20 and the positive electrode thin film member 30, the positive electrode active material directly contributes to electron transfer. The positive electrode active material oxidizes generated hydrogen in order to prevent polarization in which electrons flowing from the negative electrode react with hydrogen ions in the electrolyte to generate hydrogen and reduce the electromotive force. Therefore, in order to obtain a positive electrode active material, activated carbon capable of capturing oxygen in the air, carbon materials such as CNT and graphene, oxides such as manganese dioxide, iron oxide and silver oxide, copper chloride, lead chloride and silver chloride It is preferable to provide a positive electrode active material layer containing a chloride such as, for example, copper iodide and potassium persulfate.

  Although the place where the positive electrode active material layer is provided is not particularly limited, it is preferable that the positive electrode active material layer is provided on the main surface of the positive electrode thin film member 30 and on the side opposite to the first base material 20. FIG. 2 is a cross-sectional view illustrating a configuration example of a water injection type battery provided with a positive electrode active material layer. In FIG. 2, the positive electrode active material layer 35 is provided on both the one main surface 20a of the first base material 20 and the one main surface 30a of the positive electrode thin film member 30. By providing the positive electrode active material layer 35 on the main surface of the positive electrode thin film member 30 facing the negative electrode (one main surface 30a of the positive electrode thin film member 30), the electrode reaction is efficiently activated. Is done. If the positive electrode active material layer 35 is provided separately from the positive electrode thin film member 30, a material suitable for the positive electrode thin film member 30 and a material suitable for the positive electrode active material layer 35 can be selected. In order to promote the reaction at the positive electrode, the positive electrode active material layer 35 can be provided also on the other main surface 20b of the first base material 20. The formation of the positive electrode active material layer 35 on the first base material 20 or the positive electrode thin film member 30 can be performed by vapor deposition or adhesion using an adhesive.

  In the water injection type battery of the present invention, it is preferable that the positive electrode thin film member 30 contains a positive electrode active material or is made of a material capable of collecting the positive electrode active material. That is, the positive electrode thin film member 30 can capture oxygen in the air, such as activated carbon, carbon materials such as CNT and graphene, oxides such as manganese dioxide, iron oxide and silver oxide, copper chloride, lead chloride, and silver chloride. , Copper iodide and potassium persulfate. Thus, the positive electrode active material that directly contributes to the reaction at the positive electrode can be supplied to the positive electrode thin film member 30, so that it is not necessary to provide the positive electrode active material layer 35 separately from the positive electrode thin film member 30.

  If the thickness of the positive electrode thin film member 30 is too large, the thickness of the entire battery increases, so the thickness of the positive electrode thin film member 30 is preferably 100 μm or less, more preferably 80 μm or less, and more preferably 50 μm or less. Is more preferable. On the other hand, if the thickness of the positive electrode thin film member 30 is too small, the current density in the positive electrode thin film member 30 is limited, so that the thickness of the positive electrode thin film member is preferably 0.1 μm or more, and more preferably 0.5 μm or more. Is more preferable, and it is further preferable that it is 1 μm or more.

  The second base member 21 is provided to support the negative electrode thin film member 40, and has one main surface 21a and the other main surface 21b. Like the first base member 20, the second base member 21 has flexibility, and is preferably formed of a polymer film such as PEN, PET, PI, or polyurethane having elasticity. Thereby, a highly flexible water injection type battery can be obtained.

  The second base material 21 preferably has liquid permeability. As a result, the electrolytic solution also reaches the other main surface 21b side of the second base material 21 where the negative electrode thin film member 40 is not formed, and the electrolytic solution also contacts the surface of the negative electrode thin film member 40 on the second base material 21 side. As a result, the number of electrons transferred per unit time can be increased, so that the battery capacity can be increased.

