JP2003317794A - Fiber cell and its manufacturing method - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a cell significantly improved in both charging speed and discharging speed. <P>SOLUTION: The cell is composed by bundling or laminating as fabrics fibrous materials having electron conductivity applied with a cell active material on surfaces. For example, by contacting and fixing the cell active material on the fibrous materials having electron conductivity and bundling the fiber with the active material, a cell capable of high output is formed. <P>COPYRIGHT: (C)2004,JPO

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a fiber battery capable of high output, which is formed by bundling or laminating a fibrous substance having electron conductivity with a battery active material on the surface thereof, or bundling it or laminating it as a woven fabric. And a manufacturing method thereof.

[0002]

2. Description of the Related Art Japanese Patent No. 3051401 discloses a so-called three-dimensional battery in which a battery active material is formed into powder or particles. Also, a patent application has already been filed for stacked three-dimensional batteries (Japanese Patent Application No. 11-
309627). The present applicant has also applied for a patent for a three-dimensional battery in which a particulate active material is filled to form a fixed layer (Japanese Patent Application Nos. 2000-332281 and 2000-3).
32503). Further, a battery active material (Japanese Patent Application No. 2001-280847) obtained by adding a conductive filler to an active material powder and molding the resin into particles and curing the resin, or a primary material obtained by adding a conductive filler to the active material powder and curing the resin. A battery active material obtained by secondary molding of a molded body into a plate shape (Japanese Patent Application No. 2001-2
The present applicant has also applied for a patent for 80848).

[0003]

For example, the thickness of the battery active material of a conventionally known nickel hydrogen battery or nickel iron battery is about 1 mm, and diffusion of ions or electrons moving in the active material is rate-determining. Therefore, it is difficult to increase the output. Therefore, conventionally, in order to give nickel hydroxide having no electron conductivity electron conductivity, cobalt is added or porous metal is filled. Further, for example, the thickness of the battery active material of a lithium ion battery is around 100 μm, and the diffusion of lithium ions is rate-determining, so it is difficult to achieve high output. In this case, since lithium ions are extremely large compared to protons, there is no way to move lithium in a short time without shortening the moving distance.

Further, for example, the thickness of lead and lead dioxide, which are the active materials of a lead storage battery, is about 1 mm, the sulfate ion of the electrolytic solution which is also the active material is huge, and the movement of the sulfate ion is rate-determining. In this case, since lead dioxide has a low electronic conductivity, there is no way to increase the reaction speed by reducing the thickness, but if the thickness is forcibly reduced, a large voltage drop occurs when a large current is passed. Further, in a conventional battery, a conductive material such as nickel which is in contact with a battery active material and a current collector are welded together, which makes recycling difficult.

The present invention has been made in view of the above points, and in the case of a battery active material having a very small electron conductivity or a material which needs to move in order to react, the moving distance is shortened as much as possible. Since high output is possible by doing so, a thin battery active material layer is attached to the surface of a fibrous electron conductive material as a passage for electrons etc.
An object of the present invention is to provide a fiber battery capable of unprecedentedly high output and a manufacturing method thereof by forming a battery by bundling or laminating it as a woven fabric. Further, by arranging only the current collector to hold the battery-active material coated on the surface with a fibrous substance having electron conductivity or laminated as a woven fabric, the conventional welding is not necessary, An object of the present invention is to provide a fiber battery that can be easily recycled and a manufacturing method thereof.

[0006]

In order to achieve the above-mentioned object, the fiber battery of the present invention comprises a fibrous substance having electron conductivity, the surface of which is coated with a positive electrode active material, one by one or in a bundle. Of the positive electrode and the negative electrode of which the surface is made of a fibrous substance having electron conductivity and which is coated with the negative electrode active material one by one or in the form of a bundle or which is made of a woven fabric. At least one of the fibrous substances laid as the negative electrode is attached so that at least one end of the fibrous substance laid as the positive electrode is in contact with the separator, which is laminated with a separator having no electron conductivity and ionic conductivity therebetween. The negative electrode current collector is attached so that one end contacts,
It is configured by filling a battery cell with an electrolytic solution.

In the fiber battery of the present invention, the surface of a fibrous material having electron conductivity is coated with a positive electrode active material,
Further, the outer surface of the positive electrode coated with a porous substance having no electron conductivity but ion conductivity is arranged one by one or in a bundle or is a woven fabric and the surface of the fibrous substance having electron conductivity. A negative electrode which is coated with a negative electrode active material and is further coated with a porous substance having no electron conductivity but ion conductivity is arranged one by one or in a bundle or is laminated as a woven negative electrode. The positive electrode current collector is attached so that at least one end of the fibrous substance laid as the contact is attached, and the negative electrode current collector is attached so that at least one end of the fibrous substance laid as the negative electrode is attached, and the battery cell is filled with the electrolytic solution. It is characterized by being configured.

In the fiber battery of the present invention, the surface of the fibrous material having electron conductivity is coated with the positive electrode active material,
Furthermore, the outside of which is coated with a porous substance having no electron conductivity but ion conductivity is used as a warp thread for use in the positive electrode one by one or in a bundle, and the surface of the fibrous substance having electronic conductivity is used as the negative electrode active material. Wefts and wefts that are coated with a substance, and the outer side of which is coated with a porous substance that has no electronic conductivity but ion conductivity, are used individually or in a bundle for the negative electrode. And a positive electrode current collector in which the woven fabrics are laminated so that the vertical and horizontal directions thereof are the same, and at least one end of the fibrous substance of the vertical yarns that are the positive electrodes is in contact with the surface of the woven fabric substantially perpendicular to the warp direction. Is attached from both sides or one side, the negative electrode current collector is attached from both sides or one side so that at least one end of the fibrous substance of the weft yarn which is the negative electrode is in contact with the surface substantially perpendicular to the weft direction of the fabric,
It is characterized in that the battery cell is filled with an electrolytic solution. The fibrous material used as the positive electrode is a weft thread,
The fibrous material used as the negative electrode may be warp threads.

In the above structure, for example, a battery in which the positive electrode active material is nickel / nickel hydroxide and the negative electrode active material is cadmium, a battery in which the positive electrode active material is nickel / nickel hydroxide and the negative electrode active material is a hydrogen storage alloy, and a positive electrode Batteries in which the active material is nickel / nickel hydroxide and the negative electrode active material is iron / iron hydroxide,
Batteries with positive electrode active material of nickel / nickel hydroxide and negative electrode active material of zinc, batteries of positive electrode active material with lead / lead dioxide and negative electrode active material of lead, positive electrode active material with lithium / lithium compound and negative electrode active material of carbon Batteries, batteries with manganese dioxide as the positive electrode active material and lithium / lithium compound as the negative electrode active material, batteries with positive electrode as air and negative electrode active material as aluminum, batteries with positive electrode as air and negative electrode active material as magnesium, positive electrode active material as silver oxide Thus, a battery in which the negative electrode active material is zinc, a battery in which the positive electrode active material is silver oxide and the negative electrode active material is cadmium, and a battery in which the positive electrode active material is manganese dioxide and the negative electrode active material is zinc can be used.
The battery active material applicable to the present invention includes nickel, iron, zinc, lead, silver, calcium, tin, gold, lithium, aluminum, potassium, sodium, magnesium, or oxides or hydroxides thereof. , Carbides, hydrogen storage alloys, and the like.

