KR100658254B1 - Battery - Google Patents

Abstract

The anode active material and electrolyte solution 16 of the negative electrode are loaded in the negative electrode cell 12 on one side of the two cells connected with the separator 10 through which ions pass, and the positive electrode cell in the other cell ( In 14), the positive electrode granular active material and the electrolyte solution 18 are loaded, and the current collectors 20 and 22 of the conductor which come into contact with the granular material as the active material are provided in two cells. The granular active material forms a fixed layer.

Battery, three-dimensional, powder, active material, fixed layer

Description

Battery {BATTERY}

BACKGROUND OF THE INVENTION 1. Field of the Invention [0001] The present invention relates to a fixed bed type battery capable of large power storage in which an active material is formed as a powder and capable of simplifying the structure. In addition, the present invention is constructed by incorporating a powder of an active material that emits and absorbs electrons into an electrolyte solution stored in a cell as a minimum electrode to form a fixed layer. The structure is simple, and a large-capacity power storage is achieved. A battery of a three-dimensional structure is possible.

Conventionally, batteries have a structure in which an active material is plate-like or sheet-like immersed in an electrolyte solution. A plate-shaped separator is sandwiched between the caso and the anode to form a battery structure.

For example, Japanese Patent Laid-Open No. 7-169513 discloses a method and apparatus for continuously discharging a battery material after discharge by thermally or chemically regenerating by using combustion heat of fossil fuel. Japanese Patent No. 3040151 discloses a fluid bed type three-dimensional battery, but in the battery of this publication, the equipment for obtaining high output is complicated.

In addition, conventionally, a nickel-hydrogen battery is brought into close contact with the current collector 201, the positive electrode 202, the separator 203, the negative electrode 204, and the current collector 205, as shown in FIG. 23. It is done. This example is described, for example in Japanese Patent Laid-Open No. 9-298067. The battery described in the publication is a battery cell having a positive electrode mainly composed of nickel hydroxide, a negative electrode mainly composed of a hydrogen storage alloy, a separator composed of a polymer nonwoven fabric, and an electrolyte solution composed of an aqueous alkali solution. A battery having a structure in which a plurality of cells (single cells) are connected in series, stored in a metal rectangular container, and sealed with a sealing plate having a reversible band having an opening. The conventional battery 200 including the above-described structure has a membrane structure (two-dimensional), and when the battery 200 has a large capacity, it is rolled up as shown in FIG. 24 to be thinner, or As shown in FIG. 25, the unit cells 200 are connected in parallel, or as shown in FIG. 26, the plurality of electrode plates 206 are interposed in the plurality of unit cells 200, and each electrode plate 206 is connected to each other. It is common for the connected wiring 207 to be pulled out of the battery, and these electrodes are connected with the electrode plate 208 which differs in the polarity of another unit cell, and it is set as a laminated structure. Japanese Patent No. 3040151 discloses a fluid bed type three-dimensional battery, but in the battery of this publication, the equipment for obtaining high output is complicated.

However, the conventional battery described above has the following problems.

(1) There is a limit to scale-up or cannot be scaled up.

In other words, a conventional battery has a film structure (two-dimensional), and the current flowing through the battery is proportional to the area of the film. Thus, for example, if 1 W of power is generated in an area of 1 m ² , in order to generate 10 kW of power, An area of (100 × 100) m ² is required. Therefore, it is considered to increase the number of membranes or to expand the membranes. However, in any case, the membranes are enlarged in size, making practical use difficult. Therefore, as a result, the batteries must be connected in parallel, which complicates the whole structure.

Furthermore, if there is a battery with a film area of 1 m ² to 1 W, an area of 1 million m ² is required to make this one million kW. If it is square, it is about 32km in all directions and it is practically impossible to make a flange or the like. In addition, scale-up is not possible even in response to increasing the number of films.

(2) It cannot cope with deterioration of an active material and a catalyst.

In conventional batteries, active materials, catalysts, and the like are used as structural materials of the battery, and are fixed in a plate shape, a columnar shape, and the like, and when deteriorated, they have no choice but to be replaced. The whole battery needs to be replaced.

(3) Heat transfer surfaces corresponding to heat generation and endotherm due to charging and discharging cannot be installed.

It is necessary to provide a heat transfer surface in the battery from the characteristics of the battery that there is heat generation and endotherm according to the charging and discharging of the battery, and that the self discharge increases when the temperature is increased, and conversely, when the temperature is lowered, the reaction rate becomes slow. However, since the conventional battery has a complicated structure, no heat transfer surface is provided. In addition, since the battery is small and the battery surface area with respect to the output is small, there is a method of cooling or endotherm by natural neglect. Moreover, although the upper limit temperature is set using a thermal fuse etc., the temperature control equipment is not installed in a battery.

(4) The energy density is small.

Conventional cells have a current proportional to the surface area of the membrane. Thus, for example, in a battery having a membrane area of 1 m ² to 1 W, when a 1000 kW battery is produced, one million membrane-shaped cells having a membrane area of 1 m ² and a width of 0.1 m are required, and 100,000 m ³ It becomes size and cannot make energy density large.

(5) The manufacturing cost is very high due to the large capacity.

That is, in order to achieve a large capacity, it is necessary to increase the area of the film proportionally in the battery of the membrane structure, but the manufacturing cost increases in proportion to the increase of the battery capacity. For this reason, there is no advantage in manufacturing cost by scaling up.

(6) When the batteries are connected in series, the cost of the device and the loss of the resistive energy of the connecting portion are increased.

That is, for example, when a plurality of 1.6V to 2.0V batteries are connected to each other to obtain a high voltage such as 10V, the cells must be connected by wires or the like, thereby increasing the work cost and passing through the connection portions. An exothermic loss occurs due to an electric current that causes an energy loss.

The present invention exhibits an example of the various points described above, and an object of the present invention is to provide a fixed bed type battery in which a granular material is put in a cell by using an active material as a granular material, thereby simplifying installation and enabling scale-up. The present invention provides a battery capable of coping with deterioration of active material and catalyst, deterioration, etc., and providing a heat transfer surface in the battery, and further increasing energy density.

In addition, the object of the present invention can cope by increasing the volume (cell) of the battery when the battery capacity is increased by three-dimensionalizing the structure of the battery as a fixed layer of the granular material, and accompanying the scale up The laminated structure which produces various advantages is providing the battery of a simple three-dimensional structure.

In order to achieve the above object, in the battery of the present invention, a granular material of an active material that emits electrons in an electrolyte solution in an electrolyte solution in one cell of two cells connected via a member through which ions pass is loaded as the fixed layer, and the other The granular material of the active material which absorbs the electrons in the electrolyte solution in the cell is loaded as a fixed layer, and the current collector of the conductor in contact with the granular material as the active material is provided in two cells (see FIGS. 11 to 12).

In addition, the battery of the present invention is filled with an electrolyte solution in a cell, and a porous body in which a granule of an active material releasing electrons in the electrolyte solution is housed as a fixed layer, and a porous body in which a granule of an active material absorbing electrons is stored as a fixed layer. And a current collector for a conductor in contact with the granular material of the active material is provided in these porous bodies (see FIG. 13).

In this specification, the granular material and the fixed layer of an active material are used for the purpose of following description.

Generally, the finer the solid, the larger the surface area / volume ratio, so that various properties of the surface can be neglected, called microparticles. In the present specification, the aggregate of the solid microparticles is called a granular material.

Preferable examples of the granular material of the active material of the present invention are shown in Figs. 21 (a) to (h).

(1) powder obtained by mixing

As shown in FIG. 21 (a), a material having high electron conductivity is mixed with a material having low electron conductivity LC. In FIG.21 (a)-(h) and FIG. 22, what discolored is LC, and what was thinly colored shows HC.