  If the thickness of the second base member 21 (thickness in the thickness direction Z) is too large, the thickness of the entire battery increases, so the thickness of the second base member 21 is preferably 1000 μm or less, and more preferably 500 μm or less. Is more preferable, and further preferably 100 μm or less. On the other hand, if the thickness of the second base material 21 is too small, the base material is difficult to handle because the base material is broken or broken at the time of manufacturing the battery. Therefore, the thickness of the second base material 21 is preferably 10 μm or more, It is more preferably at least 20 μm, even more preferably at least 30 μm.

  The negative electrode thin film member 40 is a thin film formed on one main surface 21a of the second base member 21 and functions as a current collector. The negative electrode thin film member 40 is not particularly limited as long as it has conductivity and can be formed into a thin film. For example, copper, nickel, iron, stainless steel, titanium, magnesium, aluminum, zinc, or a combination thereof is used. be able to.

  In the present invention, the negative electrode active material that directly contributes to electron transfer at the negative electrode is a metal. As the negative electrode active material, a metal material having a high ionization tendency, for example, magnesium, aluminum, zinc, or a combination thereof can be used.

  It is preferable that a negative electrode active material layer is provided on the main surface of the negative electrode thin film member 40 and on the side opposite to the second substrate 21. By thus providing the negative electrode active material layer on the main surface of the negative electrode thin film member 40 facing the positive electrode, the electrode reaction is efficiently activated. Further, by providing the negative electrode active material layer separately from the negative electrode thin film member 40, a material suitable for the negative electrode thin film member 40 and a material suitable for the negative electrode active material layer can be respectively selected. The formation of the negative electrode active material layer on the second base material 21 or the negative electrode thin film member 40 can be performed by vapor deposition of the negative electrode active material or bonding with an adhesive.

  As shown in FIG. 2, the negative electrode thin film member 40 is preferably made of a material containing a negative electrode active material. Thereby, the negative electrode active material that directly contributes to the reaction at the negative electrode can be supplied to the negative electrode thin film member 40, and the negative electrode thin film member 40 can also serve as the negative electrode active material. Apart from this, there is no need to provide a negative electrode active material layer. For example, if magnesium, aluminum, zinc, or the like is selected as the negative electrode thin film member 40, there is no need to separately provide a negative electrode active material layer.

  In the water injection type battery 10A of the present invention, the positive electrode thin film member 30 and the negative electrode thin film member 40 (hereinafter, also referred to as “electrode thin film member”) are arranged to face each other, and the positive electrode thin film member 30 is A liquid passage 50 is formed between the electrode thin film members 40. 1 and 2, one main surface 30a of the positive electrode thin film member 30 and one main surface 40a of the negative electrode thin film member 40 are arranged to face each other. The liquid passage 50 is a passage through which the electrolyte flows, and also has a function of preventing a short circuit between the positive electrode thin film member 30 and the negative electrode thin film member 40.

For example, in the water injection type battery 10A shown in FIG. 2, copper is used for the positive electrode thin film member 30, activated carbon is used for the positive electrode active material layer 35, and magnesium is used for the negative electrode thin film member 30 also serving as the negative electrode active material. When water is passed as the electrolyte, the reaction represented by the formula (1) and the reaction represented by the formula (2) occurs in each electrode, and the reaction represented by the formula (3) occurs in the entire battery, and magnesium hydroxide is generated.
Positive electrode: O ₂ + 2H ₂ O + (4e ⁻ ) → (4OH ⁻ ) (1)
Negative electrode: 2Mg → (2Mg ²⁺ ) + (4e ⁻ ) (2)
The entire _{battery: 2Mg + O 2 + 2H 2} O → 2Mg (OH) 2 ↓ ··· (3)
Since the electrode reaction does not occur in the water injection type battery 10A unless water is passed through the liquid passage 50, the water injection type battery 10A can be suitably used for storage at the time of disaster.

  3 and 4 are cross-sectional views illustrating a method of insulating the positive electrode thin film member and the negative electrode thin film member of the water injection type battery according to Embodiment 1 of the present invention. In order to prevent a short circuit between the positive electrode thin film member 30 and the negative electrode thin film member 40, a separator 60 is suitably provided between the positive electrode thin film member 30 and the negative electrode thin film member 40 as shown in FIG. The separator 60 shown in FIG. 3 is made of a material having liquid permeability and insulating properties. As the material having liquid permeability and insulating properties, for example, a fibrous nonwoven fabric, a porous polymer film, or the like can be used. In this case, a fiber gap or a continuous hole forms the liquid passage 50.

