Battery manufacturing method

Abstract

To solve such a problem that an easy manufacturing method is required since manufacturing defects are likely to occur in a secondary battery.SOLUTION: A method of manufacturing a battery includes: vapor-depositing graphite on a collector electrode 208 to form a coating material 302; then applying a positive electrode material 221 on a positive electrode coating material 302a, the positive electrode material being obtained by mixing activated carbon and a metal oxide in an electrolyte 222 to be formed in a paste and applying a negative electrode material 231 on a negative electrode coating material 302b; and arranging a separator 204 between the positive electrode material 221 and the negative electrode material 231, and sealing with a gasket 207 to fill the electrolyte 222 between the separator 204 and the positive electrode material 221 and between the separator 204 and the negative electrode material 231.SELECTED DRAWING: Figure 2

Description

Technical Field

[0001] The present invention relates to a manufacturing method of a capacitor battery and a secondary battery.

Background Art

[0002] As a lithium-ion secondary battery, a manganese lithium secondary battery (ML type) that uses a manganese composite oxide for the positive electrode and a lithium-aluminum alloy for the negative electrode has become popular. Patent Document 1 discloses a lithium-ion secondary battery having characteristics such as a positive electrode material for a lithium-ion secondary battery.

Prior Art Documents

Patent Documents

[0003]

Patent Document 1

Summary of the Invention

Problems to be Solved by the Invention

[0004] Lithium-ion secondary batteries and sodium-ion secondary batteries have a risk of ignition because they use an organic electrolyte in the electrolyte. In addition, lithium-ion secondary batteries have a risk of heat generation and ignition due to lithium. Also, manufacturing defects are likely to occur in the battery manufacturing process.

Means for Solving the Problems

[0005] A coating material 302 is formed on the current collector 208 by vapor-depositing graphite or coating graphite or the like. Next, a positive electrode material 221, which is a paste obtained by mixing activated carbon and a metal oxide in an electrolytic solution 222, is applied to a positive electrode coating material 302a, and a negative electrode material 231 is applied to a negative electrode coating material 302b. A separator 204 is disposed between the positive electrode material 221 and the negative electrode material 231, sealed with a gasket 207, and the electrolytic solution 222 is filled between the separator 204, the positive electrode material 221, and the negative electrode material 231.

Effects of the Invention

[0006] By using an aqueous electrolyte (perchlorate aqueous solution) in a capacitor battery, the battery's conductivity is enhanced while eliminating the risk of fire and simplifying manufacturing. Furthermore, since the positive electrode material 221 and negative electrode material 231 can be manufactured by forming them into a paste and applying it, the capacity can be maximized while reducing costs. [Brief explanation of the drawing]

[0007] [Figure 1] This is an explanatory diagram of a capacitor battery and a secondary battery manufactured by the manufacturing method of the present invention. [Figure 2] This is an explanatory diagram of the manufacturing method for the capacitor battery and secondary battery of the present invention. [Figure 3] This is an explanatory diagram of the manufacturing method for the capacitor battery and secondary battery of the present invention. [Figure 4] This is an explanatory diagram of a capacitor battery and a secondary battery manufactured by the manufacturing method of the present invention. [Figure 5] This is an explanatory diagram of a capacitor battery and a secondary battery manufactured by the manufacturing method of the present invention. [Figure 6] This is an explanatory diagram of the manufacturing method for the capacitor battery and secondary battery of the present invention. [Figure 7] This is an explanatory diagram of a capacitor battery and a secondary battery manufactured by the manufacturing method of the present invention. [Figure 8] This is an explanatory diagram of a capacitor battery and a secondary battery manufactured by the manufacturing method of the present invention. [Figure 9] This is an explanatory diagram of the manufacturing method for the capacitor battery and secondary battery of the present invention. [Figure 10] This is an explanatory diagram of a capacitor battery and a secondary battery manufactured by the manufacturing method of the present invention. [Figure 11] This is an explanatory diagram of a capacitor battery and a secondary battery manufactured by the manufacturing method of the present invention. [Figure 12] This is an explanatory diagram of a capacitor battery and a secondary battery manufactured by the manufacturing method of the present invention. [Figure 13] This is an explanatory diagram of a capacitor battery and a secondary battery manufactured by the manufacturing method of the present invention. [Figure 14] It is an explanatory drawing of a capacitor battery and a secondary battery manufactured by the manufacturing method of the present invention.

Embodiments for Carrying Out the Invention

[0008] Hereinafter, the manufacturing method of the capacitor and the secondary battery of the present invention will be described with reference to the drawings.

[0009] In each drawing for explaining the embodiments for carrying out the invention, elements having the same function are denoted by the same reference numerals, and the description may be omitted. In addition, the embodiments of the present invention described in this specification can be combined in part or in whole with each of the embodiments. In each drawing for explaining the embodiments for carrying out the invention, for the purpose of facilitating understanding and explanation, and for facilitating illustration, there may be cases of magnification, reduction, or omission.

[0010] Note that in the description or illustration of the embodiments of the present invention, the positive electrode and the negative electrode may be described or illustrated as concepts of a container or an electrode. In addition, there may be cases of describing as concepts of the electrode material to be used. In addition, there may be cases of describing as concepts including a container and an electrode material.

[0011] FIG. 1 is a structural, compositional, and explanatory drawing of the capacitor battery and the secondary battery of the present invention. The drawings and the like of the present application are schematically illustrated with the thickness, size, etc. enlarged or reduced for the purpose of facilitating explanation and understanding.

[0012] The capacitor battery and the secondary battery of the present invention use, as the electrolytic solution of the battery, an aqueous solution of any one of lithium perchlorate (LiClO4), sodium perchlorate (NaClO4), barium perchlorate (Ba(ClO4)2), magnesium perchlorate (Mg(ClO4)2), ammonium perchlorate (NH4ClO4), potassium perchlorate (KClO4), silver perchlorate (AgClO4), or an aqueous solution obtained by mixing these aqueous solutions. In particular, it is preferable to use lithium perchlorate (LiClO4) and sodium perchlorate (NaClO4). Each aqueous perchloric acid solution is preferably a saturated aqueous perchloric acid solution of 90% or more. More preferably, it is a saturated aqueous perchloric acid solution of 98% or more.

