JP5446392B2 - Air battery - Google Patents

Description

  The present invention relates to an air battery.

  The air battery is a battery using oxygen as a positive electrode active material, and takes in air from the outside during discharge. Therefore, it is possible to increase the proportion of the negative electrode active material in the battery container as compared with other batteries having positive and negative electrode active materials in the battery. Therefore, in principle, the electric capacity that can be discharged is large, and it is easy to reduce the size and weight. Further, since the oxidizing power of oxygen used as the positive electrode active material is strong, the battery electromotive force is relatively high. Furthermore, since oxygen has a feature that it is a clean material without resource restrictions, the air battery has a small environmental load. As described above, the air battery has many advantages and is expected to be used for a battery for a portable device, a battery for an electric car, a battery for a hybrid car, a battery for a fuel cell car, and the like.

  As a form of the air battery, for example, a power generation unit having a positive electrode, a separator, and a negative electrode and an electrolytic solution are housed in a casing provided with an air supply unit and the like, and the power generation unit is impregnated with the electrolytic solution and used. There is.

  In addition, as a technique related to an electrolytic solution of an air battery, particularly an air battery, Patent Document 1 discloses a negative electrode having the ability to release metal ions, a positive electrode containing a carbon material, and an O- (C sandwiched between the negative electrode and the positive electrode. A nonaqueous electrolyte battery including a nonaqueous electrolytic solution containing an organic carbonate compound having a ═O) —O skeleton and a storage case in which air holes for taking in oxygen are formed in a positive electrode is disclosed. In Patent Document 1, the electrolyte solution is a non-aqueous electrolyte solution containing an organic carbonate compound having an O— (C═O) —O skeleton, thereby preventing volatilization of the electrolyte solution in the vicinity of the positive electrode carbon surface, and cycle performance and The non-aqueous electrolyte battery is excellent in discharge capacity.

JP 2003-100309 A

  However, the non-aqueous electrolyte solution containing an organic carbonate compound having an O— (C═O) —O skeleton as described in Patent Document 1 can be obtained by repeating the charge and discharge of the organic carbonate compound for each discharge. There was a problem that decomposition occurred, the electrolyte was depleted in the battery, and the battery life was reduced.

  This invention is made | formed in view of the said problem, and makes it a subject to provide the air battery which can prevent depletion of electrolyte solution and can suppress the fall of battery life.

In order to solve the above problems, the present invention has the following configuration. That is,
The first aspect of the present invention is calculated by the casing, the power generation unit and the electrolyte provided in the casing, the electrolyte consumption calculation means for calculating the consumption of the electrolyte, and the electrolyte consumption calculation means. An air battery comprising: an electrolytic solution amount adjusting unit that adjusts an electrolytic solution amount in a housing based on an electrolytic solution consumption amount.

  In the first aspect of the present invention and the present invention described below, the “power generation unit” includes a positive electrode, an electrolyte layer (separator, etc.), and a negative electrode, and is used in a state of being impregnated with an electrolyte solution. It is the part that can generate electricity by being sent. The form of the power generation unit in the housing is not particularly limited, and may be a single cell or a stack. “Calculating electrolyte consumption” means calculating the amount of electrolyte consumption, such as the form of calculating the amount of electrolyte consumption in the housing in accordance with a pre-defined formula for calculating the amount of electrolyte consumption. As long as it is a form to be used, there is no particular limitation. “Adjusting the amount of electrolyte in the housing based on the amount of electrolyte consumed” means that the required amount of electrolyte is replenished from the outside into the housing based on the calculated amount of electrolyte consumed. There is no particular limitation as long as the amount of the electrolytic solution in the housing is adjusted and controlled so that the electrolytic solution in the body is not depleted. For example, the electrolyte solution can be supplied from the electrolyte tank connected to the housing into the housing to adjust the amount of the electrolyte in the housing.

In the electrolyte consumption calculation means according to the first aspect of the present invention, the electrolyte consumption, Ru is calculated by the following equation (1). By calculating the electrolyte consumption according to the following formula (1), the electrolyte consumption can be easily estimated, and the electrolyte can be replenished by an appropriate amount in the housing. Therefore, the amount of the electrolytic solution in the housing can be maintained appropriately, and the electrolytic solution can be prevented from being depleted.
y = a * x * n ... Formula (1)
In equation (1), y is the electrolyte consumption, a is the electrolyte consumption coefficient, x is the electric capacity used, and n
Is the number of charge / discharge cycles of the battery.