In the above structure, for example, as fibrous substances, substances having electron conductivity such as carbon fibers and metal fibers, organic fibers having metal plated on the surface, inorganic fibers, fibrous plastics, rubber, etc. Can be used. Note that the fibrous substance having electron conductivity includes, in addition to the fibrous substance, a rod-shaped substance having a sufficiently small cross-sectional diameter, an elongated foil-shaped substance, and the like. On the surface of these fibrous, rod-shaped or foil-shaped substances, for example, 10 μm
Attach the battery active material with the following thickness.

In the above structure, for example, a resin soluble in a solvent soluble in water or alcohol is used as the porous substance having no electron conductivity but ion conductivity, and the resin dissolved in the solvent is used. It is possible to use a resin which is made porous by extracting the solvent with water or alcohol. As the resin dissolved in a water-soluble solvent, polyether sulfone (PES) resin dissolved in dimethyl sulfoxide (DMSO), polystyrene dissolved in acetone,
Polysulfone dissolved in dimethylformamide (DMF) or DMSO, polyacrylonitrile dissolved in DMF, DMSO or ethylene carbonate, DM
F, DMSO or N-methyl-2-pyrrolidone (N
Polyvinylidene fluoride dissolved in MP, polyamide dissolved in DMF or NMP, DMF or NMP
A polyimide or the like dissolved in is used. As the resin dissolved in a solvent soluble in alcohol, cellulose acetate dissolved in methylene chloride, oxide phenylene ether (PPO) dissolved in methylene chloride and the like are used.
In addition, as the porous substance having no electronic conductivity and ionic conductivity, a solid electrolyte such as NAFION (registered trademark), a polyolefin membrane film such as Teflon (registered trademark), polyethylene, polypropylene, or a non-woven fabric is used. It can be used. Further, by attaching a battery active material to a fibrous substance and further coating the outer side of the fibrous substance with a porous substance, a new cut is made to expose the cross section of the fibrous substance, and the current collector is attached to this cross section. A battery can be constructed by contacting them.

In the above structure, one cell or a plurality of basic units in which the positive electrode fibers and the negative electrode fibers are arranged side by side or laminated as a woven fabric can be used as a battery. In this case, the basic unit can be compressed and assembled into the battery cell in a compressed state. For example, the basic unit is bound with a porous or non-porous insulator or a band or string made of a meltable or non-meltable insulator to be in a consolidated state. Further, in the above structure, it is possible to fill or stack the same cell with a laminate made of a fibrous substance having a surface coated with a battery active material having different charge / discharge characteristics. It is also possible to fill or stack a large number of one fibrous substance with the surface of which a battery active material having different charge / discharge characteristics is attached, in the battery cell.

Further, in the above-mentioned structure, it is possible to obtain a high-voltage battery by stacking the single cells with the partition walls. Further, in the above structure, in addition to the case where the surface of the fibrous material is coated with the battery active material is used for both the positive electrode and the negative electrode, the surface of the fibrous material is coated with the battery active material for the positive electrode side or Instead of the fibrous material whose surface is coated with the battery active material, only the negative electrode side is used, and the other electrode side is a particulate or powdery battery active material (Japanese Patent Application No. 2001-2001).
280847) or a battery active material formed in a plate shape (Japanese Patent Application No. 2001-2804848) can be loaded to form a battery.

In the method for producing a fiber battery of the present invention, a battery active material is attached to the surface of a fibrous material having electronic conductivity, and the fibrous material coated with the positive electrode active material is used as a positive electrode.
A fibrous substance having a surface coated with a negative electrode active material is used as a negative electrode, and the fibrous substances of the positive electrode are arranged one by one or in a bundle or as a woven fabric, and there is no electron conductivity and ion-conductive separator on the fibrous substance. , And arrange the negative electrode fibrous substances one by one or in a bundle on the separator or lay them as a woven fabric, and stack the positive electrode and the negative electrode with the separator sandwiched between them, and at least one end of the positive electrode side fibrous substance. The positive electrode current collector from one side or both sides of the fibrous substance in a direction substantially perpendicular to the negative electrode side, and the negative electrode current collector from one side or both sides of the fibrous substance in a direction substantially perpendicular so that at least one end of the fibrous substance contacts. It is characterized by pressing an electric body and filling a battery cell with an electrolytic solution to complete a battery.

In the method of the present invention, a battery active material is attached to the surface of a fibrous substance having electron conductivity, and the outside is covered with a porous substance having no electron conductivity and ion conductivity. The fibrous substance coated on the surface with a positive electrode active material and further coated with a porous film is used as the positive electrode, and the fibrous substance coated on the surface with the negative electrode active material and further coated with a porous film is used as the negative electrode. The substances are arranged one by one or in a bundle or as a woven fabric, and the fibrous substance of the negative electrode is laid one by one or in a bundle or laid on the fabric as a woven fabric, and the positive and negative electrodes are alternately or randomly laminated. Then, the positive electrode current collector is pressed from one side or both sides of the substantially vertical direction of the fibrous substance so that at least one end of the fibrous substance on the positive electrode side comes into contact with the fibrous substance so that at least one end of the fibrous substance on the negative electrode side comes into contact. Stands for Pressing the negative electrode current collector from one or both sides from the straight direction, it is characterized in that to complete the cell filled with the electrolyte solution to the battery cell.

Further, in the method of the present invention, a battery active material is attached to the surface of a fibrous substance having electron conductivity, and the outside thereof is coated with a porous substance having no electron conductivity but ion conductivity. The fibrous substance coated on the surface with a positive electrode active material and further coated with a porous film is used as the positive electrode, and the fibrous substance coated on the surface with the negative electrode active material and further coated with a porous film is used as the negative electrode. A woven fabric is prepared in which the substance is used as warp yarns one by one or as a bundle, and the fibrous substance of the negative electrode as one yarn or bundle as a weft yarn, and the warp yarns and the weft yarns are used as a positive electrode and a negative electrode, respectively. And the positive electrode current collector is pressed from both sides or one side so that at least one end of the fibrous substance of the warp yarn that is the positive electrode is in contact with the surface of the fabric that is substantially perpendicular to the warp yarn direction. Filament of weft, which is the negative electrode Pressing the negative electrode current collector so that at least one end of the quality contact from both sides or one side, is characterized in that to complete the cell filled with the electrolyte solution to the battery cell.

When a fibrous substance having a surface coated with a battery active material or a fibrous substance having a surface coated with a battery active material and further coated with a porous film is used one by one or as a bundle to form a woven fabric. , Plain weave, twill weave, toncap weave, and the like. Further, when the battery active material is applied to the surface of the fibrous material, it may be carried out one by one, or may be carried out collectively. Further, as a method of attaching the battery active material (such as nickel hydroxide) to the surface of the fibrous material, electrolytic deposition method by electrolysis can be utilized. In this case, it is possible to coat the surface with a deposit having different characteristics by using electrolytic baths different in kind, concentration, pH, temperature and the like a plurality of times. Further, the current density can be changed to coat the surface with a deposit having different characteristics. Further, it is also possible to suspend the battery active material as fine particles in an electrolytic bath, and take the battery active material into the plated metal by eutectoid plating to co-deposit it.