[0013] The separator 204 is filled, permeated, and impregnated with the electrolytic solution 222. The separator 204 is installed between the positive electrode and the negative electrode, permeates the aqueous perchloric acid solution, and prevents contact between the positive electrode and the negative electrode. The separator 204 is made of or formed from a material having a porous structure.

[0014] Examples of the porous structure of the separator 204 include a porous membrane having a shape with pores opened in a resin film, and non-woven fabric, etc. From the viewpoints of chemical stability and electrochemical stability, polyolefins such as polyethylene (PE) and polypropylene (PP), aromatic polyamides, and fluororesins are preferable. In particular, for the base material of the separator 204, a polyolefin (softening point 130 °C) containing polyethylene that softens at a lower temperature and exhibits a shutdown function is preferable.

[0015] To ensure mechanical strength, polyolefins with a molecular weight of several hundred thousand or more are used. When the thickness of the separator 204 becomes as thin as 10 μm or less, those with a molecular weight exceeding 1 million are also blended.

[0016] It is preferable to coat the separator 204 with a fluorine-based compound. In each figure, for the purpose of facilitating understanding, etc., the periphery of the separator 204 is illustrated as being filled with the electrolytic solution 222, but it is not limited thereto. The separator 204 may be attached to the positive electrode material 221 and the negative electrode material 231. Also, the positive electrode material 221 and the negative electrode material 231 may be arranged so as to contact the separator 204.

[0017] The negative electrode material 231 is formed or composed of a material in which an oxide such as iron oxide is mixed with activated carbon, graphite, etc. Examples of the oxide include iron oxide (Fe2O3), triiron tetroxide (Fe3O4), vanadium pentoxide (V2O5), and vanadium trioxide (V2O3). In particular, as the oxide, iron oxide (Fe2O3) is inexpensive and preferable.

[0018] Oxides such as iron oxide, activated carbon, graphite, etc., are mixed with the charging solution 222 to form a paste, which is then applied to the collecting electrode 208, printed, or otherwise used to form the negative electrode 206. The same procedure is followed for the positive electrode 205.

[0019] In the process of mixing oxides such as iron oxide with activated carbon, graphite, etc., with the charge solution 222 to be used, beads or cylindrical rods made of inorganic materials such as glass or resin are mixed with the negative electrode material 231 and positive electrode material 221. Alternatively, after coating the negative electrode material 231 and positive electrode material 221, beads or cylindrical rods are scattered on the coated area.

[0020] Beads or cylindrical lots define the film thickness of the electrode collector 208, the positive electrode material 221, and the negative electrode material 231. In other words, the film thickness of the positive electrode material 221 and the negative electrode material 231 is uniform or defined by the diameter of the beads or lot. They also serve to support the separator 204 and prevent the positive electrode material 221 and the negative electrode material 231 from coming into contact. Alternatively, instead of beads or cylindrical or other types of rods, fine pillars that define the film thickness may be formed.

[0021] The positive electrode is composed of a positive electrode material 221 located on the inner surface of the positive electrode 205 and connected to it, while the negative electrode is positioned facing the positive electrode material 221. A separator 204 is placed between the positive electrode and the negative electrode.

[0022] In one embodiment, the positive electrode material 221 is a material containing cobalt. For example, a mixture of graphite and lithium cobalt oxide (LiCoO2) may be used. Furthermore, the ratio of the material mixed with graphite is preferably in the range of 1:0.8 to 1:1.5.

[0023] Examples of materials include mixtures of graphite and cobalt (LiCoO2), mixtures of graphite and manganese (LiMn2O4), mixtures of graphite and nickel (LiNiO2), mixtures of graphite and iron phosphate (LiFePO4), mixtures of graphite and manganese dioxide (MnO2), and mixtures of graphite and iron oxide (Fe2O, Fe2O3).

[0024] In the above embodiments, graphite is used as an example of the mixture of positive electrode material 221 and negative electrode material 231, but activated carbon or carbon quantum dots (CQDs) may also be used. In addition to lithium cobalt oxide, lithium manganese oxide, lithium iron phosphate, and the like can be used as constituent materials for the positive electrode.

[0025] The oxidizing material and graphite, etc., are mixed with the electrolyte 222 to form a paste, which is then applied to the electrode collector 208, printed, etc., to form the negative electrode material 231. The positive electrode material 221 can be formed in the same manner. In the paste-forming process, it is preferable to degas the paste using a degasser.

[0026] A degasser is a device that removes gases from solutions and pastes. Examples include those that utilize vacuum (reduced pressure) or kinetic energy. Other degassing devices that utilize ultrasound or gas-permeable membranes are also acceptable. By removing air bubbles from liquids and pastes, the strength, properties, and surface characteristics of the product can be made uniform, leading to improved yield and quality.

[0027] Vacuum degassing devices use a vacuum pump to reduce the pressure of a solution, thereby expanding air bubbles contained within the liquid. The expanded bubbles rise to the liquid surface due to buoyancy, and over time, the liquid film on the surface breaks down, releasing the bubbles into the reduced-pressure air. Centrifugal degassing devices utilize the principle that the centrifugal force generated when a container holding a solution rotates and revolves separates liquids and gases with different densities. The positive electrode material 221 is constructed or formed using an iron complex or the like. Furthermore, it is preferable to coat at least one of the electrodes, the positive or negative electrode, with Fe2O3. Because the battery of this invention has a capacitor structure, it is sometimes called a capacitor battery or an electric double-layer capacitor battery. It is also sometimes called a secondary battery.

[0028] In one embodiment of the present invention, a capacitor battery, secondary battery, etc., is composed of graphite, an activated carbon mixture, or a graphite and activated carbon mixture as the negative electrode. As the positive electrode, graphite, a LiCoO2 (or a material that does not undergo structural change upon oxidation), or graphite and LiCoO2 are used.

[0029] A separator 204 is placed between the positive electrode material 221 and the negative electrode material 231. In one embodiment, the separator 204 is impregnated with an aqueous lithium perchlorate (LiClO4) solution. The positive electrode 205 and the negative electrode 206 are insulated by a gasket 207.

