阅读说明：本技术 金属负极电池 (Metal cathode battery ) 是由 猪口正幸 无漏田正男 于 2018-02-27 设计创作，主要内容包括：在负极主要由铝、镁、锌、锂等金属构成的金属负极电池中,在负极与电解液接触时容易发生自放电,容易产生电池的容量损失大的问题。本发明的目的在于提供一种金属负极电池,其可减轻该自放电量,缓和使用时或保存时的电池的容量损失,并且根据需求稳定地改变电池输出。提供一种金属负极电池,该金属负极电池具有：正极使用正极活性物质或空气等的正极电极；主要由铝、镁、锌、锂等金属构成的金属负极电极；和电解液,其中,所述金属负极电池具备上述金属负极电极根据需求浸渍在上述电解液中的浸渍单元。(In a metal negative electrode battery in which the negative electrode is mainly composed of a metal such as aluminum, magnesium, zinc, or lithium, self-discharge is likely to occur when the negative electrode contacts an electrolyte solution, and a problem of a large capacity loss of the battery is likely to occur. The purpose of the present invention is to provide a metal negative electrode battery that can reduce the amount of self-discharge, alleviate the capacity loss of the battery during use or storage, and stably change the battery output as needed. Provided is a metal negative electrode battery having: a positive electrode using a positive active material or air as a positive electrode; a metal negative electrode mainly composed of metals such as aluminum, magnesium, zinc, lithium, and the like; and an electrolytic solution, wherein the metal negative electrode battery includes a dipping unit in which the metal negative electrode is dipped in the electrolytic solution as required.)

1. A metal negative electrode battery is provided with a positive electrode, a metal negative electrode, and an electrolyte, wherein the metal negative electrode battery is provided with a dipping unit for dipping the metal negative electrode in the electrolyte as required.

2. The metal negative electrode battery according to claim 1, wherein an electrode of the metal negative electrode is composed of a sol metal.

3. The metal negative electrode battery according to claim 1 or 2, wherein the metal negative electrode battery comprises the following impregnation unit: the metal negative electrode is immersed into the electrolyte according to the requirement by extruding or pushing the metal negative electrode back to the electrolyte or by lifting or descending the liquid level of the electrolyte.

4. The metal negative electrode battery according to any one of claims 1 to 3, wherein an electrode of the metal negative electrode is mainly composed of a metal of aluminum, magnesium, zinc or lithium, or an alloy or a mixed composition thereof.

5. The metal negative electrode battery according to any one of claims 1 to 4, wherein an output voltage of the battery and an electromotive force of a negative electrode are detected, and an area of the negative electrode immersed in the electrolyte is controlled according to increase or decrease of the detected output voltage and electromotive force, thereby performing output control.

6. The metal negative electrode battery according to any one of claims 1 to 5, wherein the metal negative electrode battery has a water level adjustment mechanism for the electrolyte, and the electrolyte is maintained at a constant water level.

7. The metal negative electrode battery according to any one of claims 1 to 6, wherein a residue after the reaction of the negative electrode is precipitated by a precipitation filter.

8. The metal negative electrode battery according to any one of claims 1 to 7, wherein the metal negative electrode battery has a separator that separates the electrolyte into a positive electrode-side electrolyte and a negative electrode-side electrolyte,

the metal negative electrode battery is provided with any one or two mechanisms of an electrolyte delivery mechanism for delivering negative electrolyte from the negative electrolyte and an electrolyte delivery mechanism for delivering positive electrolyte from the positive electrolyte, and the concentration of the negative electrolyte and the concentration of the positive electrolyte or the concentrations of the two electrolytes are controlled.

9. The metal negative electrode battery according to any one of claims 1 to 8, wherein the metal negative electrode battery comprises a reaction cassette that accommodates the metal negative electrode battery main body and the electrolyte sending-out mechanism integrally or separately from a part of these components.

10. The metal negative electrode battery according to any one of claims 1 to 9, wherein the metal negative electrode battery is formed in a sealed structure using a material through which a generated gas passes but the electrolyte does not leak.

Technical Field

The present invention relates to a metal negative electrode battery whose negative electrode is mainly composed of metal.

Background

In recent years, a metal negative electrode battery using a metal such as aluminum or magnesium having a high energy density as a cathode has been attracting attention. The metal negative electrode battery comprises an active material positive electrode battery, wherein the negative electrode of the active material positive electrode battery mainly comprises metals such as aluminum or magnesium, and the positive electrode of the active material positive electrode battery is provided with a positive electrode active material; an air battery using an air electrode as a positive electrode.

Patent document 1 proposes an aluminum negative electrode battery in which the negative electrode includes aluminum or an aluminum alloy and the positive electrode includes a positive electrode active material. Patent document 2 proposes an air battery using aluminum or magnesium as a negative electrode.

Patent document 3 proposes an air battery having a porous member in the battery, and an aluminum negative electrode columnar body capable of being continuously replenished is placed in contact with the porous member.

Patent document 4 proposes a roll-type magnesium battery in which a negative electrode film formed by laminating a magnesium foil on an insulating film is wound and unwound, and the magnesium foil is divided into blocks to make and break the power generation.

Disclosure of Invention

Problems to be solved by the invention

In a metal negative electrode battery in which the negative electrode is mainly composed of a metal such as aluminum or magnesium, self-discharge is likely to occur when the negative electrode contacts the electrolyte, and a problem of a large capacity loss of the battery is likely to occur.

In addition, the state of the electrolyte and the state of the electrode surface in the battery are also likely to change, and it is difficult to obtain the same output even if the negative electrode is supplied in an apparently identical state as in patent document 3. Even if the power generation can be turned on and off in the reel battery as in patent document 4, it is difficult to change the amount of power generation according to the demand.

The invention aims to provide a metal negative electrode battery which can reduce the self-discharge amount, alleviate the capacity loss of the battery during use or storage, and stably change the battery output according to the requirement; provided is a metal negative electrode battery which is generally a metal negative electrode battery having a large limitation in structure and size and which has a high degree of freedom.

Means for solving the problems

In order to solve the above problems, the present invention provides the following metal negative electrode battery.

(1) A metal negative electrode battery having a positive electrode, a metal negative electrode, and an electrolyte solution, wherein the metal negative electrode battery includes a dipping unit for dipping the metal negative electrode in the electrolyte solution as required.

(2) The metal negative electrode battery according to (1), wherein an electrode of the metal negative electrode is made of a sol metal.

(3) The metal negative electrode battery according to (1) or (2), wherein the metal negative electrode battery includes the following impregnation unit: the metal negative electrode is immersed in the electrolyte as needed by pushing or pushing the metal negative electrode out of or back into the electrolyte or by raising or lowering the liquid level of the electrolyte.