(2) powder granules obtained by mixing and assembling

As shown to Fig.21 (b), (c), it is obtained by adding and granulating a binder (granulator) to what mixed HC to LC. HC of FIG. 21 (c) is fibrous.

(3) powder obtained by coating

As shown in Fig. 21 (d), it is obtained by coating HC on LC. As this coating means, it is possible to employ a known one as a surface coating means such as a catfish or vacuum deposition.

(4) powder obtained by assembling what is obtained by coating

As shown in Fig. 21 (e), it is obtained by adding a binder (assembling agent) to the LC coated with HC by coating means such as Meki (see Fig. 21 (d)) and granulating.

(5) Granular material obtained by coating what is obtained by granulation

As shown in Fig. 21 (f) (g) and (h), it is obtained by coating HC on what is obtained by granulation (see Figs. 21 (b), (c) and (e)).

In the present invention, the fixed layer of the granular material of the active material is a layer loaded with the granular material as illustrated in FIGS. 21A to 21H, and the granular material as the loaded material is preferably stopped. A part of an example of the fixed layer of is enlarged and shown. FIG. 22 shows a case where a mixture (see FIG. 21 (a)) exists in the gap of the granulated material (see FIG. 21 (b)).

By forming the fixed layer which loaded the granulated material of such an active material, the electronic conductivity of a fixed layer becomes favorable and it is possible to discharge at high output.

As a substance with low electron conductivity, nickel hydroxide, a hydrogen storage alloy, etc. are mentioned, for example.

As a substance with high electronic conductivity, carbon particle | grains, nickel particle, nickel foil, carbon fiber, fibrous nickel, etc. are mentioned, for example.

As the binder, for example, polytetrafluoroethylene, polypropylene, ethylene vinyl acetate copolymer (EVA), polystyrene, or the like can be used.

As shown in Fig. 21 (b), (c) and (e), the size of the granular material is preferably about 10 µm to about 10 mm in diameter when obtained by granulation.

In the battery of the present invention described above, the current collector in contact with the granular material as the active material may be any of a rod, plate, and tubular shape (see FIGS. 1 to 3).

Moreover, in the battery of these invention, it is preferable to provide the heat-transfer surface for making constant reaction temperature in a battery in a cell. As the heat transfer surface, it is also possible to use any of the tubular current collector and plate-shaped current collector that come into contact with the granular material as the active material (see FIGS. 7 and 8).

Further, in the batteries of the present invention, it is preferable to connect the extraction means for extracting the granular material, which is the degraded active material, from the cell, and the supplying means, for supplying the granular material, which is the active material, to the cell, respectively. (See FIG. 9, FIG. 10).

In this case, at least one of a regeneration means for regenerating the granulated material that is the extracted active material and a make-up means for replenishing the granular material that is the active material is connected to the extraction means, and is composed of the regenerated or newly changed active material. It is possible for the powder to be fed into the cell from the supply means (see FIG. 9).

In addition, the extraction means is connected to a reaction means for changing the powder of the extracted active material into a charged powder by thermochemical or electrochemical reaction, so that the powder of the charged active material is supplied from the supply means into the cell. It is possible (see FIG. 10).

In addition, in the batteries of the present invention, it is possible to make the granular material, which is the active material on the negative electrode side, as a granule made of a hydrogen storage alloy, and the granular material, which is the active material on the positive electrode side, to a granule made of nickel hydroxide (see Fig. 6). .

In the batteries of the present invention, the granular material of the negative electrode side is made of a hydrogen absorbing alloy, the gas introduced into the negative electrode is made of hydrogen, and the granular material of the positive electrode is made of nickel hydroxide. It is possible to set it as powder and to make oxygen or air into the gas introduced in the anode side (refer FIG. 11).

Points of improvement of the battery of the present invention are as described below.

(1) Scale up is possible.

The current flowing through the cell is proportional to the surface area of the reactants. Therefore, when a battery is made using the active material as a granule, a battery in which the granule is placed in the cell is constituted. In other words, if the battery is made with the active material as a powder, the battery structure becomes three-dimensional. For example, if the battery is 1W per liter, 1kW for 1m cubic, 1000kW for 10m cubic, 1 million for 100m cubic. It becomes a kW battery, and scale up is attained.

Moreover, when a battery is made with the active material as a granule, the scale advantage is exhibited.

For example, if a conventional battery is 100,000 yen for 1 kW, 1 million kW is required to be 1 million, resulting in 10 billion yen. However, in the battery of the present invention, when the scale is increased, that is, the scale becomes large, the production cost is increased. The effect that decreases is exhibited, and it is possible to make about 100 million yen.

(2) It is possible to regenerate or change the deteriorated active material and catalyst.

The active material and catalyst are charged as a fixed layer in an electrolyte solution (electrolyte solution) as a granular material. And when the granule of an active material and a catalyst deteriorates, it is taken out, and it regenerates, it changes into a new active material and a catalyst, or returns to a charged state by thermochemical reaction or an electrochemical reaction, and supplies it again. For example, the powder of the active material and the catalyst is extracted from the cell as a slurry together with the electrolyte by a tube, and the powder is separated from the electrolyte, and regenerated or added as a new product, and then mixed with the electrolyte again to obtain a slurry. The battery is fed to the slurry pump.

For example, a conventional battery can be charged and discharged about 500 times in a small one, and operates for about 8000 hours in a large one. However, the active material and the catalyst are usually in the best state due to circulating regeneration of the active material and the catalyst or a maker up. Since the life of the battery becomes the life of the battery equipment, the battery life is extended from about 50 times to about 100 times.

(3) A heat transfer surface may be provided in the battery.

An active material and a catalyst are used as a granule, and it is used as a fixed layer, and a heat-transfer surface is provided in this. Since the heat transfer of the heat transfer surface provided in the battery is performed three-dimensionally with the powder, the heat transfer area may be small. The heat transfer surface provided in the battery makes it possible to keep the reaction temperature in the battery constant. As the temperature increases, the self discharge rate increases, and conversely, when the temperature decreases, the reaction rate becomes slow. do. In addition, it is possible to use the recovered heat and cold heat for cooling and heating or power generation, thereby increasing the energy generation efficiency and energy utilization rate.

(4) It is possible to increase the energy density.

The current flowing through the cell is proportional to the surface area of the reactant material. Thus, a battery is made using the active material as a powder. In the body the active material powder create a battery it may increase the surface area, for example, is a surface area of about 300000m ² for powder and granular material of 1m ^3, the greater the energy density. For example, if a conventional battery is 1 W in 1 m ² of a film, when making a 3000 kW battery, 3 million membrane-shaped batteries having a width of 0.1 m are required in an area of 1 m ² , and the size is 300000 m ³ . In the battery of this invention, when the battery of such output uses the powder of 1 micrometer of particle diameters, for example, it becomes about 10 m <^3> , the energy density becomes 30000 times, and there exists an effect which enlarges an energy density.

In addition, in the battery of the three-dimensional structure according to the present invention for achieving the above object, one cell is filled with an electrolyte solution on a set of cells connected through a member that allows ions to pass but does not pass electricity. In addition to this, a granular material composed of an active material that emits electrons is added to the electrolyte solution to form a fixed layer, and the other cell is filled with an electrolyte solution, and a granulated material composed of an active material that absorbs electrons is added to the electrolyte solution. And a plurality of sets of unit cells formed by forming a fixed layer so as to be integrally connected in series with a partition wall between the cells and a conductive current collector member in contact with the granular material therebetween to be integrated. And a current collector in which both the positive electrode and the negative electrode are used together to form a stacked three-dimensional battery. And that the features (see Fig. 14 ~ Fig. 19).

In addition, the three-dimensional battery of the present invention is filled with an electrolyte solution in a cell, and a porous body containing a granular material consisting of an active material releasing electrons in the electrolyte solution as a fixed layer, and a granular material consisting of an active material absorbing electrons as a fixed layer. A plurality of sets of unit cells formed by storing the porous body housed therein are connected to each other in series with a partition between the cells and electrically conductive current collectors in contact with the granular material so as to be integrated, and separated into cells at both ends. A stacked type three-dimensional battery is constructed by providing a current collector that is in contact with a sieve and also serves as a positive electrode and a negative electrode (see FIG. 20).