[0030] Examples of materials for gasket 207 include natural rubber, nitrile rubber, chloroprene rubber, ethylene propylene rubber, butyl rubber, silicone rubber, fluororubber, and perfluororubber. The rubber material for gasket 207 is selected according to weather resistance, chemical resistance, heat resistance, mechanical properties, gas permeability, etc.

[0031] In addition, a joint sheet (not shown) is used in combination with or on its own with gasket 207. The joint sheet is made by uniformly mixing rubber, polyamide fibers, glass fibers, expanded graphite, etc., and then pressing and rolling it with a heated roll, and then punching out a sheet with a thickness of 0.4 mm to 3.0 mm.

[0032] In one embodiment of the present invention, a capacitor battery, secondary battery, etc., has a collector electrode 208 made of a conductive material such as stainless steel (SUS), titanium, foil, film, or plate, with a positive electrode 205 and a negative electrode 206 formed on it. Needless to say, in addition to titanium foil, other metal foils and metal plates such as iron foil and silver foil can also be used.

[0033] A coating material 302 such as graphite is applied or formed on the collecting electrode 208. The positive electrode 205 and the negative electrode 206 are filled, placed, or immersed in an electrolyte solution 222.

[0034] In the embodiments shown in Figures 8, 10, 13(a), 14, etc., as one embodiment, the capacitor battery, secondary battery, etc. of the present invention has a positive electrode 205 and a negative electrode 206 formed on a single substrate or film 301. An electrolyte 222 is placed on the substrate or film 301, or the positive electrode 205 and the negative electrode 206 are immersed in the electrolyte 222.

[0035] In the embodiments shown in Figures 8, 10, 11, 12, 13, and 14, the positive electrode material 221 and the negative electrode material 231 are arranged adjacent to each other on the base film 508a and the base film 508b.

[0036] In the embodiments shown in Figures 12 and 13(b), the positive electrode material 221 is placed on the base film 508b opposite to the positive electrode material 221 of the base film 508a. The negative electrode material 231 is placed on the base film 508b opposite to the negative electrode material 231 of the base film 508a. The space between base film 508a and base film 508b is sealed with a gasket 207, and filled with an electrolyte solution 222 consisting of a perchlorate aqueous solution.

[0037] The battery of the present invention comprises a negative electrode made of a mixture of graphite and activated carbon, a positive electrode containing lithium cobalt oxide, and an aqueous lithium perchlorate solution filled between the positive and negative electrodes.

[0038] The battery of the present invention comprises a negative electrode made of a mixture of metal oxide, graphite, activated carbon, etc., a positive electrode containing graphite and lithium cobalt oxide, etc., and an aqueous lithium perchlorate solution filled between the positive and negative electrodes, wherein the content ratio of the graphite in the positive electrode to the material to be mixed is 1:0.8 to 1:1.5.

[0039] The battery of the present invention comprises a negative electrode made of a mixture of graphite and activated carbon, a positive electrode made of a low-spin iron(II) complex material, and an electrolyte filled between the positive and negative electrodes, the electrolyte being one of lithium perchlorate (LiClO4), sodium perchlorate (NaClO4), barium perchlorate (Ba(ClO4)2), or magnesium perchlorate (Mg(ClO4)2).

[0040] Low-spin iron(II) complex materials include [Fe(phen)3] 2+ [Fe(bipy)3] 2+ [Fe(terpy)3] 2+ It is preferable that it be one of the following.

[0041] Furthermore, the battery of the present invention comprises a negative electrode and a positive electrode made of a mixture of graphite and activated carbon, and an electrolyte filled between the positive electrode and the negative electrode, the electrolyte being one of lithium perchlorate (LiClO4), sodium perchlorate (NaClO4), barium perchlorate (Ba(ClO4)2), or magnesium perchlorate (Mg(ClO4)2).

[0042] Although not shown in Figure 1, the positive electrode 205 is connected to the positive terminal 202, and the negative electrode 206 is connected to the negative terminal 203. The positive electrode 205 and the negative electrode 206 are insulated from each other by a gasket 207.

[0043] Figure 1 illustrates a coin-type capacitor battery and a coin-type secondary battery as one embodiment, but the technical concept of the present invention is not limited to these. For example, it goes without saying that the shape may be cylindrical, as shown in Figure 4. Other examples include sheet shape and cubic shape.

[0044] As shown in Figure 1, in a secondary battery as an example of a capacitor battery of the present invention, a positive electrode material 221 is formed or arranged on a conductor that forms the positive electrode 205. A negative electrode material 231 is formed or arranged on a conductor that forms the negative electrode 206. A separator 204 is placed between the positive electrode material 221 and the negative electrode material 231, and the separator 204 is filled, permeated, or impregnated with an electrolyte 222. The positive electrode 205 and the negative electrode 206 are insulated from each other by a gasket 207.

[0045] The positive electrode is composed of a positive electrode material 221 located on the inner surface of the positive electrode 205 and connected to it, the negative electrode is positioned facing the positive electrode material 221, and a separator 204 is placed between the positive electrode and the negative electrode.

[0046] The positive electrode material 221 uses a material containing cobalt. For example, a mixture of graphite and lithium cobalt oxide (LiCoO2) may be used. The ratio of graphite to the material to be mixed is preferably in the range of 1:0.8 to 1:1.5.

[0047] Examples also include mixtures of materials using graphite and cobalt (LiCoO2), mixtures of materials using graphite and manganese (LiMn2O4), mixtures of materials using graphite and nickel (LiNiO2), mixtures of materials using graphite and iron phosphate (LiFePO4), and mixtures of materials using graphite and iron oxide (Fe2O, Fe2O3). Carbon quantum dots (CQDs) are also given as examples. As described above, in addition to lithium cobalt oxide, lithium manganese oxide, lithium iron phosphate, and the like can be used as the positive electrode.

[0048] The surface of the positive electrode collector electrode 208a is coated with graphite as a positive electrode coating material 302a. The coating material 302a is formed or constructed by activated carbon, graphite printing, coating, vapor deposition, coating, inkjet, or coater methods.