(4) The metal negative electrode battery according to any one of the above (1) to (3), wherein the electrode of the metal negative electrode is mainly composed of a metal of aluminum, magnesium, zinc or lithium, or an alloy or a mixed composition thereof.

(5) The metal negative electrode battery according to any one of the above (1) to (4), wherein an output voltage of the battery is detected, and an area of the negative electrode immersed in the electrolyte is controlled according to an increase or decrease in the output voltage, thereby performing output control.

(6) The metal negative electrode battery according to any one of the above (1) to (5), wherein the metal negative electrode battery has a water level adjustment mechanism for the electrolyte solution, and the electrolyte solution is maintained at a constant water level.

(7) The metal negative electrode battery according to any one of (1) to (6), wherein a residue after the reaction of the negative electrode is precipitated by a precipitation filter.

(8) The metal negative electrode battery according to any one of (1) to (7), wherein the metal negative electrode battery has a separator for separating the electrolyte into a positive electrode-side electrolyte and a negative electrode-side electrolyte, and the metal negative electrode battery has one or both of an electrolyte feeding mechanism for feeding a negative electrode electrolyte to the negative electrode electrolyte and an electrolyte feeding mechanism for feeding a positive electrode electrolyte to the positive electrode electrolyte, and the concentrations of the negative electrode electrolyte and the positive electrode electrolyte or both electrolytes are controlled.

(9) The metal negative electrode battery according to any one of the above (1) to (8), wherein the metal negative electrode battery includes a reaction cassette that accommodates the metal negative electrode battery main body and the electrolyte sending-out mechanism integrally or separately from a part of these components.

(10) The metal negative electrode battery according to any one of the above (1) to (9), wherein the metal negative electrode battery has a sealed structure using a material that allows generated gas to permeate therethrough but prevents the electrolyte from leaking.

ADVANTAGEOUS EFFECTS OF INVENTION

According to the present invention, a metal negative electrode battery capable of reducing the amount of self-discharge, alleviating the capacity loss of the battery during use or storage, and stably changing the battery output as required can be provided by devising the method of contacting the negative electrode with the electrolyte.

Drawings

Fig. 1 is a diagram illustrating the principle of an aluminum-air battery.

Fig. 2 is a diagram illustrating the structure of the metal negative electrode battery 10 according to embodiment 1.

Fig. 3 is a circuit block diagram of the control board 6 of fig. 2.

Fig. 4 is a diagram illustrating the structure of the metal negative electrode battery 20 according to embodiment 2.

Fig. 5 is a diagram illustrating the structure of the metal negative electrode battery 30 according to embodiment 3.

Fig. 6 is a diagram illustrating the structure of the metal negative electrode battery 40 according to embodiment 4.

Fig. 7 is a diagram illustrating the structure of a sealed metal negative electrode battery 50 according to embodiment 5.

Fig. 8 is a diagram showing the structure of a metal negative electrode battery 60 according to embodiment 6.

Fig. 9 is a diagram showing the structure of a sol metal negative electrode battery 70 according to embodiment 7.

Fig. 10 is a flowchart regarding the feed control of the aluminum foil.

Fig. 11 is a flowchart regarding management of the negative electrode electrolyte in fig. 5 and 6.

Fig. 12 is a flowchart regarding positive electrode potential control.

Fig. 13 is a graph showing the target positive electrode potential Vtar characteristic with the positive electrode potential Vpee as a parameter.

Detailed Description

The positive electrode of the present invention is an electrode paired with a metal negative electrode, and for example, an electrode used in an active material positive electrode battery in which a positive electrode has a positive electrode active material, an air battery in which an air electrode is used as a positive electrode, or the like can be used.

The metal negative electrode of the present invention is provided with an auxiliary material and a current collector as needed, and the metal electrode contains an alloy or a mixed composition of the metal electrodes, in addition to a simple metal such as aluminum, magnesium, zinc, and lithium.

In the case of an aluminum body, an aluminum foil for cooking used in general households can be used, and therefore, it is preferable from the viewpoint of cost and versatility.

In the case of a magnesium host, it is preferable from the viewpoint of obtaining a higher generated voltage.

In the case of zinc, the generation voltage is low, but the self-discharge is small, which is preferable in this respect.

In the case of lithium, lithium is preferable in terms of obtaining a high power generation voltage and a high energy density.

The shape of the electrode includes, in addition to foil, a plate, a wire, a rod, a sintered body, a nonwoven fabric, a composite thereof, and a laminate thereof. In the case of the use of a lead-out metal negative electrode, the lead-out metal negative electrode is easy to be taken out when the cross section is uniform.

The foil is preferable in terms of being wound and stored, and the nonwoven fabric is preferable in terms of having a large surface area. Further, embossing, corrugating, etching, embossing, and the like are also preferable in terms of the expansion of the surface area.

In addition to the above shapes, the metal sol is also included. The sol metal is obtained by kneading a particulate metal, a powder metal, or a fine powder metal composed of the above metals into a sol agent. The sol metal can be handled similarly to a liquid, and therefore, the shape of storage and preservation can be arbitrary, and the supply of the negative electrode material can be performed by a pipe such as a tube, which is preferable from the viewpoint of the ability. It is preferable that the negative electrode material be supplied to a large amount of the battery from one place.

The electrolyte of the present invention is appropriately selected depending on the battery structure. For example, in the case of an aqueous alkaline solution, potassium hydroxide, sodium hydroxide, or the like; in the case of an acidic aqueous solution, sulfuric acid, phosphoric acid, or the like can be used.

In addition, sodium sulfide (Na) may be added₂S), sodium thiosulfate (Na)₂S₂O₃) Coarsening inhibitor, sodium acid pyrophosphate (Na)₂H₂P₂O₇) And self-discharge inhibitors.

The impregnation unit of the present invention is a unit in which the metal negative electrode is wetted into the electrolyte as required, and for example, the following method or the like may be adopted according to the required area: the metal negative electrode is immersed in the electrolyte by pushing or pushing the metal negative electrode out of or back into the electrolyte, or by raising or lowering the liquid level of the electrolyte.

As a method of pushing out or pushing back the metal negative electrode to the electrolyte, in the case of a plate shape, the metal negative electrode can be pushed out or pushed back by bringing the feed roller into contact with the metal negative electrode on one side, and by bringing the contact roller into contact with the metal negative electrode from the other side, and rotating the feed roller. If the rotation of the feed roller is stopped during the reaction, the metal negative electrode may be apparently pushed back. Further, the liquid such as circulating water of the electrolytic solution can be ejected from the nozzle at the front and back surfaces, whereby the extrusion can be performed. In the case of a block or rod, extrusion can be carried out by the following method: a method of inserting a metal negative electrode into a can and utilizing the fall due to its own weight; a method of applying an air/hydraulic pressure to the end face mechanically or; or a method of applying air or hydraulic pressure to the side surface and moving it. In addition, in the case of a cylinder, if the screw is screwed on the side, it can be pushed out or pushed back by rotating its own shaft. In the case of the sol metal 10a, extrusion or push back may be performed using a pump.