In these batteries, it is preferable to use what is shown to FIG. 21 (a)-(h) with respect to the granular material of an active material. By using such a granular material, the electroconductivity of the fixed layer which loaded the granular material of an active material becomes favorable, and it is possible to discharge at high output. According to the three-dimensional battery of the present invention having the above configuration, an increase in the capacity (power amount) of the battery can be coped by increasing the volume of each cell. That is, if 1W of power is generated in a volume of 1 liter, the volume is increased to 1 m ³ to obtain 1 kW of power, and to 10 m ³ to obtain 10 kW of power. To this end, an advantage in manufacturing cost due to scale up is exerted. In other words, if the conventional battery is 10,000 yen for 10W, it is 10 million yen for 10kW, but the manufacturing cost of the battery of the present invention decreases as the scale is increased, so that about 1/100 of 1 million yen can be manufactured. .

On the other hand, the voltage is determined by the type (material) of the granular material (corresponding to a conventional general electrode) of the active material loaded in the cell. For example, when using metal lead and lead dioxide, the voltage after 2.4 V is used. If more than 12V is required, 5 ~ 6 single cells need to be connected in series. However, according to the present invention, the unit cell positioned in the middle (removing both ends) can have the same material of the current collector member as the positive electrode, and unlike the conventional battery, the electrodes of the positive electrode and the negative electrode are provided. Since there is no need, the partition wall between cells (unit cells) can be electrically and structurally connected in series by configuring a conductive current collector member. In addition, it is possible to make the thickness of the bulkhead quite thin (for example, 0.5 mm) and the area to be wide (for example, 127 mm x 127 mm), and the current flows in the thickness direction of the bulkhead, so that the large capacity is almost It flows without resistance, and the power loss is extremely small.

Furthermore, since two sets of single cells can be directly connected (directly connected) with a partition wall therebetween, a plurality of sets of single cells can be connected in series and in a stacked form, and the volume of the entire battery can be minimized to minimize the size.

Furthermore, in the three-dimensional battery of the present invention, the granular material of the active material functions as a membrane (cell body) of a conventional battery having a membrane structure, and the current flowing through the battery is proportional to the surface area of the active material. A fixed layer is formed therein, and the total surface area of all the granules is several thousand to tens of thousands of times compared to a battery having a conventional film structure, and thus the energy density is several thousand to tens of thousands. In addition, since the granular material of the active material is added to an electrolyte solution (a rare acid in lead batteries) and used as a fixed layer, when deteriorated, the granular material is separated from the electrolyte solution or exchanged with the electrolyte solution. It is possible to achieve regeneration, and battery life is greatly increased (almost 50 to 100 times).

Moreover, in these three-dimensional batteries, it is possible to provide so that a conductive stud may project integrally from the current collector member or the current collector into the cell. According to the three-dimensional battery constituted thereby, the contact area between the current collector member or the current collector and the granular material is greatly increased, and the contact resistance is reduced, so that the distance between the cells (the gap in the series direction) can be increased. And the capacity of the battery can be greatly increased.

Since the battery of this invention is comprised as mentioned above, it has the following effects.

(1) By constructing a fixed bed type battery in which the active material is used as the granular material and the granular material is put into the cell, the battery structure becomes three-dimensional and can be scaled up in a simple configuration. In addition, by constructing a battery using the active material as a granular material, when the scale up becomes large, the scale advantage is exhibited by the reduction in the manufacturing cost.

 (2) When the granular material of an active material and a catalyst deteriorates, it extracts and regenerates, replaces with a new active material and a catalyst, or returns to a state of charge by a thermochemical reaction or an electrochemical reaction, and supplies it again, Since normal active materials and catalysts are maintained in the best state, the life of the battery becomes the life of the battery equipment and the battery life can be greatly extended.

(3) It is possible to provide a heat transfer surface in the battery, and it is possible to make the reaction temperature in the battery constant by the heat transfer surface installed in the battery. It is possible to cope with battery characteristics that the reaction speed of the ground becomes slow. In addition, the recovered heat and cold heat can be used for cooling, heating and power generation, thereby increasing energy generation efficiency and energy utilization rate.

(4) By constructing a battery using the active material as a granular material, the surface area of the reactant material is increased to increase the energy density.

Moreover, as is clear from what was demonstrated above, the battery of the laminated three-dimensional structure which concerns on this invention has the following outstanding effects.

(1) The three-dimensional battery of the present invention can cope with an increase in the capacity (power amount) of the battery by increasing the volume of each cell, so that an advantage in manufacturing cost due to scale up is exhibited. Moreover, since it is a fixed bed type, it is possible to simplify a structure.

(2) In addition, the voltage is determined by the type (material) of the active material loaded in the cell in the form of a powder, and when a large voltage is required, it is necessary to connect a plurality of single cells in series. In addition, the material of the current collecting member can be common, and unlike the conventional battery, since the electrode of the positive electrode and the negative electrode is not constituted, the gap between the cells (single cells) is constituted by the conductive current collecting member, so that Since the structure can be connected in series and the thickness can be made thin, the entire battery can be compactly compacted and can be miniaturized. Since the current flows in the thickness direction, a large current flows almost without resistance.

(3) Furthermore, the granular material of the active material acts as a membrane (cell body) of a conventional battery having a membrane structure, and the current flowing through the battery is proportional to the surface area of the active material, but the granular material forms a fixed layer in the electrolyte solution. In this case, the total area of all the granules is several thousand to tens of thousands of times that of the battery of the conventional membrane structure. Therefore, the power density is several thousand to tens of thousands of times. In the case of deterioration, regeneration can be achieved by exchanging the powder together with the electrolyte solution, and the life of the battery can be greatly extended.

(4) In the case where a conductive stud is provided from the current collector member or the current collector into the cell, the contact area between the current collector member or the current collector and the granular material is greatly increased, and the contact resistance is reduced. The distance (interval in the serial direction) can be enlarged, and the battery capacity can be greatly increased.

1 is a schematic cross-sectional configuration diagram showing a first embodiment of a battery of the present invention.

2 is a schematic cross-sectional configuration diagram showing an example of a second embodiment of a battery of the present invention.

It is a schematic sectional block diagram which shows the other example of 2nd Embodiment of the battery of this invention.

4 is a schematic cross-sectional configuration diagram showing an example of a third embodiment of a battery of the present invention.

5 is a schematic cross-sectional configuration diagram showing another example of the third embodiment of the battery of the present invention.

6 is a schematic cross-sectional configuration diagram showing a fourth embodiment of the battery of the present invention.

7 is a schematic cross-sectional configuration diagram showing an example of the fifth embodiment of the battery of the present invention.

It is a schematic sectional block diagram which shows the other example of 5th Embodiment of the battery of this invention.

9 is a schematic cross-sectional configuration diagram showing an example of the sixth embodiment of the battery of the present invention.

10 is a schematic cross-sectional configuration diagram showing another example of the sixth embodiment of the battery of the present invention.

11 is a schematic cross-sectional configuration diagram showing a seventh embodiment of the battery of the present invention.

It is a schematic sectional block diagram which shows 8th Embodiment of the battery of this invention.

It is a schematic cross-sectional block diagram which shows 9th Embodiment of the battery of this invention.

Fig. 14A is a perspective view showing an example of an demonstration tester according to the first embodiment of the stacked three-dimensional battery of the present invention, and Fig. 14B is a central longitudinal sectional view conceptually showing the same three-dimensional battery.

FIG. 15 is a perspective view showing a part of main components before assembling (disassembled state) of the demonstration tester of the stacked three-dimensional battery of FIG. 14. FIG.