  As shown in FIG. 4, it is preferable that a separator 60 provided between the positive electrode thin film member 30 and the negative electrode thin film member 40 has a through hole 60a penetrating in the thickness direction. This is because the through hole 60a becomes the liquid passage 50, and the electrolyte easily spreads to the surfaces of the positive electrode active material layer 35 and the negative electrode thin film member 40 through the liquid passage 50.

  The separator 60 is preferably an insulating film layer formed on at least one of the main surfaces of the positive electrode thin film member 30 and the negative electrode thin film member 40. By forming the separator 60 with an insulating film layer, an increase in the thickness of the separator 60 can be suppressed. As the insulating film layer, a known insulating material such as a silicon oxide film or a synthetic resin such as polypropylene, polyethylene, or PET can be used. For forming the insulating film layer, for example, a spin coating method, a vacuum evaporation method, or a sputtering method can be used, and a laminate on the first base material 20 or the second base material 21 is formed by roll-to-roll. In this case, a screen printing method, a gravure printing method, a die coating method, or a spray method, which is a coating method, can be used.

  FIG. 5 is a plan view of the insulating film layer according to the first embodiment of the present invention. It is preferable that a pattern is formed on the insulating film layer 61. The positive electrode thin film member 30 and the negative electrode thin film member 40 are supported by the insulating film layer 61. On the other hand, the portion where the insulating film layer 61 does not exist becomes the liquid passage 50 through which the electrolytic solution passes. By changing the formation pattern of the insulating film layer 61, the shape of the liquid passage 50 can be changed, whereby the flow of the electrolytic solution can be controlled. Photolithography or printing can be used to form the pattern of the insulating film layer 61.

  As shown in FIG. 5A, the insulating film layer 61 can be formed in a dot shape (floating island shape). In this case, since the liquid passages 50 extending in both the left-right direction X and the up-down direction Y are provided, the electrolyte can easily spread over the entire surfaces of the positive electrode thin film member 30 and the negative electrode thin film member 40. In the case where the insulating film layer 61 has a dot shape, even if the electrolytic solution is supplied from any of the upper, lower, right and left directions in FIG.

  As shown in FIG. 5B, the insulating film layer 61 can be formed in a stripe shape. In the striped insulating film layer 61, the area of the liquid passage 50 in the horizontal direction X is smaller than that in the case of the dot shape, and the area occupied by the insulating film layer 61 with respect to the electrode thin film member is larger. For this reason, it becomes difficult for the positive electrode thin film member 30 and the negative electrode thin film member 40 to come into contact with each other, and a short circuit between the positive electrode thin film member 30 and the negative electrode thin film member 40 can be suppressed. In this case, it is preferable that the electrolyte is injected from above or below in FIG.

  As shown in FIG. 5C, the insulating film layer 61 may be formed in a pattern in which the liquid passage 50 has a vein shape. This makes it possible to spread the electrolytic solution over the entire electrode thin film member while suppressing a short circuit between the positive electrode thin film member 30 and the negative electrode thin film member 40. In this case, it is preferable that the electrolyte is injected from the vicinity of the lower center of the liquid passage 50, which is the starting point of the vein shape.

  The insulating film layer may be formed in another vein-like pattern as shown in FIG. In this case, it is preferable that the electrolyte is injected from the vicinity of the center in the vertical direction Y and the horizontal direction X of the liquid passage 50 which is the starting point of the vein shape. Compared with the vein-like pattern shown in FIG. 5C, the longest distance of the liquid passage 50 can be shortened, so that the contact between the electrolytic solution and the electrode thin film member is easily performed quickly.