[0049] The surface of the negative electrode collector electrode 208b is coated with graphite as the negative electrode coating material 302b. The coating material 302b is formed or constructed by printing, coating, vapor deposition, or other methods of applying graphite. A mixture of activated carbon and a metal oxide as the positive electrode, in paste form, is applied to the positive electrode coating material 302a to form the positive electrode material 221. The positive electrode material 221 and the negative electrode material 231 are formed into a paste and applied to the electrode collector 208, printed, or otherwise used to form the negative electrode 206.

[0050] In the process of mixing the positive electrode material 221 and the negative electrode material 231 with the charging solution 222 to be used, beads or cylindrical rods made of inorganic materials such as glass or resin are mixed in. Alternatively, after coating the negative electrode material 231 and the positive electrode material 221, beads or cylindrical rods are scattered on the coated area. Examples of beads include Micropearl (trademark of Sekisui Chemical Co., Ltd.) and Hayabeads (trademark of Hayakawa Rubber Co., Ltd.).

[0051] Beads or cylindrical lots define the film thickness of the negative electrode material 231 and the positive electrode material 221. In other words, the diameter of the beads or lot ensures uniform film thickness of the negative electrode material 231 and the positive electrode material 221. They also provide support for the separator 204.

[0052] Alternatively, instead of beads or cylindrical or other types of rods, fine pillars that define the film thickness may be formed. For example, pillars of the same height as the positive electrode material 221 or negative electrode material 231 may be formed or constructed between adjacent positive electrode materials 221 or between adjacent negative electrode materials 231 in Figure 5. The pillars are preferably made of organic materials such as acrylic resin or epoxy resin. The pillars (not shown) may also be formed on the collector electrode 208.

[0053] A mixture of graphite or activated carbon and a metal oxide as the anode, in paste form, is applied to the negative electrode coating material 302b to form the negative electrode material 231. It is preferable to coat the positive electrode material 221 and the negative electrode material 231 with Fe2O3.

[0054] Any oxide can be used for the mixture, such as LiCoO2, as long as it does not undergo structural changes upon oxidation. Furthermore, it is not limited to graphite; activated carbon, graphite-based materials, coke-based materials, and other carbon materials can be used.

[0055] A paste-like mixture of graphite and an oxide material (such as LiCoO2) using cobalt may also be used. Furthermore, the ratio of graphite to the other material is preferably in the range of 1:0.8 to 1:1.5.

[0056] The materials mixed with graphite are not limited to oxidizing materials. For example, mixtures of graphite with iron phenanthroline complexes ([Fe(phen)3](ClO4)2) and mixtures of graphite with iron cyano complexes (Li4[Fe(CN)6]) are examples. The negative electrode material 231 includes graphite (LiC6), hard carbon (LiC6), and titanate (Li4Ti5O 12 Lithium titanate (LTO) is also cited as an example.

[0057] Separator 204 is impregnated with an aqueous solution of a perchlorate, such as lithium perchlorate (LiClO4). While a saturated perchlorate solution is preferable, there is no difference in performance or efficiency even with a solution close to saturation. A concentration of 95% or higher of saturation is acceptable. More preferably, a concentration of 98% or higher is acceptable.

[0058] The negative electrode 206 is inserted into the positive electrode 205 with its end wrapped in gaskets 207 at its lower end and both sides, and the negative electrode 206 is inserted into and fixed in place by the positive electrode 205. The negative electrode 206 and the positive electrode 205 are insulated from each other by the gaskets 207.

[0059] A rechargeable battery converts oxidation-reduction reactions occurring at the negative and positive electrodes into electrical energy. The role of the electrolyte is to enable the movement of electrons and ions between the negative and positive electrodes.

[0060] A saturated lithium perchlorate aqueous solution with a potential window of 3V or higher can be used as the electrolyte in lithium-ion batteries. Even if not saturated, a concentrated aqueous solution that is close to saturated can be used as the electrolyte in secondary batteries because it has a wide potential window.

[0061] To use a saturated perchlorate solution as the electrolyte for a secondary battery, the potential window of the electrolyte is inherent, so a secondary battery with an electromotive force smaller than the potential window of the electrolyte must be selected.

[0062] A solid electrolyte may be used in the separator 204. Because the solid electrolyte suppresses the movement of ions between the negative and positive electrodes, it is applied independently to each electrode, i.e., the negative and positive electrodes. Therefore, during charging, the reduction potential at the negative electrode and the oxidation potential at the positive electrode can be kept low.

[0063] Therefore, it becomes possible to use aqueous solutions with a narrow potential window as electrolytes. Saturated lithium perchlorate (LiClO4) aqueous solution has a wider potential window than other aqueous solutions (3.2V at 25°C) and is therefore preferred as an electrolyte. The solid electrolyte acts as a separator.

[0064] Because the present invention has a wide potential window, it can be used stably for a long period of time. Similarly, a saturated sodium perchlorate aqueous solution can be used as the electrolyte in sodium-ion batteries.

[0065] Saturated perchlorate solutions include lithium perchlorate (LiClO4), sodium perchlorate (NaClO4), barium perchlorate (Ba(ClO4)2), and magnesium perchlorate (Mg(ClO4)2). These saturated perchlorate solutions are used as electrolytes in secondary batteries.

[0066] In the embodiments of the present invention, a saturated perchlorate aqueous solution is used as the electrolyte, but it is not limited to saturated solutions. There is no significant difference in effect, capacity, or performance even with a perchlorate aqueous solution that is close to saturated. Therefore, it goes without saying that a perchlorate aqueous solution may be used.

[0067] Other embodiments of the present invention will be described below. Matters and content that are the same or similar to those previously described may be omitted. In addition, some or all of the embodiments described herein and in the drawings can be combined.

[0068] Figure 2 is an explanatory diagram of the method for manufacturing a capacitor battery and a secondary battery according to the present invention. As shown in Figure 2(a), a coating material 302 is formed by depositing graphite or the like as a deposition material onto the surface of a conductive electrode 208 made of a metal or the like. In Figure 2(a), the coating material 302 is shown as "deposited," but it is not limited to this. The coating material 302 may be formed by sputtering technology, coating technology, coating technology, offset printing technology, hand coater technology, or printing technology.