FIG. 16 is a central longitudinal cross-sectional view conceptually illustrating a second embodiment of the stacked three-dimensional battery of the present invention. FIG.

Fig. 17 is a central longitudinal sectional view conceptually showing the third embodiment of the stacked three-dimensional battery of the present invention.

18 is a central longitudinal sectional view conceptually illustrating the fourth embodiment of the stacked three-dimensional battery of the present invention.

Fig. 19 is an explanatory cross-sectional view showing the main parts of a fifth embodiment of the stacked three-dimensional battery of the present invention.

20 is an explanatory cross-sectional view showing the main parts of a sixth embodiment of the stacked three-dimensional battery of the present invention.

21 (a) to (h) are views showing the concept of the granular material of the active material of the present invention.

It is a figure which expands and shows a part of an example of the fixed layer which mounted the granular material of the active material of this invention.

Fig. 23 is a central longitudinal sectional view conceptually showing a battery of a conventional general membrane structure.

24 is a central longitudinal sectional view conceptually showing a long type battery of a conventional general membrane structure.

Fig. 25 is a central longitudinal sectional view conceptually showing a state in which the Guernsey of a conventional general membrane structure is connected in parallel.

Fig. 26 is a central longitudinal cross sectional view conceptually showing a state in which batteries of a conventional general membrane structure are connected in series.

* Short description of the major reference marks *

10, 10a: ion permeable filter (separator)

12: cathode cell 14: anode cell

16: negative electrode powder active material and electrolyte solution

18: anode active material and electrolyte solution

20, 82: negative electrode current collector (cathode current collector) 22, 84: positive electrode current collector (anode current collector)

30: plate-shaped cathode current collector 32: pin-shaped anode current collector

34: tubular cathode current collector 36: tubular anode current collector

38: cathode current collector 40: anode current collector

42: negative electrode collector and agitator 44: positive electrode collector and agitator

48: hydrogen storage alloy and electrolyte solution 50: nickel hydroxide and electrolyte solution

52: cathode collector and heat pipe 54: anode collector and heat pipe

56: negative electrode current collector and a heating plate 58: positive electrode current collector and a heating plate

60: separator 62: player

64: mixer 66: powder hopper for maker up

68 reactor 70 fuel supply pipe

72 gas supply pipe 74 cell

76: electrolyte solution

78, 80: bags made of porous material

101. 101-1 to 101-3: stacked three-dimensional battery

102: unit cell (secondary battery) 103: positive electrode cell

104: cathode cell

105, 105a: ion permeable filter (separator)

106: positive electrode current collector 107: current collector member

108: negative electrode collector 109: packing

121: cell member 123: bolt

132, 133, 136: stirring means 160: cell

162, 164: bag made of porous body

166: negative electrode current collector 168: positive electrode current collector

n, h, A, B: powder (active material) k, r: electrolyte solution

EMBODIMENT OF THE INVENTION Hereinafter, although embodiment of the battery of this invention is described, this invention is not limited to the following embodiment at all, It is possible to change suitably and to implement.

1 shows a first embodiment of the present invention. As shown in FIG. 1, an anode cell 12 and an anode cell 14 are provided with an ion permeable filter (separator) 10 interposed therebetween, and the anode cell 12 has an anode active material and an electrolyte solution ( 16) is loaded, and the anode active material 14 and the electrolyte solution 18 of the positive electrode are loaded in the positive cell 14. The granular active material is present as a fixed layer in the electrolyte solution. 2 and 20 to be described later, for convenience, the size of each powder active material is the same, but it is natural that the size of each powder active material is different.

As the combination of the negative electrode and the positive electrode powder active material, for example, a hydrogen storage alloy and nickel hydroxide, cadmium, nickel hydroxide and the like can be used. As an example of a hydrogen storage alloy, La _0.3 (Ce, Nd) _0.15 Zr _0.05 Ni _3.8 Co _0.8 Al _0.5 etc. are mentioned as an example. In addition, as an electrolyte solution, KOH aqueous solution etc. are used, for example. The separator 10 is a filter for passing ions and a membrane through which the granules do not pass. For example, an element, an ion exchange resin membrane, a polymer fiber, or the like is used.

In addition, in the cathode cell 12 and the anode cell 14, a cathode current collector (sieve) 20 and a cathode current collector (sieve) 22 each made of a conductor are provided, and the current collectors 20 and 22 are provided. Is connected to a load means (in the case of discharge) or a power generation means (in the case of charging) 26. 28 is an electrolyte solution interface.

Next, the charge and discharge will be described in detail with respect to the battery of the present embodiment.

(charge)

Voltage is applied to the battery, and electrons are supplied by the negative electrode current collector 20. The electrons are reacted by the negative electrode current collector 20 by being moved directly to the powder active material of the negative electrode or with the powder therebetween. The ions generated by the reaction pass through the separator 10 and enter the positive electrode cell 14, where they react with the particulate active material of the positive electrode to emit electrons. The electrons are transported to the power generating means 26 with the granular material interposed therebetween or directly moving to the positive electrode current collector 22.                 

(Discharge)

The battery is loaded and electrons are supplied by the negative electrode current collector 20. The electrons are discharged from the active material cationized in the negative electrode cell 12 and move directly to the negative electrode current collector 20 or sandwiched therebetween. The ions generated by the reaction pass through the separator 10 and enter the positive cell 14, where they react with the positive electrode granular active material and the electrons. The electrons are supplied to the load means 26 by being moved between the granules or directly to the positive electrode current collector 22.

2 and 3 show a second embodiment of the battery of the present invention. 2 shows the contact area of the negative electrode current collector and the positive electrode current collector as the plate-shaped negative electrode current collector 30 and the plate-shaped positive electrode current collector 32, respectively, in order to improve the contact efficiency between the current collector and the granular material of the active material. Will be increased. In addition, in order to improve the contact efficiency of an electrical power collector and the granular material of an active material, FIG. 3 contacts a negative electrode collector and a positive electrode collector as the tubular cathode collector 34 and the tubular anode collector 36, respectively. The area is enlarged. In addition, as long as the surface area of a collector is large, it is also possible to employ shapes other than plate shape and tubular shape.

Other configurations and operations are the same as those in the first embodiment. 4 and 5 show a third embodiment of the present invention. 4 shows the negative electrode contactor 38 and the positive electrode current collector 40 in a fixed bed. 5 shows the negative electrode collector 42 and the positive electrode collector 44 as a stirrer which is driven by a motor etc. (not shown), respectively.

In FIG. 4, it is possible to provide stirring means, such as a right-side stirrer, in each cell 12 and 14. As shown in FIG.                 

In addition, as shown in FIG. 5, the negative electrode current collector and the stirrer 42 and the positive electrode current collector and the stirrer 44 have a function of directly contacting the powder and the direct current while stirring the powder and the powder of the active material. . As the negative electrode current collector and the stirrer 42 and the positive electrode current collector and the stirrer 44, a stirrer, etc., rotated by a motor or the like (not shown) or the like is used, but the configuration of the stirring means is not limited.

Other configurations and operations are the same as those in the first embodiment.

Fig. 6 shows a fourth embodiment of the battery of the present invention. In this embodiment, a granular material which is an active material is a hydrogen storage alloy on the negative electrode side and nickel hydroxide on the positive electrode side.

As shown in FIG. 6, the anode cell 12 is loaded with a granule made of a hydrogen storage alloy and an electrolyte solution 48, and the anode cell 14 is loaded with a granule made of nickel hydroxide and an electrolyte solution 50. It is. As the hydrogen storage alloy, La _0.3 (Ce, Nd) _0.15 Zr _0.05 Ni _3.8 Co _0.8 Al _0.5 and the like are used, for example. In addition, as an electrolyte solution, KOH aqueous solution etc. are used, for example.

The charging and discharging of the battery of this embodiment will be described in detail.