As a method of attaching the battery active material (such as nickel hydroxide) to the surface of the fibrous material, a method of fixing with a resin can be used. For example, when nickel hydroxide is used as the active material, the resin may be a thermoplastic resin having a softening temperature of 120 ° C., a resin having a curing temperature of room temperature to 120 ° C., or a resin soluble in a solvent having an evaporation temperature of 120 ° C. or less. Can be used. When nickel hydroxide is used as the active material, its activity is lost at 130 ° C. or higher, and therefore various treatments are necessary at temperatures lower than 130 ° C. As the thermoplastic resin, polyethylene, polypropylene, ethylene vinyl acetate copolymer, etc. can be used. As the resin having a curing temperature from room temperature to 120 ° C., a reaction curable resin (epoxy resin, polyurethane resin, unsaturated polyester resin) is used. Etc.), thermosetting resins (phenolic resins, etc.), the above-mentioned thermoplastic resins, etc. can be used. As the resin soluble in a solvent having a low evaporation temperature, the above-mentioned polyethylene, polypropylene, ethylene vinyl acetate copolymer, etc. can be used, and these resins are dissolved in an organic solvent such as heated toluene or xylene to be dissolved in the solvent. After coating the above resin on the surface, the solvent may be removed by heating under reduced pressure or normal pressure.

Further, as the resin, PES dissolved in DMSO which is a resin dissolved in a water-soluble solvent, polystyrene dissolved in acetone, polysulfone dissolved in DMF or DMSO, polysulfone dissolved in DMF, DMSO or ethylene carbonate. Acrylonitrile, DM
Polyvinylidene fluoride dissolved in F, DMSO or NMP, polyamide dissolved in DMF or NMP,
Cellulose acetate dissolved in methylene chloride which is a resin dissolved in a solvent soluble in alcohol such as polyimide dissolved in DMF or NMP, P dissolved in methylene chloride
When using PO or the like, the resin dissolved in a solvent soluble in water or alcohol may be coated on the surface, and then the solvent may be extracted and removed with water or alcohol.

In order to make the resin conductive, even if a conductive material such as carbon black, carbon fiber, carbon foil, carbon whiskers, nickel metal fine particles, nickel foil, or nickel metal whiskers is added to the resin. Good. As a method of adding the conductive material to the resin, a method of mixing and dispersing the resin and the conductive material dissolved in a solvent, or a method of mixing and dispersing the solvent and the conductive material and then dissolving and mixing the resin to disperse There are ways. In the method of fixing the battery active material on the surface of the fibrous material with the resin, the amount of resin and solvent,
By changing the type, substances with different characteristics can be coated.

Further, hot dipping can be used as a method of attaching the battery active material to the surface of the fibrous material. As the method of hot dipping, fibrous materials may be continuously supplied to plate the surface thereof, or fibrous materials may be supplied in batch to plate the surface. In this case, using electrolytic baths with different composition types, concentrations, temperatures, etc. multiple times,
Precipitates with different properties can be coated on the surface.
Further, the treatment time can be changed to coat the surface with a deposit having different characteristics. Further, as a method of attaching the battery active material (hydrogen storage alloy or the like) to the surface of the fibrous material, a sintering method can be used.

[0022]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, embodiments of the present invention will be described. However, the present invention is not limited to the following embodiments, and can be appropriately modified and implemented. . 1 and 2 show an example of a fiber battery according to a first embodiment of the present invention. The present embodiment uses, as an example, an electrolytic deposition method by electrolysis,
It is a nickel-iron battery composed of carbon fiber as a base material and nickel / nickel hydroxide as a positive electrode active material and iron / iron hydroxide as a negative electrode active material. A manufacturing example of the fiber battery of the present embodiment will be described. Electrolysis is performed in a nickel nitrate bath using carbon fiber as a cathode and a nickel plate as an anode to electrolytically deposit nickel / nickel hydroxide on the surface of the carbon fiber. The carbon fiber whose surface is coated with this nickel / nickel hydroxide is used as a positive electrode. In addition, electrolysis is performed using carbon fiber as a cathode and an iron plate as an anode in an iron nitrate bath to electrolytically deposit iron / iron hydroxide on the surface of the carbon fiber. The carbon fiber whose surface is coated with this iron / iron hydroxide is used as a negative electrode.

The carbon fibers 10 having the surface coated with the positive electrode active material are arranged in a line, and the separator 12 is placed thereon.
As a Teflon (registered trademark) film is laid. At this time, the end on the positive electrode current collector side is aligned with the separator 12 in a state where the cross section of the positive electrode carbon fiber 10 is exposed, and the separator 12 is longer on the end on the negative electrode current collector side. As the separator, a woven or non-woven fabric such as Teflon (registered trademark), polyethylene, polypropylene, nylon, or a membrane film can be used. Then, the carbon fibers 14 having the surface coated with the negative electrode active material are arranged in a line on the separator 12. At this time, the end on the side of the negative electrode current collector has the cross section of the carbon fiber 14 of the negative electrode exposed and the separator 12
At the same time, the positions are aligned so that the separator 12 is longer at the end on the positive electrode current collector side. Further, a separator 12 is laid on it, and a positive electrode and a negative electrode are laminated with the separator interposed therebetween. The battery cell 16 is filled with the layered carbon fiber, and the positive electrode current collector 18 is pressed against the layered carbon fiber in a direction perpendicular to the layered carbon fiber 10 and the separator 12. With the positive electrode current collector 18 side being the bottom surface,
After injecting an electrolyte (KOH, NaOH, LiOH, etc.) solution, the carbon fiber 14 of the negative electrode and the separator 12
The battery is completed by pressing the negative electrode current collector 20 from the surface where the lines are aligned, that is, the side opposite to the positive electrode current collector 18. In addition, in FIG. 2, the illustration of the negative electrode current collector on the front side is omitted.

Next, details of charging and discharging of the battery of this embodiment will be described. (Charging) A voltage is applied to the battery, and electrons are supplied to the negative electrode current collector 20 from a power generation means (not shown). Electron is the negative electrode current collector 2
It moves from 0 to the negative electrode active material and reacts. The ions generated by the reaction pass through the separator 12 and react with the positive electrode active material to emit electrons. The electrons move to the positive electrode current collector 18 and are sent to the power generation means. Electrons are supplied to the positive electrode current collector 18 from a (discharge) load (not shown). The electrons move from the positive electrode current collector 18 to the positive electrode active material and react. The ions generated by the reaction pass through the separator 12 and react with the negative electrode active material to emit electrons. The electrons move to the negative electrode current collector 20 and are sent to the load.

In this embodiment, by forming a thin battery active material layer on the surface of a fibrous material having electron conductivity such as carbon fiber, the migration distance of electrons and ions is shortened as much as possible, and the migration distance of electrons and ions is reduced. Since the diffusion is drastically promoted as compared with the conventional battery, it is possible to obtain a battery capable of high output with significantly improved charging speed and discharging speed. Further, the carbon fiber laminated body having the surface coated with the battery active material is simply pressed down by the current collector and not welded, so that it can be easily recycled.

FIGS. 3 and 4 show an example of a fiber battery according to the second embodiment of the present invention. The present embodiment uses, as an example, an electrolytic deposition method by electrolysis,
The nickel-iron battery is formed by attaching carbon / nickel hydroxide as a positive electrode active material and iron / iron hydroxide as a negative electrode active material to carbon fiber as a base material, and further coating a porous resin on the outside thereof. A manufacturing example of the fiber battery of the present embodiment will be described. Electrolysis is performed in a nickel nitrate bath using carbon fiber as a cathode and a nickel plate as an anode to electrolytically deposit nickel / nickel hydroxide on the surface of the carbon fiber. The carbon fiber is immersed in a resin solution prepared by dissolving PES in DMSO and pulled up. This is immersed in water, DMSO is extracted with water, and PES is solidified to form a porous film. A carbon fiber whose surface is coated with this nickel / nickel hydroxide and whose outside is coated with a porous film is used as a positive electrode. In addition, carbon fiber cathode in iron nitrate bath,
Electrolysis is performed using an iron plate as an anode to electrolytically deposit iron / iron hydroxide on the surface of the carbon fiber. PES to DMS
The carbon fiber is immersed in a resin solution dissolved in O and pulled up. This is immersed in water, DMSO is extracted with water, and PES is solidified to form a porous film. A carbon fiber whose surface is coated with this iron / iron hydroxide and whose outer side is coated with a porous film is used as a negative electrode.