As a method of raising the liquid level of the electrolyte, in addition to gradually accumulating the electrolyte by a pump, natural dropping, or the like, a method of gradually reducing the bath volume of the electrolyte, a method of raising the bath by a capillary phenomenon, or the like can be employed. This method is preferable in that it enables centralized control when a plurality of batteries are operated.

The separator of the present invention can be used as needed, and any conventionally known separator can be used, and the mesh size is preferably small enough that the precipitates do not mix with each other. In addition, it is preferable to have strength to the extent of not being punctured by the precipitate. For example, porous films of polyethylene, polypropylene, polyethylene terephthalate, cellulose, and the like; nonwoven fabrics such as resin nonwoven fabrics and glass fiber nonwoven fabrics; or a solid electrolyte in which ions permeate the membrane and only ions pass through; and the like.

Hereinafter, embodiments of the metal negative electrode battery according to the present invention will be described in detail with reference to the drawings. In the drawings, the same elements are denoted by the same reference numerals, and redundant description thereof is omitted.

The metal negative electrode of the present invention has an air battery structure, and the metal negative electrode is made of aluminum as an example and made of foil as an example.

[ embodiment 1]

(constitution)

Fig. 1 is a diagram illustrating the principle of an aluminum-air battery. As shown in fig. 1, an aluminum-air battery 100 is configured by interposing an electrolyte 106 between a positive electrode (air electrode) 102 and a negative electrode (aluminum electrode) 104. At the positive electrode 102, a reaction of formula (1) in which a hydroxyl group is generated from oxygen in the air, electrons of the positive electrode, and water in the electrolyte occurs.

On the other hand, in the negative electrode, a reaction of formula (2) occurs in which aluminum hydroxide and electrons are generated from aluminum and hydroxyl groups. Therefore, the reaction of formula (3) to produce aluminum hydroxide from aluminum, oxygen and water as a whole occurs, and electric energy can be obtained.

[ solution 1]

3/4O₂+3/2H₂O +3e- → 3OH- (EO ═ 0.4V) formula (1)

[ solution 2]

AI+3OH-→AI(OH)₃+3e- (EO ═ 2.31V) formula (2)

[ solution 3]

4AI+3O₂+6H₂O＝4AI(OH)₃(EO +2.71V) formula (3)

Fig. 2 is a diagram illustrating the structure of the metal negative electrode battery 10 according to embodiment 1, and the metal negative electrode battery 10 includes a battery main body 2, an aluminum foil feeding unit 4 as a dipping unit, and a control board 6 for controlling the same.

The battery main body portion 2 is divided into two regions by a separator 2a, and the inside of one region (also referred to as "positive electrode side") 2-1 is filled with a positive electrode electrolyte 2b, and the inside of the other region (also referred to as "negative electrode side") 2-2 is filled with a negative electrode electrolyte 2 c.

As the separator 2a, for example, the above-described separator can be used. As the positive electrode electrolyte solution 2b, for example, 1 to 30% by weight of potassium hydroxide, sodium hydroxide, or the like can be used. As the negative electrode electrolyte 2c, for example, a solution obtained by adding 1 to 20 wt% of potassium hydroxide or sodium hydroxide to 5 to 30 wt% of brine can be used.

The surface of the positive electrode side 2-1 facing the separator 2a has a three-layer structure, and is formed with a positive electrode material 2e, a catalyst 2f located on the back surface of the positive electrode material 2e, and a porous membrane 2g having water-repellent properties located on the back surface of the catalyst 2 f. For example, a metal mesh, a metal foam, felt carbon, carbon cloth, carbon paper, etc. can be used as the positive electrode material 2e, a platinum group element (Ru, Rh, Pd, Os, Ir, Pt), an iron group element (Fe, Co, Ni), a manganese group element (Mn, Tc, Re, Bh), etc. can be used as the catalyst 2f, and for example, a porous fluororesin (PTFE, FEP, PVF, etc.), a porous hydrocarbon resin (PE, PP, etc.), a porous silicon film, etc. can be used as the porous film 2g having water repellency. The cathode material 2e and the catalyst 2f may be replaced or integrated. For example, a material in which the catalyst 2f is supported on a substance obtained by subjecting a metal mesh or carbon paper to water repellent treatment with a fluororesin may be used.

A limit sensor (electrolyte potential detection electrode) 2d is provided inside the negative electrolyte 2c on the negative electrode side 2-2. For example, a metal (Ti, Ta, Mo, W, or the like) or a carbon rod, wire, mesh, or a combination thereof, which has a low ionization tendency and a low cost, can be used as the position limit sensor 2 d.

The aluminum foil feeding unit 4 includes: an aluminum foil feed roller 4b for feeding an aluminum foil 4d hanging downward from an aluminum foil (aluminum foil) 4a wound in a roll shape into the negative electrode electrolyte 2c to impregnate or lift the same; and a motor 4c for driving and controlling the roller. The aluminum foil feed roller 4b is formed of a rod or a tube made of a metal (stainless steel, Ti, V, Ni, Zr, Mo, Ta, W, etc.) or carbon which is not easily corroded by the electrolytic solution.

The control board 6 receives the potential Vb + of the positive pole (+) of the battery, the potential Vb + of the negative pole (-) and the potential Vlim of the limit sensor 2d as a whole, and outputs the power source voltage Vo +, Vo-, which is externally used, and the driving voltage Vmo of the aluminum foil feeding motor 4b used in the battery.

Fig. 3 is a circuit block diagram of the control board 6 of fig. 2. The control board 6 includes: a booster circuit 12 that boosts a battery voltage between a potential Vb + of the positive electrode material 2e of the battery main body 2 and a potential Vb-of the negative electrode electrolyte 2c and supplies the boosted battery voltage to the MPU32 and the motor 4 c; and a booster circuit 14 supplied between the external output terminals Vo + and Vo-. The booster circuit 12 is, for example, a DC/DC converter circuit generating 2.5V required for driving the MPU 32. The booster circuit 14 is, for example, a DC/DC converter circuit generating 5.0V for external USB or the like.

Further, the control board 6 includes: an operational amplifier 16 and an a/D converter ADC1(18) for measuring battery current; an operational amplifier 22 and an a/D converter ADC2(24) for measuring the battery voltage; an operational amplifier 26 and an a/D converter ADC3(28) for measuring the potential Vlim of the limit sensor 2D; MPU32 for controlling the feeding of aluminum foil by the current and voltage of battery and the potential Vlim of limit sensor; a DAC34 that performs analog conversion of the output of the MPU 32; and a motor drive driver 36 that outputs a motor drive voltage Vmo for aluminum foil feeding.