(charge)

Voltage is applied to the battery and electrons are supplied by the negative electrode current collector 20. The electrons are moved to the hydrogen storage alloy on the granules of the negative electrode by the negative electrode current collector 20 directly or with the granules interposed therebetween to cause the following reaction. M is a hydrogen storage alloy.                 

^{_{M + xH 2 O + xe -}} → MH X + xOH -

The hydroxyl ions generated by the reaction pass through the separator 10 and enter the anode cell 14, where it reacts with nickel hydroxide to cause the following reaction and release electrons.

^{_{Ni (OH) 2 + OH -}} → NiOOH + H 2 O + e -

The generated electrons are transported to the power generating means 26 with the granular material interposed therebetween or directly moving to the positive electrode current collector 22.

(Discharge)

The battery is loaded and electrons are supplied by the negative electrode current collector 20. The electrons are released by reaction between the hydrogen storage alloy and the hydroxyl group in the negative electrode cell 12 and move directly to the negative electrode current collector 20 or with the hydrogen storage alloy interposed therebetween. The electrons move from the anode current collector 22 to nickel oxyhydroxide and react with water by intercalating or directly moving nickel oxyhydroxide therebetween, thereby producing nickel hydroxide and hydroxyl groups. The hydroxyl group is introduced into the cathode cell 12 through the separator 10 and reacts with the hydrogen storage alloy.

Other configurations and operations are the same as those in the first embodiment. In addition, the battery of this embodiment can also be implemented with the structure of 2nd Embodiment, 3rd Embodiment, and 5th, 6th Embodiment mentioned later.

7 and 8 show a fifth embodiment of the battery of the present invention. In this embodiment, the heat transfer surface is provided in the battery, and the heat transfer surface has a function of a current collector. In addition, it is also possible to configure the heat transfer surface and the current collector separately. As shown in FIG. 7, the negative electrode current collector and heat transfer pipes 52 are installed in the negative electrode cell 12, and the positive electrode current collector and heat transfer pipes 54 are installed in the positive electrode cell 14. In addition, as shown in FIG. 8, the negative electrode current collector and heat transfer plate 56 are provided in the negative electrode cell 12, and the positive electrode current collector and heat transfer plate 58 are provided in the positive electrode cell 14.

With reference to FIG. 7, the battery of this embodiment is demonstrated in detail charge and discharge.

(charge)

A voltage is applied to the battery, and electrons are supplied by the negative electrode current collector (cumulative heat pipe) 52. The electrons are reacted by the negative electrode current collector 52 by being moved directly by the negative electrode active material of the negative electrode or between the fine particles. The ions generated by the reaction pass through the separator 10 and enter the positive electrode cell 14, where they react with the particulate active material of the positive electrode to emit electrons. The electrons are transported to the power generating means 26 by sandwiching the granules, or directly moving to the positive electrode current collector (cumulative heat pipe) 54.

As described above, the current collector is also used as a heat exchanger tube with the negative electrode and the positive electrode, and simultaneously transfers electrons and heat by the contact of the granular material. Heat medium such as water or air flows through the negative electrode current collector and heat transfer tube 52 and the positive electrode current collector and heat transfer tube 54 to perform heat recovery and heat supply.

(Discharge)                 

The battery is loaded and electrons are supplied by the negative electrode current collector 52. The electrons are released by the active material cationized in the cell 12, and move directly to the negative electrode current collector 52 or with a granular material therebetween. The ions generated by the reaction pass through the separator 10 and enter the positive cell 14, where the positive electrode reacts with the active material and electrons of the positive electrode. The electrons are supplied to the load means 26 by moving to the positive electrode collector 54 with the powder in between.

In the case of Fig. 8, the current collector is also used as a heat transfer plate in which the current collector is also a cavity with the cathode and the anode, and simultaneously transfers electrons and heat by contact of the granular material. The negative electrode current collector and heat transfer plate 56 and the positive electrode current collector and heat transfer plate 58 flow heat medium such as water and air, and heat recovery and heat supply are performed. Details of the charge and discharge are shown in FIG. The shape of the heat transfer surface is not limited to tubular and plate shapes, and other shapes may be adopted.

Other configurations and operations are the same as those in the first embodiment. In addition, the structure of this embodiment can also be combined with the structure of 2nd Embodiment, 3rd Embodiment, and 6th Embodiment mentioned later.

9 and 10 show a sixth embodiment of the battery of the present invention. The present embodiment is provided with a device for extracting the granulated material composed of the active material from the cell, and a supply device for supplying the granular material composed of the active material to the cell, and further, a device for regenerating the extracted granular material, and make up of the granular material. An apparatus for (supplement) and an apparatus for changing the extracted powder active material into a powder-based powder active material by a thermochemical reaction or an electrochemical reaction may be provided.

First, the charge and discharge will be described in detail with respect to the battery of the present embodiment.

(charge)

Voltage is applied to the battery, and electrons are supplied by the negative electrode current collector 20. The electrons are reacted by the negative electrode current collector 20 by being moved directly to the powder active material of the negative electrode or with the powder therebetween. The ions generated by the reaction pass through the separator 10 and enter the positive electrode cell 14, where they react with the particulate active material of the positive electrode to emit electrons. These electrons are transported to the discharge means 22 by directly moving to the positive electrode current collector 22 with the powder in between.

(Discharge)

The battery is loaded and electrons are supplied by the negative electrode current collector 20. The electrons are discharged from the active material which has been cationized in the negative electrode cell 12, and move directly or negatively in the negative electrode current collector 20. The ions generated by the reaction pass through the separator 10 and enter the positive cell 14, where they react with the particulate active material and electrons of the positive electrode. The electrons are supplied to the load means 26 by moving to a positive electrode current collector 22 with the powder in between.

Other configurations and operations are the same as those in the first embodiment.

Next, with reference to FIG. 9, the regeneration and make up of an active material (catalyst) are demonstrated in detail about the battery of this embodiment. In addition, although only the structure of the cathode side is shown in FIG. 9, the same apparatus etc. are provided in the anode side.

As shown in FIG. 9, the granular material composed of the active material deteriorated by charging and discharging is taken out from the negative electrode cell 12 as a slurry together with the electrolyte solution (electrolyte solution), and in the separator 60, if necessary, part or all Is discarded. The electrolyte solution is separated, and the granular material supplied from the separator 60 to the regenerator 62 is subjected to acid treatment such as washing with hydrochloric acid in the regenerator 62. The granules regenerated in the regenerator 62 are supplied to the mixer 64, where new granules corresponding to the powders discarded from the separator 60 are supplied from the granule hopper 66 for make-up. The granulated material which is regenerated and made up is mixed with the electrolyte solution again in the mixer 64 and supplied as a slurry from the slurry pump (not shown) to the negative electrode cell 12. In addition, the structure which isolate | separates and mixes electrolyte solution is abbreviate | omitted.

In addition, with reference to FIG. 10, the regeneration and make up by reaction with respect to the battery of this embodiment are demonstrated in detail. In addition, although only the structure of the cathode side is shown in FIG. 10, the same apparatus etc. are also provided in the anode side.

As shown in FIG. 10, the granules produced by charging and discharging are taken out from the negative electrode cell 12 as a slurry together with the electrolyte, and some or all of them are discarded if necessary in the separator 60. The electrolyte is separated, and the granules supplied from the separator 60 to the reactor 68 become an active material that can react with the fuel supplied from the fuel supply pipe 70 in the reactor 68 and discharge again. The charged granules in the reactor 68 are supplied to the mixer 64, where a new amount of granules equivalent to the powders discarded from the separator 60 is supplied from the powder hopper 66 for make-up. The regenerated and make-up granules are mixed with the electrolyte solution again in the mixer 64 and supplied as slurry to the negative electrode cell 12 from a slurry pump (not shown). In addition, the structure which isolate | separates and mixes electrolyte solution is abbreviate | omitted.