The carbon fiber 22 coated on the surface with a positive electrode active material and further coated with a porous film on the outer side is aligned so that one end whose exposed cross section is exposed is the positive electrode current collector side.
It arranges so that the end covered with the other porous film 24 may be the negative electrode current collector side. The carbon fiber 26 coated with the negative electrode active material on the surface and further coated with the porous film on the outer side is aligned with one end having the exposed cross section as the negative electrode current collector side, and the other end coated with the porous film 24 is Arrange them so that they are on the positive electrode current collector side. The positive electrode and the negative electrode may be arranged at random, but if they are arranged alternately, a higher performance battery is obtained. Carbon fiber 22 in which battery cells 16 are filled with layered carbon fibers and used as a positive electrode from a direction perpendicular to the layered carbon fibers (vertical direction)
The positive electrode current collector 18 is pressed against the cross section side of. Positive electrode current collector 1
After injecting the electrolytic solution in a state where the side 8 is the bottom surface, the negative electrode current collector 20 is pressed against the cross section side of the carbon fiber 26 used as the negative electrode, which is the opposite side, to complete the battery.

Next, details of charging and discharging the battery of the present embodiment will be described. (Charging) A voltage is applied to the battery, and electrons are supplied to the negative electrode current collector 20 from a power generation means (not shown). Electron is the negative electrode current collector 2
It moves from 0 to the negative electrode active material and reacts. The ions generated by the reaction pass through the porous film 24 and react with the positive electrode active material to emit electrons. The electrons move to the positive electrode current collector 18 and are sent to the power generation means. Electrons are supplied to the positive electrode current collector 18 from a (discharge) load (not shown). The electrons move from the positive electrode current collector 18 to the positive electrode active material and react. The ions generated by the reaction pass through the porous film 24 and react with the negative electrode active material to emit electrons.
The electrons move to the negative electrode current collector 20 and are sent to the load.

In the present embodiment, a battery active material is attached to the surface of a fibrous substance having electron conductivity, and the outer surface of which is coated with a porous substance having no electron conductivity but ion conductivity is alternated. It can be made to function as a battery simply by arranging in random order. Other configurations and operational effects are similar to those of the first embodiment.

5 and 6 show an example of the fiber battery according to the third embodiment of the present invention. The present embodiment uses, as an example, an electrolytic deposition method by electrolysis,
A nickel-iron battery comprising carbon fiber, which is a base material, nickel / nickel hydroxide as a positive electrode active material, iron / iron hydroxide as a negative electrode active material, and a porous resin coated on the outside thereof. The basic unit is strongly compacted and assembled into a battery cell. A manufacturing example of the fiber battery of the present embodiment will be described. The carbon fiber 22 used as the positive electrode and the carbon fiber 26 used as the negative electrode are manufactured by the same method as in the second embodiment, and are arranged alternately or randomly as in the second embodiment. These carbon fibers are bundled and, as shown in FIG. 5, tightly bound with a polypropylene band 28 and consolidated to form a basic unit. The basic unit is
A porous or non-porous insulator, or a meltable or non-meltable insulator can be bound to obtain a consolidated state,
For example, a non-woven fabric can be used as the porous insulator, the above-mentioned polypropylene or polyethylene can be used as the non-porous non-melting insulator, and polyvinyl alcohol can be used as the melting insulator.

The strongly compacted basic unit is attached to the battery cell 16
Then, the positive electrode current collector 18 is pressed against the cross section side of the carbon fiber 22 used as the positive electrode from the direction perpendicular to the bundle of carbon fibers (vertical direction). After injecting the electrolytic solution in a state where the positive electrode current collector 18 side is the bottom surface, the negative electrode current collector 20 is pressed against the cross section side of the carbon fiber 26 used as the negative electrode, which is the opposite side, to complete the battery. . Note that the polypropylene band is not shown in FIG. In this embodiment, the workability can be further improved. Other configurations and operational effects are similar to those of the first and second embodiments.

FIG. 7 shows an example of a fiber battery according to the fourth embodiment of the present invention. In the present embodiment, as an example, an electrolytic deposition method by electrolysis is used to add nickel / carbon as a positive electrode active material to a carbon fiber as a base material.
It is a nickel-iron battery in which nickel hydroxide, iron / iron hydroxide as a negative electrode active material are attached, and a porous resin is coated on the outside thereof as a woven fabric. A manufacturing example of the fiber battery of the present embodiment will be described. The carbon fiber 22 used as the positive electrode and the carbon fiber 26 used as the negative electrode are manufactured by the same method as in the second embodiment. Both ends of these carbon fibers are exposed in the cross section of the carbon fibers. The carbon fiber 22 used as the positive electrode is a warp yarn, and the carbon fiber 26 used as the negative electrode is a weft yarn. The fabric 30 is laminated. In FIG. 7, as an example, 16 layers are stacked. The laminated woven fabric 30 is loaded into the battery cell 16, and the positive electrode current collector 1 is provided on one cross-sectional side of the carbon fiber 22 used as a positive electrode from a direction perpendicular to the plane of the woven fabric 30 (vertical direction).
8 is pressed, and the positive electrode current collector 18 is also pressed on the other cross section side. The negative electrode current collector 20 is pressed against one cross-section side of the carbon fiber 26 used as the negative electrode, which is a plane perpendicular to the positive electrode current collector 18, and the other cross-section side is also covered with the negative electrode current collector 20.
Press on. After injecting the electrolytic solution, the lid 32 is closed to complete the battery. In the present embodiment, the woven fabric has four
Although the surface of the woven fabric is pressed by the current collector, it is possible to use a battery in which the woven fabric is pressed by the current collector from two or three surfaces of the woven fabric at right angles. Reference numeral 34 is an insulating member. In addition, in FIG. 7, the illustration of the negative electrode current collector on the front side is omitted. Other configurations and operational effects are similar to those of the first and second embodiments.

8 and 9 show an example of a fiber battery according to the fifth embodiment of the present invention. In this embodiment, as an example, four batteries of the first embodiment are made,
It is a high voltage battery that is stacked in series. FIG. 8 is an enlarged view of a part of the single cell. In this case, it is possible to easily increase the voltage by sharing the partition wall 36 provided between the unit cells, and by using the partition wall 36 having a large area and a small thickness, a battery having an extremely small voltage drop is obtained. be able to. Other configurations and effects are the same as those of the first embodiment.
It is similar to the case of the form.

10 and 11 show an example of a fiber battery according to the sixth embodiment of the present invention. In this embodiment, as an example, four batteries of the second embodiment are made and stacked in series to form a high voltage battery. FIG. 10 is an enlarged view of a part of the single cell. Other configurations and effects are similar to those of the first, second, and fifth embodiments.

FIG. 12 shows an example of a fiber battery according to the seventh embodiment of the present invention. In this embodiment,
As an example, 16 batteries of the fourth embodiment are made and 4 × 4 batteries are connected in series to form a high voltage battery. Reference numeral 38 denotes a connection plate, which has the same role as the partition wall.
Other configurations and operational effects are similar to those of the first, second, fourth, fifth, and sixth modes of implementation.