(operation)

See fig. 2. At the negative electrode side 2-2, when the aluminum foil 4d is dipped into the negative electrode electrolyte 2c by the aluminum foil feed roller 4b, the reaction of the formula (2) occurs, and electrons generated in the aluminum foil are supplied from the + electrode to the positive electrode side 2e through the negative electrode of the control substrate 6 via the aluminum foil feed roller 4 b. On the positive electrode side 2e to which electrons are supplied, the reaction of the formula (1) occurs, and electric power is supplied between the positive electrode and the negative electrode of the control substrate 6 as a whole by the reaction of the formula (3). The catalyst 2f accelerates and continues the reaction of formula (1).

If the internal impedance of the battery 2 is sufficiently small (for example, several m Ω to several Ω), since the current generated in the battery 2 is proportional to the contact area of the aluminum foil 4d and the negative electrode electrolyte 2c, the current output from the battery 2 can be controlled by controlling the area of the aluminum foil 4d immersed in the negative electrode electrolyte 2c (the length of immersion if the width of the aluminum foil is constant, that is, "immersion length"). That is, constant current power generation (constant current output operation) can be performed by feedback control that senses an output current with the operational amplifier 16, and the aluminum foil feeding roller 4b is driven in accordance with increase and decrease of the output current for a dipping length.

Alternatively, since the output voltage is reduced by the internal resistance in accordance with the current consumed by the load connected to the output terminal, the voltage can be kept constant even if there is a load variation by feedback-controlling the immersion length in order to sense the output voltage of the battery 2 by the operational amplifier 22 and keep the output voltage constant (constant voltage output operation).

The feed speed of the motor 4c driving the aluminum foil roller 4b can be controlled by the voltage of the DAC34, i.e., the applied voltage Vmo to the motor 4 c. The motor 4c can be intermittently driven by outputting Vmo as a pulse wave. By intermittently driving the motor, power consumption can be reduced.

The feeding length L of the aluminum foil 4d can be determined by integrating the feeding speed v [ mm/Sec ] of the motor applied voltage and the driving time t (on time of pulse) [ Sec ] of the motor, which are determined in advance.

In general, as the use time elapses, the concentration of the electrolytic solution decreases and the contamination, the deposition of reaction products, the deterioration of the catalyst of the positive electrode, and the like occur, and therefore, the impedance of the control system of the metal negative electrode battery 10 shown in fig. 2 increases. Therefore, as the resistance increases, the impregnation length of the aluminum foil gradually becomes longer.

Therefore, the impregnation length of the aluminum foil is controlled not to exceed the limit value of the control system of the metal negative electrode cell 10. In the MPU32, regarding the limit value, when the generated current flows, the potential of the limit sensor 2d (the value of the ADC3(28)) and the potential of the aluminum foil (the value of the ADC2 (24)) in which the aluminum foil 4d is positioned at the bottom of the battery cell are measured, and when the potentials are substantially the same (that is, the value of the ADC3 ≈ the value of the ADC 2), it is determined that the limit is reached, and the applied voltage Vmo to the motor 4c is set to zero. Since power can be generated for a while even in this state, an alarm signal (LED blinking or warning sound) can be issued to notify the user of the stop of power generation or the notification of the maintenance time.

In the metal negative electrode battery 10 of the present embodiment, the impregnation length of the aluminum foil (proportional to the contact area between the aluminum foil 4d and the negative electrode electrolyte 2c, and consequently proportional to the current generated in the battery 2) can be controlled according to the required battery output. In contrast, in the conventional aluminum-air battery 100 shown in fig. 1, the entire aluminum electrode 104 is immersed in the electrolyte from the beginning. In the metal negative electrode battery 10 of the present embodiment, since the aluminum foil is impregnated as long as necessary, self-discharge (corrosion) is reduced and energy generation efficiency is improved. In addition, in the case of a standby period such as no connection of a load, the immersion length can be shortened by rotating the motor 4c in reverse, thereby reducing the output. During standby, since the power required to control the operation of the substrate 6 is extremely small, a small immersion length is sufficient. Therefore, even if the aluminum foil is kept on standby for a long time, consumption due to corrosion of the aluminum foil hardly occurs.

[ 2 nd embodiment ]

(constitution)

Fig. 4 is a diagram illustrating the structure of the metal negative electrode battery 20 according to embodiment 2. The metal negative electrode battery 20 differs from the aluminum battery 10 of embodiment 1 in that a water tank 42 and some of the components of the battery main body 2 (such as filters 2h and 2i and a water inlet 2j with an exhaust valve cover) are added to maintain the amount of positive electrode electrolyte.

The water tank 42 has: a nozzle 42a with a float type water level control valve for injecting water to the positive electrode side 2-1 and keeping the water level constant; and a water filling port 42b with an air suction valve cap.

Otherwise, the aluminum battery 20 is the same as the aluminum battery 10 unless otherwise specified. That is, although not shown, the metal negative electrode battery 20 includes the aluminum foil feeding unit 4 and the control board 6 described in the metal negative electrode battery 10 shown in fig. 2.

(operation)

In the metal negative electrode battery, 6 moles of water are required for generating electricity based on 4 moles of aluminum as shown in formula (1). Therefore, when all the aluminum foil is used for power generation, the amount of water in the positive electrode electrolyte 2b may be insufficient in the aluminum battery 10 of fig. 2.

Therefore, the metal negative electrode battery 20 is configured to be able to supply water from the water tank 42 to the positive electrode side 2-1 as necessary. In principle, according to equation (1), water may be supplied only to the positive electrode side 2-1, but may be supplied to the negative electrode side 2-2 and both.

In the metal negative electrode battery 20, when water is injected into the water tank 2 from the water injection port 42b with an air intake valve cover, water is supplied to the positive electrode electrolyte tank 2-1 through the nozzle 42a with a float-type water level adjustment valve. When the positive electrode electrolytic solution tank 2-1 is filled with water, the float-type water level adjustment valve 42a is closed, the inflow of water is stopped, and water is stored at a constant water level in the tank. If the water in the positive electrode electrolyte 2b is insufficient, the float-type water level adjustment valve 42a is opened, and water flows in from the nozzle again. According to this mechanism, the electrolyte tank on the positive electrode side 2-1 is always filled with the electrolyte solution 2b without applying a pressure more than necessary.

The electrolyte solution is prepared by previously containing an electrolyte of a powder in a positive electrode electrolyte tank or a water tank, injecting water, and dissolving the electrolyte in the water.

On the other hand, in the negative electrode side 2-1, in the process of the reaction of the formula (2), for example, in the case where the electrolyte is KOH, the reaction of the formula (4) occurs to produce water-soluble potassium tetrahydroxyaluminate (K [ Al (OH) ])₄]). Therefore, the reaction rate is decreased by decreasing the concentration of KOH (i.e., pH concentration).