[0069] The positive electrode collector 208a and the negative electrode collector 208b may be made of the same material. Alternatively, the positive electrode collector 208a may be made of a stainless steel film and the negative electrode collector 208b may be made of a titanium film or the like.

[0070] The positive electrode coating material 302a and the negative electrode coating material 302b may be made of the same material. Alternatively, the positive electrode coating material 302a may be made of carbon quantum dots (CQDs), and the negative electrode coating material 302b may be made of graphite or the like.

[0071] The coating material 302 may be formed by sputtering technology, coating technology, offset printing technology, coating technology, hand coater technology, or printing technology.

[0072] The positive electrode collector 208a and the negative electrode collector 208b may be made of the same material. Alternatively, the positive electrode collector 208a may be made of a stainless steel film and the negative electrode collector 208b may be made of a titanium film or the like.

[0073] The positive electrode coating material 302a and the negative electrode coating material 302b may be made of the same material. Alternatively, the positive electrode coating material 302a may be made of carbon graphite, and the negative electrode coating material 302b may be made of activated carbon or the like.

[0074] By forming a coating material 208 such as graphite on the collecting electrode 208, and then forming a positive electrode 205 or negative electrode 206 on the coating material 208, the adhesion between the collecting electrode 208 and the positive electrode 205 or negative electrode 206 is improved, preventing peeling. In addition, the contact resistance between the collecting electrode 208 and the positive electrode 205 or negative electrode 206 is significantly reduced.

[0075] As shown in Figure 2(b), a positive electrode material 221 or a negative electrode material 231 is formed on the coating material 302. The positive electrode material 221 or negative electrode material 231 is formed into a paste by mixing graphite, activated carbon, metal oxide, and electrolyte 222. The mixing is carried out by heating to 50°C or higher. The viscosity of the paste is made to be between 5 Pa·s and 50 Pa·s.

[0076] In Figure 2(b), the coating material 302 is shown to be formed by coating technology, but it is not limited to this. For example, it may also be formed by vapor deposition technology, sputtering technology, printing technology, coating technology, etc. The oxides such as iron oxide and graphite are mixed with the charging solution 222 to form a paste, which is then applied to the collecting electrode 208, and its viscosity is increased using an oven or the like.

[0077] The positive electrode 205 is electrically connected to the positive electrode collector 208a. The positive electrode collector 208a and the positive electrode material 221 are electrically connected via the positive electrode coating material 302a.

[0078] The negative electrode 206 is electrically connected to the negative electrode collector 208b. The negative electrode collector 208b and the negative electrode material 231 are electrically connected via the negative electrode coating material 302b. In the process shown in Figure 2(b), the positive electrode material 221 or the negative electrode material 231 may be formed using the coating apparatus shown in Figure 3. Figure 3 is a configuration diagram and explanatory diagram of a coating apparatus for forming the electrode material 502 (positive electrode material 221, negative electrode material 231) of the present invention.

[0079] The carrier film 506 is transported onto the flat surface of the coating table 504. The carrier film 506 is unwound from the unwinding roller 510 and wound onto the winding roller 509.

[0080] The electrode material 502 (positive electrode material 221, negative electrode material 231) is a paste made by stirring graphite or activated carbon with metal oxide and electrolyte 222. The supply tank 503 has a degasser (not shown).

[0081] A degasser is a device that removes gas from a solution. Examples include those that utilize vacuum (reduced pressure) or kinetic energy. Other degassing devices that utilize ultrasound or gas permeable membranes are also acceptable. By removing air bubbles from a liquid, the strength, properties, and surface characteristics of the product can be made more uniform, leading to improved yield and quality.

[0082] Vacuum degassing devices use a vacuum pump to reduce the pressure of a solution, thereby expanding air bubbles contained within the liquid. The expanded bubbles rise to the liquid surface due to buoyancy, and over time, the liquid film on the surface breaks down, releasing the bubbles into the reduced-pressure air. Centrifugal degassing devices utilize the principle that the centrifugal force generated when a container holding a solution rotates and revolves separates liquids and gases with different densities.

[0083] The paste (electrode material 502 (positive electrode material 221, negative electrode material 231)) is supplied to the supply tank 503. The carrier film 506 is unwound from the unwinding roller 510 and wound onto the winding roller 509. The paste (electrode material 502a) is supplied to the carrier film 506 from the supply tank 503.

[0084] The film thickness of the paste (electrode material 502a) is adjusted by a squeegee (not shown) at the outlet of the supply tank 503. The paste (electrode material 502b) formed to a predetermined film thickness is conveyed across the surface of the coating table 504. The carrier film 506 maintains its flatness with respect to the rollers 505a and 505b and the application stand 504. The electrode material 502 is formed on the carrier film 506 by transporting the carrier film 506 (Figure 3(b)).

[0085] The print head 501 moves vertically. By lowering the print head 501, the paste (electrode material 502) is transferred to the coating material 302 of the electrode collector 208. The electrode material 502 becomes either the positive electrode material 221 or the negative electrode material 231. By transporting the carrier film 506, the electrode material 502 can be transferred to the next electrode collector 208 (Figure 3(b)). As shown in Figure 2(c), the positive electrode collector 208a, on which the positive electrode material 221 is formed, and the negative electrode collector 208b, on which the negative electrode material 231 is formed, are arranged facing each other.

[0086] A separator 204 is placed between the positive electrode collector 208a and the negative electrode collector 208b. Alternatively, the separator 204 is attached to the positive electrode material 221 or the negative electrode material 231. Alternatively, the separator 204 is placed in contact with the positive electrode material 221 or the negative electrode material 231. As shown in Figure 2(d), the positive electrode collector 208a and the negative electrode collector 208b are sealed around the periphery with a gasket 207.

[0087] As shown in Figure 2(e), the electrolyte 222 is injected through the inlet / outlet hole 305, as illustrated in Figure 13. Alternatively, the separator 204, etc., may be permeated into the electrolyte 222 before or at the same time as the gasket 207 is installed.