In the reactor 68, for example, in the case of a nickel hydrogen battery, the following reaction is performed.

M + x / 2H ₂ → MH _x M: hydrogen absorption alloy

Whereby the active material is produced with _X MH produced by the reaction is conducted in the following by charging.

^{_{M + xH 2 0 + xe -}} → MH x + xOH -

In the case of a nickel-metal hydride battery, the following reaction is performed in an anode reactor by oxygen or air.

Ni (OH) ₂ + 1/4 O ₂ → NiOOH + 1 / 2H ₂ 0

Thereby, an active material is produced like NiOOH produced | generated by the following reaction performed at the time of charge.

^{_{Ni (OH) 2 + OH -}} → NiOOH + H 2 0 + e -

In addition, the structure of this embodiment can also be combined suitably with the structure of 2nd embodiment, 3rd embodiment, and 5th embodiment.

11 shows a seventh embodiment of the battery of the present invention. In this embodiment, the granular material comprising the active material of the negative electrode is a hydrogen storage alloy, the stirring gas of the negative electrode is hydrogen, the granular material of the positive electrode is nickel hydroxide, and the stirring gas of the positive electrode is oxygen or air. It is done. As shown in FIG. 11, the hydrogen storage alloy and the electrolyte solution 48 are loaded in the cathode cell 12, and the nickel hydroxide and electrolyte solution 50 are loaded in the cathode cell 14. 72 is a gas supply line. By the gas supply pipe 72, hydrogen is supplied to the cathode cell 12, and oxygen or air is supplied to the anode cell 14. As the hydrogen storage alloy, La _0.3 (Ce, Nd) _0.15 Zr _0.05 Ni _3.8 Co _0.8 Al _0.5 or the like is used, for example. In addition, as an electrolyte solution, KOH aqueous solution etc. are used, for example.

In the negative electrode cell 12, the following reaction occurs in which hydrogen is supplied into the hydrogen storage alloy M and the electrolyte solution 48.

M + x / 2H ₂ → MH _x

When the load of the load means 26 is applied, hydrogen stored in the hydrogen storage alloy reacts with a hydroxyl group in the electrolyte solution to release electrons and water.

^{_{MH x + x0H - → M +}} xH 2 O + xe -

The emitted electrons move directly to the negative electrode current collector 20 or with the hydrogen storage alloy interposed therebetween. Electrons move through the load means 26 by the negative electrode current collector 20 and move to the positive electrode current collector 22. The electrons move from the anode current collector 22 to nickel oxyhydroxide, and the nickel oxyhydroxide is interposed or directly moves to react with water to produce nickel hydroxide and hydroxyl groups. The hydroxyl group is introduced into the cathode cell 12 through the separator 10 and reacts with the hydrogen storage alloy.

^{_{NiOOH + H 2 0 + e -}} → Ni (OH) 2 + OH -

In the case of a nickel-metal hydride battery, the following reaction is performed on the positive electrode cell 14 by oxygen or air.

Ni (OH) ₂ + 1/4 O ₂ → NiOOH + 1/2 H ₂ O

Thereby, an active material is produced like NiOOH produced | generated by the following reaction performed at the time of charge.

^{_{Ni (OH) 2 + OH -}} → NiOOH + H 2 O + e -

Other configurations and operations are the same as those in the first embodiment. In addition, the battery of this embodiment can also be implemented with the structure of 2nd Embodiment, 3rd Embodiment, 5th Embodiment, and 6th Embodiment.

12 shows an eighth embodiment of the battery of the present invention. In this embodiment, the cell is not completely divided into ion permeable separators. Instead, the cell is divided into ion permeable separators 10a in a state in the upper part of the cell. Other configurations and operations are the same as those in the first to seventh embodiments.

Fig. 13 shows a ninth embodiment of the battery of the present invention. In this embodiment, the bag 74 is formed of a porous body filled with the electrolyte solution 76 in the cell, and the granular material of the active material releasing electrons in the electrolyte solution 76 is stored as a fixed layer without dividing the cell 74. ), And a bag 80 made of a porous body in which a granule of an active material absorbing electrons is accommodated as a fixed layer, and a current collector of a conductor that contacts the granules of the active material, ie, in these bags (78.80), The negative electrode collector 82 and the positive electrode collector 84 are provided. It is possible to use a cell or the like instead of a bag, and the shape does not matter. A porous nickel sheet is mentioned as a porous body. Other configurations and operations are the same as those in the first to seventh embodiments.

EMBODIMENT OF THE INVENTION Hereinafter, embodiment of the battery of the three-dimensional structure which concerns on this invention is described based on drawing.

 Fig. 14 is a perspective view and a schematic sectional view showing an example of an demonstration tester according to a first embodiment of a stacked three-dimensional battery of the present invention, and Fig. 15 is a perspective view showing a part of main components before assembly (disassembled state) thereof.

As shown in Fig. 14, the stacked three-dimensional battery 101 of this example is a nickel-metal hydride battery, with two cell members 121 installed through the central central opening 121a as shown in Fig. 15 in the thickness direction. In this example, two sets (four in total) of cell members 121b are provided. Around the opening part 121a of one surface of each cell member 121, a shallow concave portion 121b is formed in an annular shape in the annular form, and the cell member 121 is formed. An approximately square alkaline ion permeable separator (Teflon separator in this example) 105 is sandwiched in the concave portion 121b. The cell separator 105 is a membranous body which allows only ions to pass but does not pass through the active materials n and h and electricity. In addition to the above, an element plate, an ion exchange resin film, glass, and the like are used.

In addition, two liquid inlets 121c are formed on the upper surface of each cell member 121 so as to face the opening 121a and penetrate up and down to be spaced apart in the width direction. The rubber stopper 122 is detachably attached thereto.

Alkali-resistant and conductive plate-shaped current collectors (nickel plates in this example) 107 are sandwiched in the concave portion 121b between the inner cells 121 and 121 of each set. Further, at both ends of the two sets of cell members 121, a plate-shaped current collector (nickel plate in this example) having a height higher than that of the cell member 121 in the same width as that of the cell member 121 which is alkaline in conductivity and conductive. And 108). The rubber packing 109 having the same shape as that of the opening 121a and having the opening 109a at the center thereof is formed between the cell members 121 and 121 and between the cell members 121 and 121. It is contained between the whole 106 or 108. In the cell member 121, the packing 109, and the current collectors 106 and 108, a plurality of insertion holes 121d, 109d, 106d, 108d penetrating in the thickness direction are formed around the openings 121a and 109a. It is snow-covered integrally at intervals in the direction of). Then, a plurality of non-conductive bolts 123 are inserted into the plurality of insertion holes 121d, 109d, 106d, and 108d in series, and the nut (not shown) is filled in the tip threaded portion 123a of the bolt 123 to be coupled ( Are tightly tightened. Further, small holes 106e and 108e are laid at the upper ends of the current collectors 106 and 108e at the left end (anode) and the right end (cathode), with the left end and the right end in this example. The positive terminal 124 and the negative terminal 125 are attached to the small holes 106e and 108e at both ends of the whole 106 and 108, respectively, and one end of the wirings 126 and 127 are connected.                 

A potassium hydroxide aqueous solution k as an electrolyte solution is injected into each cell member 121 by a liquid injection port 121c, and the powder active material of the positive electrode is sequentially formed from the left inner cell member 121 in FIG. 14B. Nickel hydroxide (n), hydrogen occlusion alloy (h) as a particulate active material of a negative electrode, nickel hydroxide (n) as a particulate active material of a positive electrode, and hydrogen occlusion alloy (h) as a particulate active material of a negative electrode are potassium hydroxide aqueous solution (k) It is put in. As a result, the anode cell 103, the cathode cell 104, the anode cell 103, and the cathode cell 104 are sequentially formed from the left end to the right end of the drawing.