[ solution 4]

AI+3OH^-+KOH→K[AI(OH)₄]+3e^-Formula (4)

In the metal negative electrode cell 20, a method of dissolving in a large amount of water in advance is employed in order to secure the amount of KOH consumed. By suppressing the pH to 8 to 10, safety due to leakage and the like is ensured.

On the negative electrode side 2-2, the aluminum foil 4d causes the reaction of formula (4) at the position (a) in fig. 4, and the electrolyte is supplied to the vicinity of the impregnated aluminum foil by convection along the dotted line, passing through the precipitation filter 2s, the 1 st filter 2h, and the 2 nd filter 2 i. K [ Al (OH)₄]Since it has a property of being heavier in specific gravity than the electrolyte and being easily adsorbed, it precipitates at the position (b), is collected by the precipitation filter 2s, and when it passes, the reaction of the formula (5) occurs to generate aluminum hydroxide, and KOH is returned to the electrolyte.

[ solution 5]

K[AI(OH)₄]→AI(OH)₃↓ + KOH type (5)

[ embodiment 3]

(constitution)

Fig. 5 is a diagram illustrating the structure of the metal negative electrode battery 30 according to embodiment 3. The aluminum battery 30 is different from the aluminum battery 20 of embodiment 2 shown in fig. 4 in that an electrolyte sending-out mechanism 44 for controlling the concentration of the negative electrode electrolyte is attached.

The electrolyte delivery mechanism 44 discharges the negative electrode electrolyte 44a from the powder discharge nozzle 44c via the screw-type powder delivery mechanism 44b, and adjusts the pH concentration of the negative electrode electrolyte. The screw-type powder delivery mechanism 44b rotates a helical screw by an electrolyte delivery motor 44d, and delivers the negative electrode electrolyte 44a in the form of powder or granules located in the electrolyte storage chamber to the powder delivery nozzle 44 c.

The metal negative electrode battery 30 includes a connection terminal 2m of the positive electrode liquid potential sensor 2n and a connection terminal 2k of the position limit sensor 2d in the battery main body 2. The positive electrode liquid potential sensor 2n is a rod, wire, mesh, or the like made of a metal (Ti, V, Zr, Mo, Ta, W, or the like) or carbon having a small ionization tendency and low cost.

In other respects, the metal negative electrode battery 30 is the same as the aluminum battery 20 unless otherwise specified. That is, although not shown, the aluminum battery 30 includes the aluminum foil feeding unit 4, the control board 6, and the like described in embodiment 2.

(operation)

In the metal negative electrode cell 20 of embodiment 2, when power generation is performed using a large amount of aluminum foil, the KOH concentration decreases according to the reaction of the above formula (4). When the reaction of formula (5) is insufficient, KOH does not return to the electrolyte solution, and therefore the pH concentration decreases and the power generation stops.

In contrast, in the metal negative electrode battery 30 according to embodiment 3, the electrolyte delivery mechanism 44 is provided, and the insufficient KOH is stored in the electrolyte tank in advance in the form of powder, and is discharged from the powder discharge nozzle 44c and added to the electrolytic solution, thereby maintaining the electrolyte concentration.

The electrolyte (KOH powder/granules) is discharged from the discharge nozzle 44c in proportion to the rotation amount of the helical screw 44b, falls into the electrolyte tank on the negative electrode side 2-2, and is mixed with the electrolyte. Regarding the discharge amount, the rotation speed of the screw 44b is controlled by the MPU32 of the control substrate 6 of fig. 3. Although not shown in the block circuit diagram of the control board 6 in fig. 3, the control may be performed for a short time by using the driving time of the motor (i.e., the discharge amount w ∞ driving time t). Here, since the electrolyte potential on the negative electrode side (negative electrode solution potential) can be detected by the potential difference { Vlim- (Vb-) } between the potential Vb-of aluminum 4d on the negative electrode side 2-2 and the potential Vlim of the limit sensor, the electrolyte concentration is maintained by feedback-controlling the drive time t of the motor in order to keep the negative electrode solution potential within a certain range.

In general, when the negative electrode solution potential is 0.8V or less, hydrogen is not generated from aluminum, but when it is 1.2V or more, a reaction is vigorously generated and aluminum is consumed. Therefore, it is preferable to control the concentration so as to always maintain 0.8V to 0.9V, thereby minimizing the consumption of aluminum and improving the power generation efficiency.

In the metal negative electrode battery 30 of embodiment 3, only the negative electrode electrolyte (for example, KOH) can be added, and therefore the pH concentration cannot be lowered. However, although not shown, the pH concentration can be lowered by adding an acidic electrolyte for neutralization (acetic acid, citric acid, or the like) by the same mechanism. In addition, although the electrolyte is a solid electrolyte in the present embodiment, a mechanism for dropping a liquid electrolyte solution may be used.

As described above, since the output current of the battery can be controlled by the immersion length of the aluminum foil in the electrolyte solution, the power generation can be performed in an optimum state according to the output power by controlling the immersion length according to the negative electrode solution potential.

The positive electrode liquid potential sensor 2n can measure the positive electrode-side electrolyte potential (positive electrode liquid potential — positive electrode liquid potential sensor voltage) Vpe. The potential (electromotive force of the positive electrode) Vpee of the positive electrode can be determined from the potential difference { (Vb +) -Vpe } between the positive terminal potential Vb + and the positive electrode potential Vpe. The deterioration state of the air electrode can be monitored by the electromotive force Vpee of the positive electrode. For example, as shown in formula (1), the electromotive force of the positive electrode is 0.4V, but is reduced to 0.4V or less when the positive electrode is degraded. The deterioration is larger as the reaction rate of formula (1) is lower, and the deterioration is larger as the current is larger, because of the decrease in the oxygen concentration, the electrolyte concentration, the catalytic reaction, the temperature, and the like.

In order to prevent deterioration, it is effective to reduce the generated current or stop the generation of electricity, and therefore the potential Vpee of the positive electrode is often measured to limit the generated current to a range where deterioration does not occur. The generated current limiting process can be realized by limiting the output current of the 5V booster circuit 14 with the MPU32 of fig. 3. The positive electrode potential Vpe can be easily measured by the MPU32 using a circuit (amplifier 26 and ADC3(28)) similar to Vlim in the block diagram of fig. 3.

Further, since the reaction efficiency of the formula (1) of the positive electrode also varies depending on the concentration of the positive electrode electrolyte, the concentration of the positive electrode electrolyte can be controlled so as to maximize the reaction efficiency by using the positive electrode electrolyte delivery mechanism as in the negative electrode. For density management, Vpee can be used.