  As shown in FIG. 5E, the insulating film layer 61 may be formed radially. In this case, it is preferable that the electrolyte is injected from the vicinity of the center of the liquid passage 50 which is the radial center point in the vertical and horizontal directions. Compared with the vein-like pattern shown in FIG. 5D, the longest distance of the liquid passage 50 can be shortened, so that the contact between the electrolytic solution and the electrode thin film member is more easily performed.

  The water supply type battery of the present invention preferably has a water supply port connected to the liquid passage. Thereby, water as an electrolytic solution can be injected from the water inlet into the liquid passage. Although the position of the water injection port is not particularly limited, it is preferable that the water injection port be provided at a position other than the position located below when the battery is used, in order to suppress the electrolyte from leaking out of the battery. The water inlet is suitably provided with a check valve for preventing the water injected into the battery from flowing back out of the battery.

  The water inlet may be directly connected to the liquid passage or may be connected indirectly. When the water inlet is directly connected to the liquid passage, a part of the liquid passage also serves as the water inlet. When the water inlet is indirectly connected to the liquid passage, the electrolyte injected from the water inlet into the battery reaches the liquid passage through a part other than the liquid passage because the water inlet and the liquid passage are separated from each other. . Examples of the case where the water injection port is indirectly connected to the liquid passage include a case where a water injection port 81 is provided in the outer body 70 that stores a positive electrode thin film member 30, a negative electrode thin film member 40, and an electrolyte, which will be described later. There is a case where the water injection port 81 is formed at a part where the ends of the base material 20 and the second base material 21 are not partially joined.

  FIG. 6 is a perspective view showing a configuration example in which an exterior body is provided on the water injection type battery, and FIG. 7 is a view of the water injection type battery of FIG. As shown in FIG. 6, the water injection type battery of the present invention is preferably provided with an exterior body 70 for accommodating the positive electrode thin film member 30, the negative electrode thin film member 40, and an electrolyte (not shown). Thus, the electrolyte required for the electrode reaction can be held in the battery.

  In the water injection type battery 10 (10A) of FIG. 7, the first base material 20, the second base material 21, the positive electrode thin film member 30 having the positive electrode active material layer 35 provided in the rectangular parallelepiped exterior body 70, and the negative electrode active material A negative electrode thin film member 40 also serving as a material layer is accommodated. The shape of the exterior body 70 is not particularly limited, and may be a box shape or a bag shape provided with an electrolyte solution inlet. In FIG. 6, the entire upper surface of the water injection type battery 10 </ b> A is a water injection port 81, but it is preferable that the water injection port 81 be provided with a lid (not shown) in order to suppress leakage of the electrolytic solution.

  It is preferable that the outer package 70 is liquid-impermeable in order to reliably hold the electrolytic solution. For this reason, for the exterior body 70, for example, PEN, PET, PI, or the like can be used. Thereby, a highly flexible water injection type battery can be obtained.

  FIG. 8 is a perspective view showing an example of a configuration in which an electrolytic solution accommodating portion is formed in the water injection type battery, and FIG. 9 is a cross-sectional view of the water injection type battery of FIG. 8 in the XZ plane direction. As shown in FIGS. 8 and 9, it is preferable that the end portion of the first base member 20 and the end portion of the second base member 21 are joined to each other to form the electrolyte solution accommodating portion 80. Accordingly, it is not necessary to newly provide a member for accommodating the electrolytic solution, so that an increase in the thickness and size of the battery can be suppressed as compared with the case where the exterior body 70 is provided.

  In the water-filled battery 10A shown in FIGS. 8 and 9, the first base material 20 and the second base material 21 having substantially the same rectangular shape are arranged to face each other, and the first base material 20 and the The ends of the two base materials 21 are joined to each other, and the electrolytic solution accommodating portion 80 is formed in a bag shape. On the upper side of the first base material 20 and the second base material 21, a water injection port 81 is formed at a portion where the ends of the first base material 20 and the second base material 21 are not partially joined. The first base material 20 and the second base material 21 may be bonded to each other by a bonding means such as an adhesive, heat fusion, and ultrasonic fusion.