[0088] While the embodiments in Figures 1 and 2 illustrate the configuration or manufacturing method of a planar capacitor battery or secondary battery, the present invention is not limited thereto. It goes without saying that the battery may also be cylindrical, as shown in Figure 4. Other examples include film-shaped, box-shaped, and curved-shaped batteries.

[0089] As shown in Figure 4, the capacitor battery (secondary battery) of the present invention consists of a container 107 comprising a positive electrode material 221, a negative electrode material 231, and a separator 204. In addition, an insulating film 108 is placed between the positive electrode material 221, the negative electrode material 231, and the separator 204 as needed. The space between the separator 204, the positive electrode material 221, and the negative electrode material 231 is filled with electrolyte 222, and the positive electrode material 221 and the negative electrode material 231 are also filled with electrolyte 222.

[0090] The electrolyte 222 in container 107 is sealed with gasket 207. The positive electrode 205 is electrically connected to the positive electrode material 221, and the negative electrode 206 is electrically connected to the negative electrode material 231. In the transfer apparatus shown in Figure 3, if the print head 501 is made roller-shaped and the collector electrode 208 is also made roller-shaped, a cylindrical battery as shown in Figure 4 can be manufactured.

[0091] The embodiment shown in Figure 1 was an embodiment in which the positive electrode material 221 and the negative electrode material 231 were formed in a planar shape. The present invention is not limited thereto. For example, as shown in Figure 5, the positive electrode material 221 and the negative electrode material 231 may be formed in a striped, rectangular, or dotted shape.

[0092] Figure 5 shows a configuration diagram and explanatory diagram of a capacitor battery and a secondary battery in another embodiment. In Figure 5, a striped or dotted positive electrode material 221 is formed on the positive electrode coating material 302a. A striped or dotted negative electrode material 231 is formed on the negative electrode coating material 302b.

[0093] During battery manufacturing, the separator 204 becomes charged due to peeling during unwinding of the separator film and friction during roll transport. When the charged film approaches the roller, it discharges, causing pinholes (small holes) in the film. In addition, foreign matter contamination during manufacturing, or metal leaching from the electrode material, can cause deposits (metal deposition), which can also cause holes in the separator 204. When holes occur in the separator 204, the positive electrode material 221 and the negative electrode material 231 come into contact. This contact causes an electrical short circuit, resulting in a defect.

[0094] In the embodiment of the present invention shown in Figure 5, the negative electrode material 231 is not positioned opposite the positive electrode material 221. Therefore, even if a hole occurs in the separator 204, the positive electrode material 221 and the negative electrode material 231 will not come into contact. Furthermore, even if the negative electrode 206 and the positive electrode 205 are pressed together and the collector electrode 208 is distorted, the positive electrode material 221 and the negative electrode material 231 will not come into contact. Therefore, the battery of the present invention will not experience short-circuit failures between the positive electrode material 221 and the negative electrode material 231.

[0095] In the embodiment shown in Figure 5, the positive electrode material 221 and the negative electrode material 231 are shown as convex, but the present invention is not limited to this. As shown in Figure 7, the positive electrode material 221 and the negative electrode material 231 may be triangular in shape. Furthermore, the positive electrode material 221 and the negative electrode material 231 are not limited to a triangular shape, and it goes without saying that they may be other shapes such as sawtooth or sinusoidal. They may also be striped or dotted in these shapes.

[0096] Figure 11 shows a configuration in which the batteries in the configuration of Figure 8 are placed facing each other. A separator 204 is placed between the base film 508a and the base film 508b. The space between the base film 508a and the base film 508b is filled with electrolyte 222 and sealed with a gasket 207 to prevent leakage of the electrolyte 222.

[0097] In Figure 11(a), the negative electrode material 231 is positioned opposite the positive electrode material 221. The present invention is not limited thereto. As shown in Figure 11(b), the positive electrode material 221 may be positioned opposite the positive electrode material 221, and the negative electrode material 231 may be positioned opposite the negative electrode material 231.

[0098] As shown in Figures 11(b) and 12, when the positive electrode material 221 is in a opposing position to the negative electrode material 221, even if there are holes or other defects in the separator 204, an electrical short circuit will not occur even if they come into contact because they are electrically the same polarity. Similarly, when the negative electrode material 231 is in a opposing position to the negative electrode material 231, even if there are holes or other defects in the separator 204, an electrical short circuit will not occur even if they come into contact because they are electrically the same polarity. In this configuration, a battery or the like can be constructed even without the separator 204. Furthermore, as illustrated in Figure 12, it goes without saying that the structure in Figure 11 can be constructed by stacking multiple layers. As shown in Figure 8, an example is provided in which the negative electrode material 231 and the positive electrode material 221 are formed on a single base film 508.

[0099] Positive electrode collectors 208a and negative electrode collectors 208b are arranged alternately on the base film 508. A positive electrode coating material 302a is formed on the positive electrode collector 208a, and a negative electrode coating material 302b is formed on the negative electrode collector 208b.

[0100] A positive electrode material 221 is formed on the positive electrode coating material 302a using the apparatus shown in Figures 3 and 6. A negative electrode material 231 is formed on the negative electrode coating material 302b. The area around the positive electrode material 221 and the negative electrode material 231 is filled with electrolyte 222, and the electrolyte 222 is sealed with a cap-shaped gasket. The positive electrode collector 208a is electrically connected to the positive electrode 205. The negative electrode collector 208b is electrically connected to the negative electrode 206.

[0101] Figure 9 shows an embodiment in which a positive electrode collector 208a and a negative electrode collector 208b are formed on the base film 508 in Figure 8. The base film 508 in Figure 9 is the same as the base film 508 in Figure 8, etc.

[0102] The positive electrode collector 208a and the negative electrode collector 208b are formed as a single collector 208 and separated into positive electrode collector 208a and negative electrode collector 208b by forming grooves 512. The grooves 512 are formed by a YAG laser, a CO2 laser, or by etching techniques such as sandblasting or chemical etching. The end of the positive electrode collector 208a becomes the positive terminal 202 and is electrically connected. The end of the negative electrode collector 208b becomes the negative terminal 203 and is electrically connected. In the batteries shown in Figures 5, 7, and 8, the positive electrode material 221 and the negative electrode material 231 are formed in a dot or stripe pattern. Figure 6 is a configuration diagram and explanatory diagram of a coating apparatus for forming the electrode material 502 (positive electrode material 221, negative electrode material 231) of the present invention into a dot pattern or stripe pattern.