[ 4 th embodiment ]

(constitution)

Fig. 6 is a diagram illustrating the structure of the metal negative electrode battery 40 according to embodiment 4. The metal negative electrode battery 40 is different from the metal negative electrode battery 30 according to embodiment 3 shown in fig. 5 in that the battery main body 2 and the electrolyte delivery mechanism 44 are integrated and housed in the reaction cassette 52. An aluminum foil insertion guide 54 is provided in the reaction cassette 52, whereby the aluminum foil 4d is impregnated into the negative electrode electrolyte 2 c. Further, the metal negative electrode battery 40 is provided with a sealed water tank 43 in place of the water tank 42. Although not shown, the control board 6 is provided outside the reaction cassette 52.

In other respects, the metal negative electrode cell 40 and the metal negative electrode cell 30 are not particularly described. That is, although not shown, the aluminum battery 40 includes the aluminum foil feeding unit 4, the control board 6, and the like described in embodiment 3.

To achieve these differences, the electrolyte delivery motor connection gear (flat gear) 44e can be gear-connected to a delivery motor (not shown). The positive potential sensor connection terminal 2m, the limit sensor connection terminal 2k, and the positive terminal + are electrically connected to terminals of the main body, respectively, by a connector mechanism (not shown).

On the other hand, the water tank water supply cover 43a is configured to be attachable to and detachable from the water suction port 52a of the reaction cassette 52 (for example, screw type), so that the sealed water tank 43 can be directly supplied with water from a tap water pipe or the like. The tank 43 can be sealed by attaching the tank water supply cover 43 a. At this time, the tank-closing valve of the tank water supply cover 43a is pressed against the cover (lower side in the drawing) by the valve-closing spring, and thus water leakage does not occur.

When the sealed water tank 43 is provided in the reaction cassette 52, a water tank water supply cover 43a is provided in a water receiver 52a of the reaction cassette 52 as indicated by an arrow in the figure.

(operation)

The reaction cassette 52 is assembled with the separator 2a and the positive electrode material 2e, and the negative electrode electrolyte is accommodated in advance in the negative electrode side 2-2, the positive electrode electrolyte is accommodated in the positive electrode side 2-1, and the negative electrode electrolyte is accommodated in the electrolyte feeding mechanism 44. In this case, the entire reaction cassette 52 is covered with a packaging film, for example, having an airtight structure, so that the reaction cassette can be stored stably for a long period of time while preventing the entry of water and excess air.

The electrolyte sending-out motor 44d is connected to the electrolyte sending-out motor connecting gear 44e of the reaction cassette 52. The positive potential sensor connection terminal 2m, the limit sensor connection terminal 2k, and the positive terminal are electrically connected to the terminals of the control board 6, respectively. The sealed-type water tank 43 is connected to the water supply port 52a of the reaction cassette 52.

When the reaction cassette 52 is set and the sealed water tank filled with water is set, water supply is started. Water is supplied to the positive electrode reaction tank and the negative electrode reaction tank through the water receiver 52a by the nozzles 2p and 2q of the float-equipped water level adjustment valve, respectively. By the float type water level adjusting mechanism, if the water level reaches a constant water level, the valve is closed, and the water level is always kept constant. When the valve of the nozzle is closed, the water receiver 52a is filled with water, whereby the air inlet of the sealed tank is blocked and the supply of water from the sealed tank is stopped. With this mechanism, since the water level is maintained constant in the water receiver without the water overflowing from the water receiver, the pressure applied to the water level adjustment valve is maintained constant, and thus the water level can be adjusted with high accuracy.

With the above-described function, the user can replace the reaction cassette 52 without directly contacting the electrolyte at the time of the end of power generation, and therefore, safety can be improved. In addition, power generation can be rapidly continued, and recirculation of the reaction cassette 52 can also be performed. As described above, the reaction cassette 52 is assembled with the separator 2a and the positive electrode material 2e, and the negative electrode electrolyte is stored in advance in the negative electrode side 2-2, the positive electrode side 2-1 and the negative electrode electrolyte in the electrolyte delivery mechanism 44, but some of them may be stored in the main body.

Thereby, the same operation as that of the metal negative electrode battery 30 of embodiment 3 is performed.

[ 5 th embodiment ]

(constitution)

Fig. 7 is a diagram illustrating the structure of a sealed metal negative electrode battery 50 according to embodiment 5. The metal negative electrode batteries 10 to 40 of embodiments 1 to 4 are different in that the entire batteries are sealed. In order to realize a sealed battery, the periphery of the reaction portion of the battery is surrounded by the porous PTFE film 58. Thus, regardless of the direction in which the cell is arranged (upside down, toward the side), the generated gas is released to the outside through the porous membrane, but the electrolyte does not leak to the outside.

The motor unit 62 is an ultrasonic motor, and a sliding surface 62a of the motor is electrically conductive, and is brought into close contact with the aluminum foil 4d to be electrically conductive with the aluminum foil 4 d. Thereby, leakage of the electrolytic solution is prevented. Otherwise, unless otherwise specified, the aluminum battery 50 is the same as the aluminum batteries 10 to 40 of the other embodiments.

(operation)

In the sealed metal negative electrode battery 50, the positive electrode electrolyte 2b, the negative electrode electrolyte 2c, and the like are previously injected into the battery. The aluminum foil end 4d is inserted into the ultrasonic motor 62, but is isolated from the electrolyte 2 c. In this state, the entire battery is covered with a packaging film, an aluminum foil, or the like, whereby the battery can be stably stored for a long period of time.

The ultrasonic motor 62 is started by a backup battery (not shown) such as a button cell, and the aluminum foil 6d is immersed in the electrolyte solution 2c, thereby starting power generation. The aluminum foil 4a is disposable because it cannot be replaced, but no liquid leaks, and thus can be used for various purposes. For example, the portable vehicle can be made compact and can be mounted on a mobile body such as a vehicle in a large size.

Further, the organic electrolytic solution is sealed, so that the odor can be sealed even when the organic electrolytic solution is used as the electrolytic solution. Similarly, since the battery is sealed and can prevent water from entering, an electrolyte solution specifically containing water is not necessary, and the battery may be developed as an aluminum secondary battery.

[ 6 th embodiment ]

(constitution)

Fig. 8 is a diagram showing the structure of a metal negative electrode battery 60 according to embodiment 6. The metal negative electrode battery 60 is a battery in which the positive electrode formed of the air electrode of the metal negative electrode battery 50 of embodiment 5 shown in fig. 7 is replaced with a collector electrode 2 r. The air electrode current collector 2r composed of the positive electrode material 2e, the catalyst 2f, and the porous PTFE film 2g for air introduction in the metal negative electrode battery 50 is replaced with an oxide such as manganese dioxide for the positive electrode electrolyte solution 2b, and functions as a battery.