  Although not shown, in order to extract a current flowing between the electrodes, extraction wires are respectively connected to the positive electrode thin film member and the negative electrode thin film member. Known lead wires such as vinyl wires, enamel wires, tin-plated wires, and printed wires formed on the first base material and the second base material as in the case of the electrode thin film member can be used for the lead-out wiring. For example, when a conducting wire is used as the lead-out wiring, one end of the conducting wire can be connected to the electrode thin film member by soldering, laser welding, or the like.

  Next, a water injection battery different from the water injection battery shown in FIGS. 1 to 9 will be described with reference to FIGS. The same components as those in the first embodiment are denoted by the same reference numerals, and description thereof will be omitted.

(Embodiment 2)
FIG. 10 is a cross-sectional view of a water injection type battery according to Embodiment 2 of the present invention. The first base material 20 and the second base material 21 of the water injection type battery 10 (10B) shown in FIG. 10 are continuously formed via a bent portion 22c. Specifically, the positive electrode thin film member 30 and the negative electrode thin film member 40 are respectively formed on one main surface 22a of the base material 22, and the base material 22 is bent such that the other main surface 22b of the base material 22 is located outside. By bending at the portion 22c, the positive electrode thin film member 30 and the negative electrode thin film member 40 are arranged to face each other. Thereby, the number of members constituting the battery can be reduced as compared with the case where the first base material 20 and the second base material 21 are formed of different base materials. Properly providing the bent portion 22c on the base material 22 makes it easier to position the relative position between the positive electrode and the negative electrode.

  The bending lines 22m and 22n that guide the position of the bending portion 22c may be grooves formed by pressing a cutting edge such as a rotary blade against the base material 22, for example.

  FIGS. 11 and 12 are a developed view and a cross-sectional view, respectively, showing another example of the configuration of the water injection type battery according to Embodiment 2 of the present invention. As shown in FIG. 11, a plurality of positive electrode thin film members 30 each having a positive electrode active material layer 35 provided on one main surface 22a of a substrate 22 and a plurality of negative electrode thin film members 40 each having an insulating film layer 61 provided thereon. The bending lines 22m and 22n are provided between the adjacent positive electrode thin film member 30 and negative electrode thin film member 40. A bent portion 22c is formed by valley-folding the base material 22 at the bending line 22m so that the adjacent positive electrode thin film member 30 and negative electrode thin film member 40 are arranged to face each other. A folded portion 22d is formed by mountain folding. As a result, a water injection type battery 10 (10B) in which a plurality (three in the case of FIG. 12) of water injection type batteries as shown in FIG. 10 are stacked is obtained. By stacking a plurality of batteries in the thickness direction as described above, the battery capacity can be increased.

(Embodiment 3)
13 and 14 are a developed view and a sectional view, respectively, showing a configuration example of a water-injection type battery according to Embodiment 3 of the present invention. As shown in FIG. 13A, a plurality of positive electrode thin film members 30 each having a positive electrode active material layer 35 provided on one main surface 20a of the first base member 20 are formed, and two adjacent positive electrode thin film members 30 are formed. Bending lines 20m and 20n are provided between the two. Further, as shown in FIG. 13B, a plurality of negative electrode thin film members 40 each having an insulating film layer 61 provided on one main surface 21a of the second base member 21 are formed, and two adjacent negative electrode thin film members 40 are formed. Bending lines 21m and 21n are provided between the two. A bent portion 20c is formed by valley-folding the first base material 20 at a bending line 20m, and a bent portion 20d is formed by mountain-folding the first base material 20 at a bending line 20n. Similarly, a bent portion 21c is formed by valley-folding the second base material 21 at the bending line 21m, and a bent portion 21d is formed by mountain-folding the second base material 21 at the bending line 21n. The bent part 21d of the second base 21 is stored inside the bent part 20c of the first base 20, and the bent part 20d of the first base 20 is stored inside the bent part 21c of the second base 21. Thus, the first base material 20 and the second base material 21 are laminated. In the water-filled battery 10 (10C), at least one type of electrode thin film member may be formed on one base material, so that the process of forming the electrode thin film member can be simplified.