13 and 14 show an example of the fiber battery according to the eighth embodiment of the present invention. In this embodiment, as an example, a resin is used, nickel / nickel hydroxide as a positive electrode active material and a hydrogen storage alloy as a negative electrode active material are attached to a carbon fiber as a base material, and a porous resin is further coated on the outside thereof. It is a nickel-hydrogen battery configured as described above. A manufacturing example of the fiber battery of the present embodiment will be described. For example, 150 g of particulate graphite (acetylene black, Ketjen black) is put into a Henschel mixer with an internal volume of 10 liters, and about 3 rpm at 1000 rpm.
Stir for a minute to sufficiently disperse the particulate graphite. To this, 1000 g of nickel hydroxide powder for batteries is added and mixed at 1000 rpm for about 3 minutes. Separately, add 3 parts of ethylene vinyl acetate copolymer to 2000 g of xylene heated to 60 ° C.
Add 00 g and dissolve. A resin dissolved in heated xylene is added to the mixture of the particulate graphite and the nickel hydroxide powder heated to 60 ° C., and the mixture is stirred and dispersed with a Henschel mixer while being heated and maintained at 60 ° C. The carbon fiber is dipped in this and pulled up. Then, it is vacuum dried at 50 ° C. in a vacuum heating furnace to vaporize xylene. Next, the carbon fiber is immersed in a resin solution prepared by dissolving PES in DMSO and pulled up. This is immersed in water, DMSO is extracted with water, and PES is solidified to form a porous film. A carbon fiber whose surface is coated with this nickel / nickel hydroxide and whose outside is coated with a porous film is used as a positive electrode.

Further, for example, 150 g of particulate graphite (acetylene black, Ketjen black) was put into a Henschel mixer having an internal volume of 10 liters, and about 3 rpm at 1000 rpm.
Stir for a minute to sufficiently disperse the particulate graphite. To this, add 1000g of hydrogen storage alloy powder for battery and
Mix at 000 rpm. Separately, 30 g of ethylene vinyl acetate copolymer was added to 2000 g of xylene heated to 60 ° C.
Add 0 g and dissolve. A resin dissolved in heated xylene is added to the mixture of the particulate graphite and the hydrogen storage alloy heated to 60 ° C., and the mixture is stirred and dispersed with a Henschel mixer while being heated and maintained at 60 ° C. The carbon fiber is dipped in this and pulled up. And 5 by the vacuum heating furnace
Vacuum dry at 0 ° C. to evaporate xylene. Next, P
The carbon fiber is immersed in a resin solution prepared by dissolving ES in DMSO and pulled up. Dip this in water, D
MSO is extracted with water and PES is solidified to form a porous film. A carbon fiber whose surface is coated with this hydrogen storage alloy and whose outside is coated with a porous film is used as a negative electrode.

The carbon fiber 22 coated on the surface with a positive electrode active material and further coated with a porous film on the outer side is aligned so that one end whose exposed section is exposed is the positive electrode current collector side.
It arranges so that the end covered with the other porous film 24 may be the negative electrode current collector side. The carbon fiber 26 coated with the negative electrode active material on the surface and further coated with the porous film on the outer side is aligned with one end having the exposed cross section as the negative electrode current collector side, and the other end coated with the porous film 24 is Arrange them so that they are on the positive electrode current collector side. The positive electrode and the negative electrode may be arranged at random, but if they are arranged alternately, a higher performance battery is obtained. A carbon fiber 22 in which a layered carbon fiber is loaded in a battery cell 16 and used as a positive electrode from a direction perpendicular to the layered carbon fiber (vertical direction).
The positive electrode current collector 18 is pressed against the cross section side of. Positive electrode current collector 1
After injecting the electrolytic solution in a state where the side 8 is the bottom surface, the negative electrode current collector 20 is pressed against the cross section side of the carbon fiber 26 used as the negative electrode, which is the opposite side, to complete the battery. Other configurations and effects are similar to those of the first and second embodiments. The positive electrode and the negative electrode of the present embodiment are
Of course, it is also possible to apply to the configurations of the third, fourth, sixth and seventh embodiments.

FIGS. 15 and 16 show an example of the fiber battery according to the ninth embodiment of the present invention. In this embodiment, as an example, electrolytic deposition by electrolysis is used to attach nickel / nickel hydroxide as a positive electrode active material and iron / iron hydroxide as a negative electrode active material to nickel fiber as a base material. Nickel-iron battery. A manufacturing example of the fiber battery of the present embodiment will be described. Electrolysis is performed in a nickel nitrate bath using nickel fiber as a cathode and nickel plate as an anode to electrolytically deposit nickel / nickel hydroxide on the surface of the nickel fiber. The nickel fiber whose surface is coated with this nickel / nickel hydroxide is used as a positive electrode. Further, electrolysis is performed in a ferric nitrate bath using nickel fiber as a cathode and an iron plate as an anode to electrolytically deposit iron / iron hydroxide on the surface of the nickel fiber. The nickel fiber whose surface is coated with this iron / iron hydroxide is used as a negative electrode.

The nickel fibers 40 coated with the positive electrode active material are arranged in a line, and the separator 12 is placed thereon.
As a Teflon film is laid. At this time, the end on the positive electrode current collector side is aligned with the separator 12 with the cross section of the nickel fiber 40 of the positive electrode exposed, and the separator 12 is longer on the end on the negative electrode current collector side. Then, the nickel fibers 42 having the surface coated with the negative electrode active material are arranged in a line on the separator 12.
At this time, the end on the negative electrode current collector side is aligned with the separator 12 with the cross section of the nickel fiber 42 of the negative electrode exposed, and the separator 12 is longer on the end on the positive electrode current collector side. Further, a separator 12 is laid on it, and a positive electrode and a negative electrode are laminated with the separator interposed therebetween. Layered carbon fiber is used for battery cells 16
Then, the positive electrode current collector 18 is pressed against the surface where the positive electrode nickel fiber 40 and the separator 12 are aligned from the direction perpendicular to the layered carbon fiber (vertical direction).
After injecting the electrolytic solution in a state where the positive electrode current collector 18 side is the bottom surface, the negative electrode current collector is the surface where the nickel fiber 42 of the negative electrode and the separator 12 are aligned, that is, from the side opposite to the positive electrode current collector 18. Press 20 to complete the battery. Other configurations and operational effects are similar to those of the first embodiment. The positive electrode and the negative electrode of the present embodiment are
It is of course possible to apply to the configuration of the seventh embodiment.