Although the stacked three-dimensional battery 101 is configured as described above, the battery 101 of the present example has a structure in which two nickel-metal hydride cells (secondary batteries) are connected in series to form a battery having a voltage of about 2.4V. . Thus, the load means 130 such as a 2.4V light bulb is connected between the positive terminal 124 and the negative terminal 125 of the battery 101 by wirings 126 and 127. In the charged state, nickel oxyhydroxide (n) in the positive electrode cell 103 in contact with the left positive electrode collector 106 having the positive electrode terminal 124 is electron (e ⁻ ) as the positive electrode current collector 106. Electrons (e ⁻ ) are supplied together with hydrogen ions to nickel oxyhydroxide (n) which is in contact with each other in series and becomes nickel hydroxide. In the cathode cell 104, the hydrogen storage alloy h emits electrons e ⁻ and hydrogen ions H ⁺ , and the hydrogen ions pass through the ion permeable separator 105 to the anode cell 103. Goes. That is, NiOOH + H ⁺ + e ^- is a → Ni (OH) _2.

MH _X → M + xH ⁺ + xe ^- M: hydrogen absorption alloy

Subsequently, electrons (e ⁻ ) are collected (collected) into the current collector member 107 constituting a partition wall with the positive electrode cell 103 of the second unit battery through the contact portion of the hydrogen storage alloy h. The nickel oxyhydroxide (n) in the positive electrode cell 103 of the battery receives electrons (e ⁻ ) from the battery member 107, and electrons (e ⁻ ) are supplied to the nickel oxyhydroxide (n) in series contact. It is made of nickel hydroxide. In addition, the hydrogen storage alloy h emits electrons e ^{− in the} cathode cell 104, thereby generating hydrogen ions H ⁺ . Electrons (e ⁻ ) emitted into the negative electrode cell 104 are collected in the negative electrode current collector 108, move from the negative electrode terminal 125 to the load means 130 through the wire 127, and to the wire 126. The positive electrode current collector 106 moves to the positive electrode current collector 106. Thereby, the current by the positive electrode terminal 124 of the positive electrode current collector 106 is supplied to the load means 130, and flows to the negative electrode terminal 125 of the negative electrode current collector 108. In this manner, a voltage of 1.2 V x 2 (2.4 V) is generated.

On the other hand, charging to the three-dimensional battery 101 is performed in the following aspects. A predetermined voltage is applied to the battery 101 by the charger 131, and electrons e ⁻ are supplied to the negative electrode cell 104 by the negative electrode current collector 108 (negative electrode terminal 125). Electron (e ^-) is caused to move into the hydrogen absorbing alloy (h) and, thereby, the following reaction occurs hydroxyl ions.

^{_{M + xH 2 O + xe -}} → MH x + x0H - M: hydrogen storage alloy

The hydroxyl ions (OH ⁻ ) generated in the cathode cell 104 move into the anode cell 103 on the left side through the ion permeable separator 105, and react with nickel hydroxide (n) as follows to form electrons (e ⁻ ). Emits.

_{Ni (OH) · 2 + OH} - → NiOOH + H 2 O + e -

In the anode cell 103, the emitted electrons (e ⁻ ) are collected by the current collecting member 107 and are transferred to the hydrogen storage alloy (h) in the cathode cell 104 near the left side, whereby the reaction shown in the above formula is represented. Occurs, and hydroxyl ions are generated. The hydroxyl ions (OH ⁻ ) generated in the cathode cell 104 move into the anode cell 103 at the left end through the ion permeable separator 105, and react with nickel hydroxide (n) as described above to form electrons (e ⁻ ). Release. Electrons e ⁻ are collected in the positive electrode current collector 106 (positive electrode terminal 124) and sent to the charger 131.

Fig. 16 is a central longitudinal sectional view conceptually showing the second embodiment of the stacked three-dimensional battery of the present invention.

As shown in FIG. 16, the three-dimensional battery 101-1 of the present example is a lead battery, and has a structure in which the lead battery 102 is connected in series of six sets. The lead acid battery 102 is provided with the positive electrode 103 and the negative electrode 104 which divided the intermediate part into the acid-resistant ion permeable separator 105. As shown in FIG. The left end wall of the positive cell 103 of the unit cell 102 of the left end (Article 1) and the right end wall of the negative cell 104 of the unit cell 102 of the right end (Article 6) are respectively the current collector 106. , 108, which is formed of sidewalls of the entire acid resistance road (platinum plate or lead plate), and includes the right end wall of the negative electrode cell 104 of the first unit cell 102 and the positive cell 103 of the unit cell 102 of the sixth unit. The left end wall of) is made of the side wall (platinum plate or lead plate) of the acid resistant conductor as the current collector member 107. In addition, the four sets of unit cells 102 located in the middle are connected in series with the acid resistant conductor (platinum plate or lead plate) interposed between the sets of the unit cells 102 as the current collector member 107 serving as a partition. In addition, the unit cells 102 at the left end (Article 1) and the right end (Article 6) are also connected in series with a side wall (platinum plate or lead plate) of the acid resistant conductor serving as the current collector member 107 interposed therebetween.

Each cell 103, 104 is filled with a common oil solution, in this example, a rare oil solution (sulfuric acid solution) r. In the dilute acid solution in the anode cell 103, a powder A of lead dioxide (PbO ₂ ) is introduced to form a fixed layer. On the other hand, in the rare oil solution in the negative electrode cell 104, the powder B of metal lead (Pb) is thrown in, and the fixed layer is formed.

The three-dimensional battery 101-1 according to the second embodiment having the above configuration is discharged as follows. That is, the positive electrode cell 103 in contact with the positive electrode current collector 106 at the left end receives electrons from the current collector 106, and electrons are supplied to lead dioxide (A) and react with lead sulfate (PbSO ₄ ). And ions are generated.

_{PbO 2 + H 2 SO 4 +} 2H + + 2e - → PbSO 4 + 2H 2 0

Next, ions in the anode cell 103 are moved into the cathode cell 104 by the ion permeable separator 105, react with the metal lead B to release electrons, and oxidize to lead sulfate.

_{Pb + H 2 SO 4 → PbSO} 4 + 2H + + 2e -

The electrons in the negative electrode cell 104 are collected by the current collecting member 107, move into the positive electrode cell 103 near the left side, and the electrons are supplied to the lead dioxide (A) and react to form lead sulfate (PbSO ₄ ). , Ions are generated. Ions in the anode cell 103 move into the cathode cell 104 by the ion permeable separator 105, react with the metal foil B to release electrons, oxidize, and become lead sulfate. This reaction is repeated sequentially in each unit cell 102, and electrons move from the negative electrode collector 108 at the right end to the positive electrode collector 106 at the left end with a load means (not shown) interposed therebetween. Thus, current flows from the positive electrode current collector 106 to the negative electrode current collector 108 at the right end with the load means 130 (FIG. 14) interposed therebetween. In this example, a voltage of about 13.6V is generated. In addition, as long as it is an acid-resistant conductor, any thing can be used for an electrical power collector and an electrode, for example, carbon and a conductive polymer may be sufficient.

Fig. 17 is a central longitudinal sectional view conceptually showing the third embodiment of the stacked three-dimensional battery of the present invention.

As shown in FIG. 17, the three-dimensional battery 101-2 of this example is the same as the second embodiment of FIG. 16, but is a lead battery, but rotation of the rotating shaft 132 penetrating the battery 101-2 in the axial direction is not possible. Freely arranged and rotated by manual or rotary drive (not shown). At a position corresponding to each cell 103 or 104 on the rotating shaft 132, a plurality of stirring roots 132a are provided so as to protrude in a direction orthogonal to each other. Although the rare oil solution r in 104 is comprised so that it can be stirred with lead dioxide (A) or metal lead (B), it differs from the battery 101-1 of 2nd Embodiment.