(Embodiment 4)
FIG. 15 is a plan view showing a configuration example of a water injection type battery according to Embodiment 4 of the present invention, and FIG. 16 is a cross-sectional view taken along line XVI-XVI of FIG. As shown in FIGS. 15 and 16, the water injection type battery 10 (10 </ b> D) of the present invention penetrates the first base material 20, the positive electrode thin film member 30, the positive electrode active material layer 35 and the separator 60 in the thickness direction. A plurality of openings 60b are formed. Therefore, the electrolyte can be injected into the battery from the one main surface 20a side of the first base material 20 through the plurality of openings 60b. The electrolytic solution injected from the one main surface 20a side of the first base material 20 passes through the opening 60b and is guided to the liquid passage 50 formed by the separator 60.

  FIGS. 15 and 16 show a configuration example in which the first base member 20, the positive electrode thin film member 30, the positive electrode active material layer 35, and the opening 60b are formed in the separator 60, but the second base member 21, the negative electrode An opening may be formed in the thin film member 40 and the separator 60.

  FIGS. 15 and 16 show an example in which a plurality of openings 60b are formed, but the number of openings may be one. For example, when one opening 60b penetrating in the thickness direction Z is formed substantially at the center of the first base 20, the positive electrode thin film member 30, the positive electrode active material layer 35, and the separator 60, FIG. As shown in FIG. 5E, an insulating layer 61 provided with an electrolyte injection port 81 near the center of the separator 60 can be suitably used.

  The water-filled battery 10 of the present invention is a sensor incorporated in bed sheets for detecting incontinence, vomiting, bleeding, etc. of a sick person or a cared person, and a living body incorporated in clothing used in water such as swimwear and wet suits. It is also suitable for supplying power to monitoring sensors for information (heart rate, body temperature, pulse, respiration rate, etc.). In addition, by combining such a monitoring sensor with a wireless sensor network, the sensor can be used as a water leak detection sensor that does not require a power source, and can also be used as an emergency power source in the event of a power failure.

(Embodiment 5)
FIG. 17 is a perspective view illustrating a method for manufacturing a water-injection cylindrical battery according to Embodiment 5 of the present invention. The present invention also includes a water injection type cylindrical battery in which the water injection type batteries 10 of Embodiments 1 to 4 are wound in a roll shape. Water-filled battery 10 is wound from one side of water-filled battery 10 described in the first to fourth embodiments to the opposite side. In more detail, as shown in FIG. 17, the water injection type battery 10 is wound from the P side to the Q side of the water injection type battery. Then, the water injection type battery 10 wound around the Q side is accommodated in a cylindrical exterior body (not shown) to manufacture the water injection type battery. As described above, since the water-filled battery 10 of the present invention has high flexibility and can be easily wound, it is suitable for processing into a general cylindrical battery.

2. Method for Producing a Water-Injection Battery The method for producing a water-injection battery according to the present invention comprises: (1) forming a positive electrode thin film member on one principal surface of a flexible first base material; Forming a positive electrode active material layer on at least one of the substrate and the positive electrode thin film member; and (3) forming a negative electrode thin film member on one main surface of the flexible second base material And (4) forming a liquid passage between the positive electrode thin film member and the negative electrode thin film member by disposing the positive electrode thin film member and the negative electrode thin film member so as to face each other.

  Hereinafter, a preferred example of the method of manufacturing the water-injection type battery according to the embodiment of the present invention will be described with reference to FIGS.

(1) Step of Forming Positive Electrode Thin Film Member on One Main Surface of Flexible First Base Material First, as shown in FIG. The base material 20 is prepared, and the positive electrode thin film member 30 is formed on one main surface 20a of the first base material 20.