17 to 20 show a tenth embodiment of the present invention.
1 shows an example of a fiber battery according to a form. In the present embodiment, as an example, a carbon fiber, which is a base material using a resin, and a battery active material attached thereto is used as a positive electrode, and the negative electrode side is formed by filling a battery active material formed into a plate shape. It is a nickel-hydrogen battery. A manufacturing example of the fiber battery of the present embodiment will be described. (1) Manufacture of negative electrode For example, a Henschel mixer with an internal volume of 10 liters is charged with particulate graphite (acetylene black, Ketjen black).
(150 g) and stirred at 1000 rpm for about 3 minutes to sufficiently disperse the particulate graphite. To this, 2500g of hydrogen storage alloy powder for battery, carbon fiber (Brand name: Dona S-247)
Is added at 100 rpm and mixed at 1000 rpm for about 3 minutes. Separately, 150 g of ethylene vinyl acetate copolymer is added to 1000 g of xylene heated to 60 ° C. and dissolved. 6
A resin dissolved in heated xylene was added to the mixture of the hydrogen storage alloy powder and the conductive filler heated to 0 ° C., and 6
Stir with a Henschel mixer while heating at 0 ° C. Next, the Henschel mixer is cooled with stirring, and the kneaded product is cooled and ground to give a powder. This powder is put into a high speed mixer, and the particle size of the granulated particles is adjusted with a chopper while stirring the whole powder with an agitator. The high speed mixer has a capacity of 2 liters, the agitator rotation speed is 600 rpm, and the chopper rotation speed is 1500 r.
The temperature of the powder is from room temperature to 5
Heat to 0 ° C. After the granulated particles are generated, stirring is stopped while cooling. Since the particles contain xylene, the particles are placed in a vacuum dryer and heated to 50 ° C. to remove xylene. After the particles are cooled, they are sieved through a 2.88 mm sieve and a 1 mm sieve to obtain 1 to 2.88 mm primary molded particles. 90 g of the primary molded particles are filled in a 100 mm square mold, and the mold is heated to 100 ° C. to soften the resin (ethylene vinyl acetate copolymer) contained in the primary molded particles. Next, the resin is cured by lowering the temperature while applying a pressure of 0.1 MPa in the mold. This is taken out of the mold and the obtained plate-shaped active material 44 is used as a negative electrode (FIG. 17).

(2) Production of positive electrode For example, a Henschel mixer with an internal volume of 10 liters is charged with particulate graphite (acetylene black, Ketjen black).
(150 g) and stirred at 1000 rpm for about 3 minutes to sufficiently disperse the particulate graphite. To this, 1000 g of nickel hydroxide powder for batteries is added and mixed at 1000 rpm for about 3 minutes. Separately, 300 g of ethylene vinyl acetate copolymer is added to 2000 g of xylene heated to 60 ° C. and dissolved. A resin dissolved in heated xylene is added to the mixture of the particulate graphite and the nickel hydroxide powder heated to 60 ° C., and the mixture is stirred and dispersed with a Henschel mixer while being heated and maintained at 60 ° C. Dip carbon fiber in this,
Pull up. Then, it is vacuum dried at 50 ° C. in a vacuum heating furnace to vaporize xylene. In the carbon fiber 46 having the surface coated with the positive electrode active material, the fiber portion not covered with the active material is fixed with one nickel plate to form the positive electrode external terminal 48. The obtained fibrous active material 50 with external terminals is used as a positive electrode (FIG. 1).
8).

(3) Assembly As shown in FIG. 19, the plate-like active material 44, which is a negative electrode.
Is laid on its side and the separator 12 is laid on it. A fibrous active material 50 with an external terminal, which is a positive electrode, is placed thereon and the positive electrode external terminal 48 is projected to the outside. Further, the insulating sheet 52 (which can be a separator) is covered from above. As shown in FIG. 20, the battery cell 16 is filled with the material in this state so that the plate-like active material 44, which is a negative electrode, comes into contact with the negative electrode external terminal 54, which is a negative electrode current collector and also serves as a battery cell. After the electrolytic solution is added, the lid 32 is closed to complete the battery. Note that in this embodiment mode, the positive electrode and the negative electrode can be formed in any combination. It is also possible to construct a battery by inserting into the battery cell filled with the particulate active material a carbon fiber whose surface is coated with the battery active material and whose outside is covered with a porous film.

[0044]

Since the present invention is configured as described above, it has the following effects. (1) Battery active materials with extremely low electron conductivity or huge materials that must move in order to react, because high output is possible by shortening the moving distance as much as possible. Compared with conventional batteries, by constructing a battery by bundling or stacking a thin battery active material layer on the surface of a fibrous electron conductive material as a moving passage It is possible to obtain a battery capable of high output, which is dramatically improved in both charging speed and discharging speed. (2) A battery active material is attached to the surface of a fibrous material having electron conductivity, and a porous material having no electron conductivity and ion conductivity is coated on the outside of the fibrous material. Alternatively, it can be made into a woven fabric, and these can be laminated to function as a battery. (3) Since it suffices to hold down a current collector with a battery-active material coated on the surface and arranged with electron conductive fibrous substances or laminated as a woven fabric, welding unlike the conventional battery is unnecessary. Easy to recycle. (4) When the unit cells are stacked to have a high voltage, the partition walls provided between the unit cells can be commonly used to increase the voltage, and the partition walls have a large area and a small thickness. As a result, it is possible to obtain a battery in which the voltage drop is extremely small.

[Brief description of drawings]

FIG. 1 is a schematic view of an example of a fiber battery according to a first embodiment of the present invention when viewed from the longitudinal direction of a fiber.

FIG. 2 is a schematic view of an example of the fiber battery according to the first embodiment of the present invention as seen from the cross-sectional direction of the fiber.

FIG. 3 is a schematic view of an example of a fiber battery according to a second embodiment of the present invention as seen from the longitudinal direction of the fiber.

FIG. 4 is a schematic view of an example of a fiber battery according to a second embodiment of the present invention, as seen from the cross-sectional direction of a fiber.

FIG. 5 is a schematic view of an example of a basic unit in a consolidated state according to the third embodiment of the present invention as seen from the cross-sectional direction of fibers.

FIG. 6 is a schematic view of an example of a fiber battery according to a third embodiment of the present invention as viewed from the longitudinal direction of the fiber.

FIG. 7 is a schematic diagram showing an example of a fiber battery according to a fourth embodiment of the present invention.

FIG. 8 is an enlarged view of a part of a single cell according to a fifth embodiment of the present invention and is a schematic view seen from a longitudinal direction of a fiber.

FIG. 9 is a schematic diagram showing an example of a fiber battery according to a fifth embodiment of the present invention.

FIG. 10 is an enlarged view of a part of a single cell according to a sixth embodiment of the present invention, as seen from the longitudinal direction of the fiber.

FIG. 11 is a schematic diagram showing an example of a fiber battery according to a sixth embodiment of the present invention.

FIG. 12 is a schematic diagram showing an example of a fiber battery according to a seventh embodiment of the present invention.

FIG. 13 is a schematic view of an example of a fiber battery according to an eighth embodiment of the present invention as seen from the longitudinal direction of the fiber.

FIG. 14 is a schematic diagram showing an example of a fiber battery according to an eighth embodiment of the present invention, as seen from the cross-sectional direction of the fiber.

FIG. 15 is a schematic view of an example of a fiber battery according to a ninth embodiment of the present invention as viewed from the longitudinal direction of the fiber.

FIG. 16 is a schematic view of an example of a fiber battery according to a ninth embodiment of the present invention as seen from the cross-sectional direction of the fiber.

FIG. 17 is a schematic diagram showing an example of a plate-like active material according to the tenth embodiment of the present invention.

FIG. 18 is a schematic diagram showing an example of a fibrous active material with external terminals according to the tenth embodiment of the present invention.

FIG. 19 is a schematic diagram showing an assembling step according to the tenth embodiment of the present invention.

FIG. 20 is a schematic view of an example of the fiber battery according to the tenth embodiment of the present invention as seen from the longitudinal direction of the fiber.