[0103] As shown in Figure 6(a), the carrier film 506 is transported onto the flat surface of the coating table 504. The carrier film 506 is unwound from the unwinding roller 510 and wound onto the winding roller 509. The carrier film 506 is unwound from the unwinding roller 510 and wound onto the take-up roller 509.

[0104] The electrode material 502 is made into a paste by stirring graphite or activated carbon, metal oxide, and electrolyte 222. The paste (electrode material 502) is supplied to the supply tank 503. The carrier film 506 is unwound from the unwinding roller 510 and wound onto the winding roller 509. The paste (electrode material 502a) is supplied to the carrier film 506 from the supply tank 503.

[0105] The thickness of the paste (electrode material 502a) is adjusted using a squeegee (not shown) at the outlet of the supply tank 503 to match the thickness of the positive electrode material 221 and the negative electrode material 231. The paste (electrode material 502b), formed to a predetermined thickness using the squeegee (not shown), is conveyed across the surface of the coating table 504. The print head 501 has protrusions 507 formed on it that correspond to the position, size, and shape of the positive electrode material 221 and the negative electrode material 231.

[0106] The print head 501 moves vertically. By lowering the print head 501, the electrode material 502b (positive electrode material 221 or negative electrode material 231) is transferred to the protrusion 507 (Figure 6(b)). The remaining electrode material 502b is peeled off by the peeling blade 511. The peeled electrode material 502b is mixed again with the electrolyte 222 and used as electrode material 502a.

[0107] Next, as shown in Figure 6(c), the electrode material 502 (positive electrode material 221 or negative electrode material 231) is transferred by pressing the print head 501 onto the coating material 302 on the electrode collector 208, thereby transferring the electrode material 502. The electrode material 502 becomes either the positive electrode material 221 or the negative electrode material 231. By transporting the carrier film 506, the electrode material 502 can be transferred to the next electrode collector 208.

[0108] A coating material 302 is formed on the collector electrode 208. A laser beam or the like is irradiated onto the collector electrode 208 and the coating material 302 to form grooves 512, separating them into a positive electrode collector electrode 208a and a negative electrode collector electrode 208b. A positive electrode material 221 is formed on the positive electrode collector electrode 208a by transfer or the like, and a negative electrode material 231 is formed on the negative electrode collector electrode 208b by transfer or the like.

[0109] Figure 10 shows a configuration in which a positive electrode material 221 and a negative electrode material 231 are formed adjacent to each other on a base film 508. A step t is formed on the base film 508. The step t may be formed on the base film 508 using resin or the like, or it may be formed by cutting the base film 508 into grooves or dots.

[0110] In the embodiment shown in Figure 10, the positive electrode material 221 is formed on the convex portion and the negative electrode material 231 is formed on the concave portion. However, the positions of the positive electrode material 221 and the negative electrode material 231 may be reversed. For example, the negative electrode material 231 may be formed on the convex portion and the positive electrode material 221 may be formed on the concave portion.

[0111] The step height t is determined by the film thickness of the positive electrode material 221 and the negative electrode material 231. If the film thickness of the positive electrode material 221 + positive electrode collector 208a + positive electrode coating material 302a, or the negative electrode material 231 + negative electrode collector 208b + negative electrode coating material 302b is a, then the layers are formed such that t > a, and more preferably, 2t > a.

[0112] In Figure 10, a positive electrode material 221, a negative electrode material 231, etc., are formed on a base film 508 which has recesses, protrusions, or uneven surfaces, and an electrolyte 222 is filled between the base film 508 and the gasket 207. The positive electrode material 221, the negative electrode material 231, and the electrolyte 222 constitute a capacitor battery or the like. In the configurations of Figures 5, 7, 8, and 10, the separator 204 can be omitted.

[0113] In the battery manufacturing method of the present invention, the positive electrode material 221 and the negative electrode material 231 are formed by printing technology, inkjet technology, vapor deposition technology, coater technology, sputtering technology, coating technology, etc.

[0114] Figure 13(a) shows that the base film 508b has filling holes (inlet / outlet holes) 305 for the electrolyte 222. The electrolyte can be injected through the inlet / outlet hole 305a and poured out through the inlet / outlet hole 305b. Therefore, the electrolyte 222 can be replaced.

[0115] The electrolyte 222 deteriorates with use. Therefore, it is preferable to replace the electrolyte 222 after a certain period of time. Furthermore, the manufacturing of the battery is made easier if the electrolyte is injected after assembling the base film 508a and base film 508b with the gasket 207.

[0116] The inlet / outlet holes 305 may be formed or arranged in both the base film 508a and the base film 508b. Alternatively, inlet / outlet holes (not shown) for the electrolyte 222 may be formed in the gasket 207, container 107, etc., and the electrolyte 222 may be injected and poured out through these inlet / outlet holes (not shown). Alternatively, the electrolyte 222 may be continuously or intermittently injected through the inlet / outlet hole 305a and poured out through the inlet / outlet hole 305b, thereby circulating the electrolyte 222.

[0117] In the battery of the present invention, as shown in Figure 13(b), it is preferable to arrange the positive electrode material 221 of the base film 508a and the positive electrode material 221 of the base film 508b in opposing positions, and the negative electrode material 231 of the base film 508a and the negative electrode material 231 of the base film 508b in opposing positions. This is because even if the base film 508a and the base film 508b are deformed by external pressure, etc., and the positive electrode material 221 of the base film 508a and the positive electrode material 221 of the base film 508b come into contact, and the negative electrode material 231 of the base film 508a and the negative electrode material 231 of the base film 508b come into contact, there are few problems in the operation of the battery.