Therefore, according to the three-dimensional battery 101-2 of this example, each of the electrode granules A and B and the current collectors 106 and 108 are stirred by stirring lead dioxide (A) and metal foil (B) as electrode granules. Or the contact with the current collector member 107 becomes good, it is possible to increase the capacity of each cell 103, 104 (cell member 121, see Fig. 14), and the amount of power can be increased. In addition, since adhesion of lead sulfate particles can be prevented, a lead plate can be used for the current collectors 106 and 108 and the current collector member 107. In addition, since the point provided with the stirring means 132 is removed and it is common with the battery 101-1 which concerns on 2nd Embodiment, it shows using the same code | symbol as the member common to 2nd Embodiment, and abbreviate | omits description. .

18 is a central longitudinal sectional view conceptually illustrating the fourth embodiment of the stacked three-dimensional battery of the present invention.

As shown in FIG. 18, the three-dimensional battery 101-3 of this example is made of a nickel hydride secondary battery as in the first embodiment of FIG. 14, but the capacitance of the positive electrode 103 and the negative electrode 104 is considerably increased. It was enlarged. Instead, the plurality of studs 106a, 107a, 108a are each extended apart from the current collectors 106 and 108 and the current collector member 107 into the positive cell 103 or the negative cell 104, respectively.出) is installed. In this example, since the nickel plates are used for the current collectors 106 and 108 and the current collector member 107, the studs 106a, 107a, and 108a are also integrally formed of a nickel plate. In the battery 101-3 of this example, the volume of each cell 103, 104 is greatly enlarged, but the electrode granules n, h have a current collector 106, 108 and a current collector with the studs interposed therebetween. Since the member 107 is reliably contacted, it is possible to sufficiently transmit electricity (electron / current). In addition, it is possible to use combining the stirring means 132 of 3rd Embodiment with the battery 101-3 of this example.

Fig. 19 shows a fifth embodiment of the stacked three-dimensional battery of the present invention. In this embodiment, the cell is not completely divided into ion permeable separators, and the upper part of the cell is divided into open ion permeable separators 105a. Other configurations and operations are the same as those in the first to fourth embodiments.

20 shows a sixth embodiment of the stacked three-dimensional battery of the present invention. The present embodiment does not distinguish the cell 160, and the bag 162 is made of a porous body in which the electrolyte solution r is filled in the cell, and the granular material of the active material absorbing electrons in the electrolyte solution r is stored as a fixed layer. ) And a bag 164 made of a porous body in which the granules of the active material emitting electrons are stored as a fixed layer, and the current collectors of the conductors contacting the granules of the active material, i.e., the anodes, in these bags 162 and 164. The current collector 166 and the negative electrode current collector 168 are provided. It is possible to use a thing on a cell etc. instead of a bag, and the shape does not matter. A porous nickel sheet is mentioned as a porous body. Other configurations and operations are the same as those of the first to fourth embodiments.

As mentioned above, although embodiment of the three-dimensional battery of this invention was described, it can also be implemented as follows.

① In addition to the above, for example, a combination of the active material powder of the positive electrode and the negative electrode may be combined with nickel hydroxide and cadmium, or nickel hydroxide and iron, nickel hydroxide and iron carbide (Fe ₃ C), cobalt (or manganese) and lithium. Alternatively, it is possible to use a combination of nickel hydroxide and zinc.

(2) In the above embodiment, the structure in which the unit cells 102 are connected in series of two to six in series with the conductive member 107 of conduction (acid resistance or alkali resistance) interposed therebetween, is any number corresponding to the required voltage. It is also possible to connect in series.

(3) The volume of the cell member 121 can also be increased in response to the required voltage capacity of the battery, and it is possible to cope by providing a stirring means or a stud if necessary.

Since this invention is comprised as mentioned above, it is suitable for the fixed bed type battery which put granular material in the cell using an active material as a granular material, and the laminated three-dimensional battery which produces various advantages according to scale up.

Claims (15)

In an electrolyte solution in one cell of two cells connected through a member through which ions pass, a granular material of an active material that emits electrons, and contains a material having high electron conductivity or coating a material having high electron conductivity on its surface. Powder is formed as a fixed layer, and in the electrolyte solution in the other cell, the powder is a powder of an active material that absorbs electrons, and the powder is formed by coating a material having high electron conductivity or coating a material having high electron conductivity on the surface thereof. And a current collector for a conductor that is charged and contacts with the granules as active materials in two cells, and wherein the fixed layer makes the granules of the active materials contact with the granules of adjacent active materials. The battery according to claim 1, wherein the powder of the active material is a porous body. delete The battery according to claim 1 or 2, wherein the current collector that comes into contact with the granular material as the active material is any of a rod, a plate, and a tubular shape. The battery according to claim 1 or 2, wherein a heat transfer surface for providing a constant reaction temperature in the battery is provided in the cell. The method of claim 5, A battery, wherein the heat transfer surface is any one of a tubular current collector and a plate current collector in contact with the granular material as the active material. The battery according to claim 1 or 2, wherein the cell is connected with extraction means for extracting the deteriorated granular material from the cell and supply means for supplying the granular material, which is an active material, to the cell, respectively. The method of claim 7, wherein At least one of the regeneration means for regenerating the granulated material which is the extracted active material and the make-up means for replenishing the granular material which is the active material is connected to the extraction means, and the granulated material of the regenerated or newly changed active material is supplied from the cell. A battery characterized by being supplied to the inside. The method of claim 7, wherein The extraction means is connected with a reaction means for changing the granulated material, which is the extracted active material, into a granular material in a charged state by a thermochemical reaction or an electrochemical reaction, so that the granular material of the active material in a charged state is supplied into the cell from the supply means. Battery. The battery according to claim 1 or 2, wherein the granular material which is an active material on the negative electrode side is a granule of hydrogen storage alloy, and the granular material which is an active material on the positive electrode side is a granule of nickel hydroxide. The granular material as claimed in claim 1 or 2, wherein the granular material as the active material on the negative electrode side is a granule of hydrogen storage alloy, the gas introduced into the negative electrode side is hydrogen, and the granular material as the active material on the positive electrode side is granular material of nickel hydroxide. The gas introduced into the side is oxygen or air. One cell is filled with an electrolyte solution and connected to a set of cells connected through a member that passes ions but does not pass electricity, and is a granule of an active material that emits electrons in the electrolyte solution. A powder containing a high substance or coating a substance having high electron conductivity on a surface thereof is added to form a fixed layer, and the other cell is filled with an electrolyte solution, and the active material which absorbs electrons in the electrolyte solution is separated. And a granular material containing a substance having high electron conductivity or coating a substance having high electron conductivity on a surface thereof to form a fixed layer, and a plurality of sets of unit cells having these two fixed layers are formed. By connecting in series with a conductive current collecting member which is also used in contact with the powder To form a sieve, and to contact the granules at both ends of the cell, and to install a current collector that combines the positive electrode and the negative electrode. The battery characterized by the above-mentioned. It is a granule of an active material which fills an electrolyte solution in a cell, and discharge | releases an electron, The porous body which accommodated as a fixed layer the granule which contains the substance with high electron conductivity, or coats the substance with high electron conductivity on the surface, and absorbs an electron A plurality of unit cells comprising a porous body of a porous body which is a granular material of an active material and contains a porous material containing a material having high electronic conductivity or coating a material having high electronic conductivity on its surface as a fixed layer in the electrolyte solution. The tank serves as a unit by interposing a partition wall between the cells and a conductive current collecting member in contact with the powder in series so as to be integrated, and in contact with the powder at both ends of the cell. A current collector is used, and in the fixed layer, the powder of the active material is adjacent to the active material. And in contact with the powder and granular material of the battery, characterized in that configured a multi-layer three-dimensional battery. delete  The battery according to claim 12 or 13, wherein a conductive stud is provided so as to protrude integrally from the current collector member or the current collector into the cell.

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