[Explanation of symbols]

10, 46 Carbon fiber 12 coated on the surface with a positive electrode active material 12 Separator 14 Carbon fiber 16 coated on the surface with a negative electrode active material 16 Battery cell 18 Positive electrode current collector 20 Negative electrode current collector 22 Surface coated with a positive electrode active material and further outside Carbon fiber 24 coated with a porous film 24 porous film 26 carbon fiber coated with a negative electrode active material on the surface and further coated with a porous film 28 polypropylene band 30 woven fabric 32 lid 34 insulating member 36 partition wall 38 connection plate 40 positive electrode Nickel fiber 42 coated with active material on the surface Nickel fiber 44 coated with negative electrode active material on the surface Plate-shaped active material 48 Positive electrode external terminal 50 Fiber active material with external terminal 52 Insulation sheet 54 Negative electrode external terminal

─────────────────────────────────────────────────── ─── Continued Front Page (51) Int.Cl. ⁷ Identification Code FI Theme Coat (Reference) H01M 4/62 H01M 4/62 Z 5H032 4/75 4/75 Z 5H050 10/12 10/12 K 10 / 30 10/30 Z 10/40 10/40 Z 12/08 12/08 K (72) Inventor Kazuya Nishimura 1-1 Kawasaki-cho, Akashi-shi, Hyogo Kawasaki Heavy Industries Ltd. Akashi factory (72) Inventor Mitsuda Susumu Osaka City Chuo-ku, Hiranocho 4-1-2, F-term in Osaka Gas Co., Ltd. CC22 5H028 AA05 BB03 BB04 CC01 CC05 CC08 CC11 CC20 CC26 5H029 AJ02 AK02 AL06 AL12 AM16 CJ03 CJ05 CJ06 CJ22 CJ23 CJ24 DJ05 DJ07 DJ15 EJ04 5H032 AA01 AS01 BB04 CC06 CC09 CC11 5H050 AA02 BA20 BA02 BA09 BA02 BA02 BA02 BA09 BA02 A06 CA07 CA12 CB11 CB12 CB13 CB14 CB15 CB16 DA04 DA19 DA20 EA02 EA03 EA08 EA09 EA10 FA09 FA16 FA18 GA03 GA08 GA22 GA23 GA24

Claims (30)