[0118] The above embodiments describe an embodiment in which the positive electrode material 221 and the negative electrode material 231 are arranged in a comb-like manner. The present invention is not limited thereto. For example, as shown in Figure 14, they may be formed in a spiral or helical shape. In other words, the present invention may be any configuration or structure in which a positive electrode made of positive electrode material 221 and a negative electrode made of negative electrode material 231 are formed adjacent to one substrate or film, and an electrolyte 222 is filled between the positive electrode material 221 and the negative electrode material 231.

[0119] The capacitor battery and secondary battery of the present invention not only function as a capacitor, but also as a secondary battery, or a secondary battery-like function. When a voltage is applied, charging begins as the voltage rises. When a predetermined voltage (electromotive force) is exceeded, an oxidation-reduction reaction similar to that of a lithium-ion battery occurs. In other words, it is a new concept of energy storage device that incorporates an oxidation-reduction reaction into an electric double-layer capacitor. Therefore, it has both high-speed charging and discharging capabilities and secondary battery-like voltage generation capabilities, configurations, and structures. [Industrial applicability]

[0120] The capacitor battery of this invention enables faster charging and discharging compared to conventional secondary batteries. With its superior high-power characteristics, the capacitor battery is expected to have applications in various fields, such as energy storage for new energy sources.

[0121] Water-based capacitor batteries and secondary batteries, which use aqueous electrolytes, have high conductivity, excellent electrolyte dissociation and ion mobility, high safety due to the water solvent, non-volatility, easy moisture management, and low cost. They also offer high-speed charging and discharging capabilities. The capacitor battery and secondary battery of the present invention can overcome the limitations of water electrolysis and are expected to be used in various fields. Furthermore, since the battery manufacturing method of the present invention allows for easy and stable production, it is possible to reduce manufacturing costs and lower the price of the battery. [Explanation of symbols]

[0122] 107 Container 108 Insulating film 202 Positive terminal 203 Negative terminal 204 Separator 205 Positive electrode 206 Negative electrode 207 Gasket 208a Positive collector electrode 208b Negative collector electrode 222 Electrolyte 221 Cathode Material 231 Negative electrode materials 302a Positive electrode coating material 302b Negative electrode coating material 305 Inlet / Outlet Hole 309 Vapor deposition materials 501 Printhead 502 Electrode materials 503 Supply tank 504 Application stand 505 Laura 506 Carrier Film 507 Convex part 508 Base Film 509 Winding roller 510 unwinding roller 511 Peeling Blade 512 Groove

Claims

1. A first step involves mixing a metal oxide with at least one of activated carbon and graphite to form a paste-like mixture, A second step involves coating the negative electrode collector with the paste-like mixture, At least one of the beads and the cylindrical rod is scattered onto the mixture coated on the negative electrode collector, The third step involves placing a separator between a positive electrode collecting electrode and a negative electrode collecting electrode, each of which is formed from a material containing an iron complex, and filling the space between the positive electrode collecting electrode and the negative electrode collecting electrode with an aqueous perchlorate solution. The beads and the lot are made of an inorganic material or resin. A method for manufacturing a battery, characterized in that at least one of the beads and the lot determines the film thickness of the mixture coated on the negative electrode collector.

2. A first step of mixing a metal oxide with at least one of activated carbon and graphite and at least one of beads and cylindrical rods to form a paste-like mixture, A second step involves coating the negative electrode collector with the paste-like mixture, The third step involves placing a separator between a positive electrode collecting electrode and a negative electrode collecting electrode, each of which is formed from a material containing an iron complex, and filling the space between the positive electrode collecting electrode and the negative electrode collecting electrode with an aqueous perchlorate solution. The beads and the lot are made of an inorganic material or resin. A method for manufacturing a battery, characterized in that at least one of the beads and the lot determines the film thickness of the mixture coated on the negative electrode collector.

3. A first step involves mixing a metal oxide with at least one of activated carbon and graphite and at least one of beads and cylindrical rods to form a paste-like first mixture, and mixing graphite and an iron complex with at least one of beads and cylindrical rods to form a paste-like second mixture. A second step involves coating the negative electrode with the first mixture and coating the positive electrode with the second mixture. The third step involves placing a separator between the positive electrode and the negative electrode, and filling the space between the positive electrode and the negative electrode with a perchlorate aqueous solution. The beads and the lot are made of an inorganic material or resin. A method for manufacturing a battery, characterized in that at least one of the beads and the lot determines the film thickness of the first mixture coated on the negative electrode and the second mixture coated on the positive electrode.

4. A first step of mixing a metal oxide with at least one of activated carbon and graphite and at least one of beads and cylindrical rods to form a paste-like mixture, The paste-like mixture is applied to the carrier film. A second step involves transferring the paste-like mixture to the negative electrode collector, The third step involves placing a separator between a positive electrode collecting electrode and a negative electrode collecting electrode, each of which is formed from a material containing an iron complex, and filling the space between the positive electrode collecting electrode and the negative electrode collecting electrode with the perchlorate aqueous solution. The beads and the lot are made of an inorganic material or resin. A method for manufacturing a battery, characterized in that at least one of the beads and the lot determines the film thickness of the mixture coated on the negative electrode collector.

5. The method for manufacturing a battery according to claim 1, claim 2, claim 3, or claim 4, characterized in that the iron complex is a low-spin iron(II) complex.

6. The method for manufacturing a battery according to claim 1, claim 2, claim 3, or claim 4, characterized in that the perchlorate aqueous solution is an aqueous solution with a concentration of 95% or more of the saturated state.

7. The perchlorate aqueous solution is lithium perchlorate (LiClO 4 ), sodium perchlorate (NaClO 4 ), barium perchlorate (Ba(ClO 4 ) 2 ), magnesium perchlorate (Mg(ClO4) 2 ), ammonium perchlorate (NH 4 ClO 4 ), potassium perchlorate (KClO 4 ), silver perchlorate (AgClO 4 ), and is an aqueous solution of any one of these or an aqueous solution obtained by mixing these aqueous solutions. A method for manufacturing a battery according to claim 1 or claim 2 or claim 3 or claim 4.

8. The method for manufacturing a battery according to claim 1, claim 2, claim 3, or claim 4, characterized in that the viscosity of the paste-like mixture is 5 Pa·s or more and 50 Pa·s or less.

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