  The positive electrode thin film member 30 is preferably formed by a sputtering method or a coating method. If these methods are used, the thickness of the positive electrode thin film member 30 can be reduced, so that the flexibility of the battery can be further improved. In particular, when the laminate on the first substrate 20 is formed by a roll-to-roll method, a screen printing method, a gravure coater method, a die coating method, or a spray method, which is a coating method, can be used. For example, if the sputtering method is used, the thickness of the positive electrode thin film member 30 can be suppressed to several hundred nm or less, and if the screen printing method is used, the thickness of the positive electrode thin film member 30 can be suppressed to several tens μm or less.

(2) Step of forming a positive electrode active material layer on at least one of the first base material and the positive electrode thin film member Next, the positive electrode active material layer is formed on at least one of the first base material 20 and the positive electrode thin film member 30. A material layer 35 is formed. That is, the positive electrode active material layer 35 may be formed only on the first base material 20, may be formed only on the positive electrode thin film member 30, or may be formed on the first base material 20 as shown in FIG. It may be formed on both of the electrode thin film members 30. The formation of the positive electrode active material layer 35 on the first base material 20 or the positive electrode thin film member 30 can be performed by vapor deposition of the positive electrode active material or bonding with an adhesive.

(3) Step of Forming Negative Electrode Thin Film Member on One Main Surface of Flexible Second Base Material As shown in FIG. 20, a flexible second base material 21 is prepared, and the second base material is prepared. The negative electrode thin film member 40 is formed on one main surface 21 a of the first electrode 21. Similar to the method of forming the positive electrode thin film member 30, the negative electrode thin film member 40 is preferably formed by a sputtering method or a coating method. If these methods are used, the thickness of the negative electrode thin film member 40 can be reduced, so that the flexibility of the battery can be further improved. In particular, when the laminate on the second substrate 21 is formed by a roll-to-roll method, a screen printing method, a gravure coater method, a die coating method, or a spray method, which is a coating method, can be used. For example, if the sputtering method is used, the film thickness of the negative electrode thin film member 40 can be suppressed to several hundred nm or less, and if the screen printing method is used, the film thickness of the negative electrode thin film member 40 can be suppressed to several tens μm or less.

  It is more preferable to use a sputtering method or a coating method for forming the positive electrode thin film member 30 and the negative electrode thin film member 40. If the sputtering method or the coating method is used, both the thickness of the positive electrode thin film member 30 and the thickness of the negative electrode thin film member 40 can be reduced, so that the flexibility of the battery can be further improved.

  The negative electrode thin film member 40 is preferably made of a material containing a negative electrode active material. Since such a negative electrode thin film member 40 can not only function as a current collector but also serve as a negative electrode active material layer, there is no need to provide a negative electrode active material layer separately from the negative electrode thin film member 40.

  On the other hand, a negative electrode active material layer may be formed on at least one of the second base member 21 and the negative electrode thin film member 40. That is, the negative electrode active material layer may be formed only on the second substrate 21, may be formed only on the negative electrode thin film member 40, or may be formed on both the second substrate 21 and the negative electrode thin film member 40. It may be formed. The negative electrode active material layer can be formed by vapor deposition of the negative electrode active material or adhesion by an adhesive.

(4) Step of Forming a Liquid Channel Between the Positive Electrode Thin Film Member and the Negative Electrode Thin Film Member by Placing the Positive Electrode Thin Film Member and the Negative Electrode Thin Film Member Face to Face As shown in FIG. The liquid passage 50 is formed between the positive electrode thin film member 30 and the negative electrode thin film member 40 by disposing the and the negative electrode thin film member 40 to face each other. In FIG. 21, one main surface 30a of the positive electrode thin film member 30 on which the positive electrode active material layer 35 is formed and one main surface 40a of the negative electrode thin film member 40 are arranged to face each other.

  In the above step (4), when the positive electrode thin film member 30 and the negative electrode thin film member 40 are arranged to face each other, a separator 60 for preventing short circuit is provided between the positive electrode thin film member 30 and the negative electrode thin film member 40. Can be.