[Claims] 1. A positive electrode in which the surface of a fibrous material having electron conductivity is coated with a positive electrode active material, arranged one by one or in a bundle or formed into a woven fabric, and the surface of a fibrous material having electron conductivity. A negative electrode in which the negative electrode active material is coated one by one, or arranged in a bundle, or a woven negative electrode is laminated by sandwiching a separator having no electron conductivity but ion conductivity between the positive electrode and the negative electrode. The positive electrode current collector is attached so that at least one end of the fibrous substance laid as the contact is attached, and the negative electrode current collector is attached so that at least one end of the fibrous substance laid as the negative electrode is attached, and the battery cell is filled with the electrolytic solution. A fiber battery characterized by being configured as follows. 2. A method in which a surface of a fibrous substance having electron conductivity is coated with a positive electrode active material, and the outer side thereof is coated with a porous substance having no electron conductivity but ion conductivity.
The positive electrode, which is arranged in the form of a book, a bundle, or is woven, and the surface of a fibrous substance having electron conductivity are coated with a negative electrode active material, and the outside thereof is made of a porous substance having no electron conductivity and ion conductivity. A negative electrode formed by laying ones coated with a substance one by one or in a bundle or formed as a woven fabric is attached, and a positive electrode current collector is attached so that at least one end of a fibrous substance laid as a positive electrode is in contact, and laid as a negative electrode. A fiber battery, wherein the negative electrode current collector is attached so that at least one end of the fibrous substance is in contact with the fibrous substance, and the battery cell is filled with an electrolytic solution. 3. A method in which the surface of a fibrous substance having electron conductivity is coated with a positive electrode active material, and the outside thereof is coated with a porous substance having no electron conductivity but ion conductivity.
The warp yarns to be used for the positive electrode are formed in a bundle or in bundles, the surface of a fibrous substance having electron conductivity is coated with a negative electrode active material, and the outside thereof is made of a porous substance having no electron conductivity and ion conductivity. As the weft yarns used for the negative electrode, the coated yarns are bundled one by one or as a bundle, and a woven fabric having warp yarns and weft yarns as a positive electrode and a negative electrode, respectively, is formed, and the woven fabrics are laminated so as to have the same orientation in the vertical and horizontal directions. The positive electrode current collector is attached from both sides or one side so that at least one end of the fibrous substance of the warp yarn that is the positive electrode is in contact with the surface that is substantially perpendicular to the direction, and the fiber of the weft yarn that is the negative electrode is on the surface that is substantially perpendicular to the weft direction of the fabric. A fiber battery, wherein negative electrode current collectors are attached from both sides or one side so that at least one end of the substance is in contact, and the battery cell is filled with an electrolytic solution. 4. A resin in which a porous substance having no electron conductivity but ion conductivity is dissolved in a solvent soluble in water or alcohol, and the solvent is extracted with water or alcohol from the resin dissolved in the solvent. 3. A resin that is made porous by
Alternatively, the fiber battery according to item 3. 5. A resin dissolved in a water-soluble solvent is a polyether sulfone resin dissolved in dimethyl sulfoxide, polystyrene dissolved in acetone, dimethylformamide or polysulfone dissolved in dimethyl sulfoxide, dimethylformamide, Polyacrylonitrile dissolved in dimethyl sulfoxide or ethylene carbonate, dimethylformamide,
Dimethyl sulfoxide or N-methyl-2-
Polyvinylidene fluoride dissolved in pyrrolidone, polyamide dissolved in dimethylformamide or N-methyl-2-pyrrolidone, or polyimide dissolved in dimethylformamide or N-methyl-2-pyrrolidone, dissolved in a solvent soluble in alcohol The resin is cellulose acetate dissolved in methylene chloride or oxide phenylene ether dissolved in methylene chloride.
The described fiber battery. 6. The porous substance having no electron conductivity but ion conductivity is a solid electrolyte, Teflon (registered trademark), or a polyolefin membrane film or non-woven fabric represented by polyethylene or polypropylene.
Alternatively, the fiber battery according to item 3. 7. The fibrous substance is a substance having electron conductivity represented by carbon fiber or metal fiber, or organic fiber, inorganic fiber, fibrous plastic or rubber whose surface is metal-plated. Item 7. The fiber battery according to any one of items 1 to 6. 8. A battery in which the positive electrode active material is nickel / nickel hydroxide and the negative electrode active material is cadmium, a battery in which the positive electrode active material is nickel / nickel hydroxide and the negative electrode active material is hydrogen storage alloy, and the positive electrode active material is nickel / water. Batteries with nickel oxide and negative electrode active material of iron / iron hydroxide, positive electrode active material with nickel / nickel hydroxide and negative electrode active material of zinc, positive electrode active material with lead / lead dioxide and negative electrode active material with lead, Batteries in which the positive electrode active material is a lithium / lithium compound and the negative electrode active material is carbon, batteries in which the positive electrode active material is manganese dioxide and the negative electrode active material is a lithium / lithium compound, batteries in which the positive electrode is air and the negative electrode active material is aluminum, and the positive electrode is air. And the negative electrode active material is a magnesium battery, the positive electrode active material is a silver oxide and the negative electrode active material is a zinc battery,
A battery in which the positive electrode active material is silver oxide and the negative electrode active material is cadmium,
Alternatively, the fiber battery according to any one of claims 1 to 7, wherein the positive electrode active material is manganese dioxide and the negative electrode active material is zinc. 9. The fiber battery according to claim 1, wherein one cell or a plurality of basic units in which positive electrode fibers and negative electrode fibers are arranged or laminated as a woven fabric are filled in one cell. 10. The fiber battery according to claim 9, wherein the basic unit is assembled in a battery cell in a compressed and compressed state. 11. The fiber battery according to claim 10, wherein the basic unit is bound and squeezed with a strip or string made of a porous or non-porous insulator or a meltable or non-meltable insulator. 12. The fiber battery according to claim 1, wherein the same cell is filled or laminated with a laminated body made of a fibrous material having a surface coated with a battery active material having different charge / discharge characteristics. 13. The fiber according to claim 1, wherein a large number of one fibrous substances each having a surface on which a battery active material having different charge / discharge characteristics is attached are filled or laminated in a battery cell. battery. 14. A fiber battery characterized in that a single cell composed of the battery according to any one of claims 1 to 13 is stacked with a partition wall to obtain a high voltage. 15. A fibrous material having a surface coated with a battery active material is used only on the positive electrode side or the negative electrode side, and the other electrode side is replaced with a fibrous material having a surface coated with the battery active material.
The fiber battery according to any one of claims 1 to 14, which is filled with a battery active material in the form of particles or a powder, or a battery active material formed in a plate shape or the like. 16. A fibrous substance having a battery active material attached to the surface of an electronically conductive fibrous substance, the surface of which is coated with a positive electrode active material is a positive electrode, and the fibrous substance having a surface of which is coated with a negative electrode active material is a negative electrode. As a positive electrode fibrous substance, the fibrous substances are arranged one by one or in a bundle or as a woven fabric, and a separator having no electron conductivity but ion conductivity is laid on the fibrous substance and the fibrous substance of the negative electrode is placed on the separator. Are laid one by one or in a bundle or laid as a woven fabric, and the positive electrode and the negative electrode are laminated with the separator sandwiched therebetween, and one side of the fibrous substance on the one side from the substantially vertical direction of the fibrous substance is in contact with at least one end of the fibrous substance. Or, press the positive electrode current collector from both sides and press the negative electrode current collector from one side or both sides from the substantially vertical direction of the fibrous substance so that at least one end of the fibrous substance on the negative electrode side comes into contact, and the battery cell is filled with the electrolytic solution. A method of manufacturing a fiber battery, characterized by completing the battery. 17. A battery active material is attached to the surface of a fibrous substance having electron conductivity, and the outside thereof is covered with a porous substance having no electron conductivity but ion conductivity, and the surface is coated with a positive electrode active material. The fibrous substance coated with a porous film is used as a positive electrode, and the fibrous substance coated on the surface with a negative electrode active material and further coated with a porous film is used as a negative electrode. Put them in a bundle or woven them,
The fibrous substances of the negative electrode are laid one by one or in a bundle or laid on them as a woven fabric, and the positive electrodes and the negative electrodes are alternately or randomly laminated so that at least one end of the fibrous substances on the positive electrode side is in contact with each other. Press the positive electrode current collector from one side or both sides of the fibrous substance in a substantially vertical direction, and press the negative electrode current collector from one side or both sides of the fibrous substance in a substantially vertical direction so that at least one end of the fibrous substance contacts. A method for producing a fiber battery, comprising filling a battery cell with an electrolytic solution to complete the battery. 18. A battery active material is attached to the surface of a fibrous substance having electron conductivity, and the outside is covered with a porous substance having no electron conductivity and ion conductivity, and the surface is coated with the positive electrode active material. The fibrous substance coated with a porous film is used as a positive electrode, and the fibrous substance coated on the surface with a negative electrode active material and further coated with a porous film is used as a negative electrode. A woven fabric in which the warp and the weft are respectively used as a positive electrode and a negative electrode is prepared by bundling them into warp yarns, and the fibrous substance of the negative electrode is bundled one by one or as a weft yarn, and the woven fabrics are laminated in the same longitudinal and transverse directions. The positive electrode current collector is pressed from both sides or one side so that at least one end of the fibrous substance of the warp yarn, which is the positive electrode, is in contact with the face substantially perpendicular to the warp direction of the fabric, and the negative electrode is the face substantially perpendicular to the weft direction of the fabric. At least one end of the fibrous material of the weft thread A negative electrode current collector is pressed from both sides or one side so as to contact with each other, and the battery cell is filled with an electrolytic solution to complete the battery. 19. The battery active material is attached to the surface of the fibrous material by electrolytic deposition by electrolysis.
Or the method for producing a fiber battery according to item 18. 20. At the time of electrolytic deposition by electrolysis, the battery active material is suspended as fine particles in an electrolytic bath, and the battery active material is incorporated into the plating metal by a co-deposition plating method to cause co-deposition. Fiber battery manufacturing method. 21. The method for producing a fiber battery according to claim 16, wherein the battery active material is fixed on the surface of the fibrous material using a resin. 22. As the resin, a thermoplastic resin of at least one of polyethylene, polypropylene and ethylene vinyl acetate copolymer, or a reaction curable resin of at least one of epoxy resin, polyurethane resin and unsaturated polyester resin, or phenol resin 22. The method for producing a fiber battery according to claim 21, wherein the thermosetting resin represented by 1 is used alone or in combination. 23. As the resin, polyethylene dissolved in heated toluene or xylene, which is a resin dissolved in a solvent,
The production of a fiber battery according to claim 21, wherein a thermoplastic resin of at least one of polypropylene and ethylene vinyl acetate copolymer is used, the surface is coated with a resin dissolved in a solvent, and then the solvent is removed by heating under reduced pressure or atmospheric pressure. Method. 24. As the resin, a polyether sulfone resin dissolved in dimethyl sulfoxide, which is a resin dissolved in a water-soluble solvent, polystyrene dissolved in acetone, polysulfone dissolved in dimethylformamide or dimethyl sulfoxide, Polyacrylonitrile dissolved in dimethylformamide, dimethylsulfoxide or ethylene carbonate, dimethylformamide, polyvinylidene fluoride dissolved in dimethylsulfoxide or N-methyl-2-pyrrolidone, dimethylformamide or N-methyl-2
-Polyamide dissolved in pyrrolidone, polyimide dissolved in dimethylformamide or N-methyl-2-pyrrolidone, cellulose acetate dissolved in methylene chloride which is a resin dissolved in a solvent soluble in alcohol, or dissolved in methylene chloride 22. The method for producing a fiber battery according to claim 21, wherein a resin dissolved in a solvent soluble in water or alcohol is coated on the surface using oxide phenylene ether, and then the solvent is extracted and removed with water or alcohol. 25. To make the resin conductive, a conductive material of at least one of carbon black, carbon fiber, carbon foil, carbon whiskers, nickel metal fine particles, nickel foil and nickel metal whiskers is added to the resin. The method for manufacturing a fiber battery according to any one of claims 21 to 24. 26. As a method for adding a conductive material to a resin, a resin dissolved in a solvent and the conductive material are mixed and dispersed, or a solvent and the conductive material are mixed and dispersed, and then the resin is dissolved. The method for producing a fiber battery according to claim 25, wherein the fiber battery is mixed and dispersed. 27. The method of producing a fiber battery according to claim 16, 17 or 18, wherein the surface of the fibrous material is provided with a battery active material by hot dipping. 28. The method for producing a fiber battery according to claim 16, 17 or 18, wherein the surface of the fibrous material is provided with a battery active material by sintering. 29. A resin dissolved in a solvent soluble in water or alcohol is used as a porous substance having no electron conductivity but ion conductivity for coating a fibrous substance having a surface coated with a battery active material, The method for producing a fiber battery according to claim 17 or 18, wherein after coating the surface with a resin dissolved in a solvent soluble in water or alcohol, the solvent is extracted and removed with water or alcohol. 30. A fibrous material is provided with a battery active material, the outer surface of which is covered with a porous material is cut to expose a cross section of the fibrous material, and a current collector is provided on the cross section. 30. The method for producing a fiber battery according to claim 17, wherein the fiber battery is contacted.