(operation)

In general, when the output is increased in an air battery, the reaction efficiency of the air electrode is low, and therefore, a large area is required, and it is difficult to realize the air battery compactly. In the present embodiment, a large current can be passed through the positive electrode 2r by using an oxide having a reducing ability such as manganese dioxide. The same operation as in embodiments 1 to 5 can be performed except that the reaction of the positive electrode is different. When manganese dioxide and KOH are used for the positive electrode electrolyte, the reaction of formula (6) occurs instead of formula (1). Since air is not required, the reaction is fast, and a large current can flow.

[ solution 6]

MnO₂+H₂O+e^-→MnOOH+OH^-Formula (6)

In the present embodiment, the electrolyte solution requires an oxide or the like, and therefore has a disadvantage of lowering the energy density per unit weight, but is a closed type except for gas generated by emission, and can be miniaturized. In addition, air is not required, and thus the restriction on the use environment is small.

[ 7 th embodiment ]

(constitution)

Fig. 9 is a diagram showing the structure of a sol metal negative electrode battery 70 according to embodiment 7. The sol metal negative electrode battery is a battery in which the negative electrode made of aluminum foil of the metal battery 10 of embodiment 1 shown in fig. 2 is replaced with a sol metal 10 a. The sol metal 10a stored in the negative electrode material storage tank 4e is pushed out to the negative electrode current collector 4f by the negative electrode material feed pump 44f, and functions as a battery.

In order to reduce self-discharge, the surface of the metal particles or metal powder used for the sol metal 10a may be coated with a metal having a low ionization tendency (for example, zinc, indium, tin, or the like), or the surface may be coated with a polymer containing a conductive material containing carbon or a metal oxide (graphite, carbon black, acetylene black, cobalt oxide, cobalt oxyhydroxide, silver oxide, silver nickel oxide, nickel oxyhydroxide, and indium oxide), or a mixture thereof. The peptizer may use starch, cellulose derivatives, emulsifiers, etc. having a thickening effect, and may contain particles or microparticles having conductivity. The conductive particles have the effect of reducing the resistance of the battery. The negative electrode current collector 4f may be made of porous or sponge-like, net-like, felt-like, or woven metal (stainless steel, Ti, V, Ni, Zr, Mo, Ta, W, etc.) or carbon.

(operation)

In embodiments 1 to 6, a solid metal is used for the negative electrode, but in the case of a solid metal, the degree of freedom in the shape and size of the negative electrode is insufficient, and the extrusion structure is also limited. Further, when a plurality of batteries are connected in series or in parallel, an independent electrode and a drive system are required, and there is a disadvantage that the number of components increases and the size increases.

In the present embodiment, the negative electrode metal can be treated in the same manner as the solid metal by using the sol metal 10a obtained by kneading the metal particles, the metal powder, the metal fine powder, and the sol agent, extruding the sol metal 10a into the negative electrode current collector 4f using the storage tank, and reacting the sol metal in the negative electrode current collector 4 f. That is, when the sol metal 10a passes through the porous metal, for example, the reaction of the formula (2) occurs, and the generated electrons are transferred to the current collector, thereby generating power. The position limit sensor detects that the potential difference between the position limit sensor and the negative electrode current collector 4f is zero, and detects that the reaction vessel is filled with the sol metal 10 a.

[ operation common to all embodiments ]

The operation common to the above-described embodiments will be described. The specific processing is shown in the flowcharts of fig. 10 to 12. These processes are executed by the MPU 32.

Fig. 10 is a flowchart regarding the feed control of the aluminum foil.

In step S01, the inter-electrode voltage is obtained from the positive potential Vb + and the negative potential Vb { (Vb +) - (Vb-) } in fig. 2.

In step S02, it is determined whether the obtained Vout is lower than a preset control target voltage Vtar.

In step S03, when Vout < Vtar, the aluminum foil is slightly (for example, about 1 to several mm) motor-driven and transported into the electrolyte in order to increase the Vout voltage. Otherwise, the process proceeds to step S04.

In step S04, when the aluminum foil is immersed in the electrolytic solution and the reaction is promoted, Vout rises, and the reaction is waited for. The waiting time is determined by experiments and is about several seconds to tens of seconds.

In step S05, it is determined whether the immersion length of the aluminum foil in the electrolytic solution exceeds a limit value. In this judgment, the difference { Vlim- (Vb-) } between the limit sensor potential Vlim and the Vb-potential is taken, and if the potential difference is zero, it is judged that the limit value is exceeded. In the case where the limit value is not exceeded, the flow returns to step S01.

In step S06, the remaining amount of the negative electrode electrolyte is checked. If not, ending the use of the battery; in some cases, the process returns to step S01.

Fig. 11 is a flowchart regarding management of the negative electrode electrolyte in fig. 5 and 6.

In S11, an electrolyte solution of a desired concentration is produced by filling a battery or a case with an amount of electrolyte required for an initial operation and filling the battery or the case with water in advance. At this time, the electrolyte tank shown in fig. 6 and 7 was filled with a negative electrode electrolyte, and the remaining amount was Qe [ g ]. The variable of the remaining amount for control is Qre, and the initial value is Qe.

In step S12, the potential Vlim of the limit sensor is compared with a predetermined reference potential Vref. The potential Vlim of the limit sensor is the potential of the negative electrode electrolyte with the aluminum foil as a reference. The reference potential Vref is usually set to 0.7V to 1.0V at which hydrogen generation is difficult.

In step S13, when the limit sensor potential Vlim is lower than the reference potential Vref, the electrolyte is discharged because the electrolyte concentration is considered to be low. The discharge amount skip is subtracted from Qre (Qre ═ Qre — skip). Drip is determined experimentally.

In step S14, the process waits until the electrolyte is dissolved in the electrolytic solution. The waiting time can be shortened by making the electrolyte into powder or granules.

In step S15, it is determined whether or not there is a remaining amount of electrolyte and whether or not the variable Qre is greater than zero. If there is a remaining amount, the process returns to S12 and repeats. If there is no remaining amount, the process is ended.

Fig. 12 is a flowchart regarding positive electrode potential control. This processing is processing for setting the control target voltage Vtar between the positive electrode and the negative electrode of the battery to the voltage shown in fig. 12. Fig. 13 is a graph showing the target positive electrode potential Vtar characteristic with the positive electrode potential Vpee as a parameter. That is, Vtar is the following function: when the positive electrode potential Vpee is between Vpeel and Vpeeh (positive electrode voltage Vb + -positive electrode liquid potential sensor voltage Vpe), it decreases at a constant gradient as shown in the figure, and when it exceeds Vpeeh, it becomes a fixed value of Vtl. When Vpee is equal to or less than Vpeel, the discharge is stopped because the discharge is over-discharged.