  The separator 60 is preferably an insulating film layer 61 formed on at least one main surface of the positive electrode thin film member 30 and the negative electrode thin film member 40. For forming the insulating film layer 61, a printing method or a photolithography method can be suitably used. According to the printing method or the photolithography method, even a complicated drawing pattern can be formed. The formation of the insulating film layer 61 on the positive electrode thin film member 30 is performed after the step (2). Further, the formation of the insulating film layer 61 on the negative electrode thin film member 40 is performed after the above step (3).

  Although not shown, the method for manufacturing a water-injected battery according to the present invention includes: (5) forming a mask layer on one of the first base material 20 and the second base material 21 and bringing the mask layer into contact with an etching solution; An opening is formed in the first substrate 20, the positive electrode thin film member 30, the positive electrode active material layer 35, and the separator 60, or the second substrate 21, the negative electrode thin film member 40, and the separator 60 by removing a part of the region. Preferably, a step is included. The opening thus formed serves as a liquid passage 50 through which the electrolytic solution passes. When the electrolytic solution is supplied from the side surface on which the opening is formed, the electrolytic solution easily spreads to the entire electrode thin film member through the liquid passage 50.

  An example of a method for forming a mask layer will be described. A known photosensitive resin (resist) such as a dry film resist or a liquid resist is applied on the first base material 20 or the second base material 21 and irradiated with an electron beam or light (ultraviolet light) from above the resist. Draw a pattern. The resist is exposed using an exposure device, and a pattern is transferred and printed on the resist. Then, a mask layer is formed on the first base material 20 and the second base material 21 by bringing the developer into contact with the resist.

  By contacting the etchant with the first base material 20 on which the mask layer is formed, a part of the first base material 20, the positive electrode thin film member 30, the positive electrode active material layer 35, and a part of the separator 60 are removed. On the other hand, when the mask layer is formed on the second substrate 21, a part of the second substrate 21, the negative electrode thin film member 40, and a part of the separator 60 are removed by the contact of the etching solution.

10, 10A, 10B, 10C, 10D: Injection type battery 20: First base material 21: Second base material 30: Positive electrode thin film member 35: Positive electrode active material layer 40: Negative electrode thin film member 50: Liquid passage 60: Separator 70: Outer body 80: Electrolyte container

Claims (4)

A first base material having flexibility;
A positive electrode thin film member formed on one main surface of the first base material;
A second substrate having flexibility;
A negative electrode thin film member formed on one main surface of the second base material,
The positive electrode thin film member and the negative electrode thin film member are arranged to face each other, and a liquid passage is formed between the positive electrode thin film member and the negative electrode thin film member,
A separator is provided between the positive electrode thin film member and the negative electrode thin film member,
The separator is an insulating film layer formed on at least one main surface of the positive electrode thin film member and the negative electrode thin film member,
A water injection type battery in which a pattern is formed on the insulating film layer. A first base material having flexibility;
A positive electrode thin film member formed on one main surface of the first base material;
A second substrate having flexibility;
A negative electrode thin film member formed on one main surface of the second base material,
The positive electrode thin film member and the negative electrode thin film member are arranged to face each other, and a liquid passage is formed between the positive electrode thin film member and the negative electrode thin film member,
A water-filled battery in which an end of the first base and an end of the second base are joined to each other to form an electrolyte container. A first base material having flexibility;
A positive electrode thin film member formed on one main surface of the first base material;
A second substrate having flexibility;
A negative electrode thin film member formed on one main surface of the second base material,
The positive electrode thin film member and the negative electrode thin film member are arranged to face each other, and a liquid passage is formed between the positive electrode thin film member and the negative electrode thin film member,
A water injection type battery in which the first base material and the second base material are continuously formed via a bent portion. A first base material having flexibility;
A positive electrode thin film member formed on one main surface of the first base material;
A second substrate having flexibility;
A negative electrode thin film member formed on one main surface of the second base material,
A water injection battery in which the positive electrode thin film member and the negative electrode thin film member are arranged to face each other, and a liquid passage is formed between the positive electrode thin film member and the negative electrode thin film member,
A water injection type cylindrical battery in which the water injection type battery is wound in a roll shape.