In step S21, Vth is set as the target voltage upper limit value, which is the range of setting Vtar voltage, and Vtl is set as the target voltage lower limit value. The upper limit voltage of Vpee (positive electrode voltage — positive electrode liquid potential sensor voltage) is Vpeeh, and the lower limit voltage is Vpeel. Vtl and Vth are set as normal operating ranges of the battery, and are usually set to arbitrary values of 0.9V to 1.8V through experiments. Vpeel and Vpeeh are voltages for the reaction of formula (1), and are usually set to values of 0V to 0.4V.

In step S22, Vpee is determined.

In step S23, Vpee and Vpeeh are compared. If Vpee > Vpeeh, Vtar is not changed, and the process returns to S22.

In step S24, Vpee and Vpeel are compared. In the case of Vpee < Vpeel, the process proceeds to S26. If Vpee > ═ Vpeel, the process proceeds to S25.

In step S25, Vtar is obtained by the following equation, and the process is repeated from S22.

[ solution 7]

Vtar Vth- (Vth-Vtl)/(Vpeeh-Vpeel) ((Vpee-Vpeel)) formula (7)

In step S26, the 5.0V booster circuit in fig. 3 is stopped, and the entire process is stopped.

[ features common to all embodiments ]

Features common to the above-described embodiments will be described.

The objects of these embodiments are to provide a metal negative electrode battery in which the positive electrode is an air electrode in embodiments 1 to 5 and 7, and to provide a metal negative electrode battery in which the positive electrode of the air electrode is replaced with a positive electrode active material and a current collector in embodiment 6. The characteristics of these metal batteries include, for example, the following.

(1) A metal negative electrode battery having an automatic feeding mechanism of metal.

(2) The metal negative electrode battery is capable of controlling at least one of (a) a surface water level or a liquid amount of an electrolytic solution, (b) a length (immersion length) or an area of a metal impregnated into the electrolytic solution by metal feeding, and (c) an amount of an electrolyte in the electrolytic solution (i.e., an electrolyte concentration) by 1 to 2 or more parameters described below.

(i) Generated current, generated voltage, generated power, accumulated generated power, or operating time.

(ii) Electrolyte temperature, atmospheric temperature, metal electrode temperature.

(iii) The pH of the electrolyte.

(iv) Conductivity of the electrolyte (electrolyte resistance value).

(v) The potential of the anolyte or the potential of the catholyte with respect to the potential of the anode, cathode or separator.

(vi) Amount of metal (amount of metal reacted) or cumulative feed time

(3) When the main component of the electrolyte is a solid, the electrolyte can be maintained in a dry state for a long time, and an electrolyte can be generated and started by injecting a solvent.

(4) The solvent may be a metal negative electrode battery using an aqueous solution such as water or seawater.

(5) The reaction part can be made into a cassette type, and an electrolyte or an electrolytic solution necessary for power generation can be supplied, and the above-mentioned metal negative electrode battery capable of recovering waste after the reaction can be replaced by the cassette.

[ advantages and effects of the embodiments ]

(1) Has no electrolyte leakage and self-discharge, and can be stored for a long time.

(2) The length of immersion of the metal in the electrolytic solution can be optimally controlled by the output of the microcomputer, so that efficient power generation can be continued and a standby state can be maintained for a long time (a state in which the load current during operation is substantially zero).

(3) The battery using the aluminum foil as the negative electrode material has the following effects.

(i) Although compact and lightweight, one aluminum foil can obtain large electric power. In addition, since the replacement is possible, power generation can be performed for a long time.

(ii) An aluminum foil for cooking used in general households can be used instead of a special aluminum foil, and thus the electrode material can be daily prepared although a main body and an electrolyte cartridge are additionally required.

(iii) Since the electrolyte and the reaction container are integrated in the case, power generation can be performed only by placing an aluminum foil in the apparatus and injecting water or seawater, and a large-capacity battery that can be used by any person, anywhere, and anytime and can be stored for a long period of time can be provided.

(4) Thus, the metal negative electrode battery can be provided for applications such as an emergency power supply for disaster time and the like which can be stored for a long period of time, a light and small power supply for a non-electrified region, and a quiet power supply which does not emit harmful substances in the open air or at a construction site. Further, the size of the battery can be increased, and the battery can be used as an auxiliary power supply or a UPS power supply for EV vehicles and the like.

(5) The sealed structure can be realized in a compact manner, and can be applied to portable use or vehicle-mounted use.

(6) By using the sol metal, it is easy to supply the metal from one place to a plurality of battery cells connected in series or in parallel, or to increase the output and the size.

Description of the symbols

2: battery body, 2-1: positive electrode side, 2-2: negative electrode side, 2 a: separator, 2 b: positive electrode electrolyte, 2 c: negative electrode electrolyte, 2 d: limit sensor, 2 e: positive electrode material, 2 f: catalyst, 2 g: porous membrane, 2 h: filter, 2 i: filter, 2 j: water injection port with exhaust valve cover, 2 k: spacing sensor connection terminal, 2 m: connection terminal, 2 n: positive electrode liquid potential sensor, 2 p: nozzle, 2 q: nozzle, 2 r: positive electrode collector electrode, 2 s: sediment filter, 2 t: residue after reaction, 2 u: porous membrane, 4: aluminum foil feeding unit, 4 a: aluminum foil (aluminum foil), 4 b: aluminum foil feed roller, 4 c: motor, 4 d: aluminum foil, 4 e: negative electrode material storage tank, 4 f: negative electrode current collector, 6: control substrate, 8: liquid level, 10: metal negative electrode battery, 10 a: sol metal, 12: boost circuit, 14: boost circuit, 16: operational amplifier, 20: aluminum battery, 22: operational amplifier, 24: ADC2, 26: operational amplifier, 28: ADC3, 30: metal negative electrode battery, 32: MPU, 34: DAC, 36: motor drive driver, 40: metal negative electrode battery case, 42: water tank, 42 a: nozzle with float type water level control valve, 42 b: water filling port with air suction valve cover, 43: sealed-type water tank, 43 a: water tank water supply cover, 44: electrolyte delivery mechanism, 44 a: negative electrode electrolyte, 44 b: screw type powder delivery mechanism, 44 c: powder discharge nozzle, 44 d: electrolyte delivery motor, 44 e: electrolyte delivery motor connecting gear, 44 f: negative electrode material pressure pumps 44f, 50: metal negative electrode battery, 52: reaction cartridge, 52 a: water supply port with water receiver, 54: aluminum foil insertion guide, 58: porous PTFE membrane, 60: sealed metal negative electrode battery, 62: ultrasonic motor, 62 a: sliding surface, 100: aluminum air battery schematic diagram, 102: positive electrode, 104: aluminum electrode, 106: electrolyte solution, 108: a separator.