  Here, the “electrolytic solution consumption coefficient” is a coefficient determined for each type of electrolytic solution used in the air battery. The “electric capacity used” is the amount of electricity used during the discharge reaction (output). The “electric capacity used” can be measured, calculated, or determined based on, for example, the time required to reach a preset lower limit voltage under a constant current. The “number of times of charging / discharging” means the number of charging / discharging cycles of the battery, and one charging / discharging cycle is counted as one time. The “number of times of charging / discharging” can be measured and calculated by, for example, a known counter. Formula (1) calculates the electrolyte consumption amount y by multiplying the cumulative electrical capacity value when the predetermined electrical capacity x is obtained by n times of charge and discharge times by the electrolytic solution consumption coefficient a. is there. Here, the predetermined electric capacity x and the number of times of charging / discharging n are defined separately. However, as shown below, instead of x and n, an equation using a cumulative electric capacity X obtained from the battery ( The electrolytic solution consumption y may be calculated by 2).

That is, in the electrolytic solution consumption calculating means according to the first aspect of the present invention, the electrolytic solution consumption may be calculated by the following formula (2).
y = a · X Equation (2)
In equation (2), y is the electrolyte consumption, a is the electrolyte consumption coefficient, and X is the cumulative electric capacity obtained from the battery.

  The “cumulative electric capacity obtained from the battery” in the expression (2) is an electric capacity value obtained from the battery by discharging or cumulatively obtained from the battery by repeating charging and discharging of the battery. For example, it can be measured, calculated or determined based on the accumulated time during which the battery is discharged under a constant current.

  In the first aspect of the present invention, the electrolytic solution amount adjusting means includes an electrolytic solution tank in which the electrolytic solution is stored, an electrolytic solution supply channel extending from the electrolytic solution tank to the housing, and a valve provided in the electrolytic solution supply channel. It is preferable that the opening and closing of the valve is controlled based on the calculated amount of electrolyte consumption, so that the amount of electrolyte in the housing is adjusted. If it does in this way, electrolyte solution can be appropriately replenished from an electrolyte solution tank in a case by opening and closing control of a valve. Therefore, the amount of the electrolytic solution in the housing can be maintained appropriately, and the electrolytic solution can be prevented from being depleted.

The second aspect of the present invention is based on the casing, the power generation unit and the electrolytic solution provided in the casing, the state of the electrolytic solution in the casing, the detection unit, and the electrolyte state detected by the detection unit, An electrolyte amount adjusting means for adjusting the amount of the electrolyte solution in the housing, and the detecting means measures a metal wire for measuring the ionic conductivity of the electrolyte solution or a dissolved oxygen concentration in the electrolyte solution. It is an air battery that is a dissolved oxygen meter .

  In the second aspect of the present invention, the electrolyte amount adjusting means includes an electrolyte tank containing the electrolyte, an electrolyte supply channel extending from the electrolyte tank to the housing, and a valve provided in the electrolyte supply channel. It is preferable that the amount of the electrolyte in the housing is adjusted by controlling the opening / closing of the valve based on the detected state of the electrolyte. If it does in this way, electrolyte solution can be appropriately replenished from an electrolyte solution tank in a case by opening and closing control of a valve. Therefore, the amount of the electrolytic solution in the housing can be maintained appropriately, and the electrolytic solution can be prevented from being depleted.

  In the first and second aspects of the present invention, it is preferable that the amount of the electrolytic solution in the housing is adjusted by supplying the electrolytic solution from the upper surface of the housing into the housing.

  In the first aspect of the present invention, the electrolyte consumption amount in the housing is calculated by the electrolyte consumption amount calculation means while the battery is stopped or in operation. Then, by supplying the necessary amount of electrolyte into the housing based on the calculated amount of electrolyte consumption, the amount of electrolyte in the housing can be adjusted, and the amount of electrolyte in the housing can be maintained appropriately. . Therefore, according to the first aspect of the present invention, it is possible to provide an air battery that can prevent depletion of the electrolytic solution and suppress a decrease in battery life.

  In the second aspect of the present invention, the state of the electrolytic solution in the casing is detected by the electrolytic solution amount detecting means while the battery is stopped or in operation. Then, by supplying the required amount of electrolyte into the housing based on the detected state of the electrolyte, the amount of electrolyte in the housing is adjusted, and the state of electrolyte in the housing and the amount of electrolyte are appropriately adjusted. Can be kept in. Therefore, according to the second aspect of the present invention, it is possible to provide an air battery that can prevent depletion of the electrolytic solution and suppress a decrease in battery life.

1 is a diagram schematically showing a configuration of an air battery 100. FIG. 2 is a diagram schematically showing a configuration of an air battery 200. FIG. It is a figure for demonstrating the adjustment method of the electrolyte solution amount in a housing | casing. 2 is a diagram schematically showing a configuration of an air battery 300. FIG. It is a figure for demonstrating the adjustment method of the electrolyte solution amount in a housing | casing.

  Hereinafter, the case where the present invention is applied to a lithium-air battery will be mainly described. However, the present invention can also be applied to other air batteries (other alkali metal air batteries, alkaline earth metal air batteries, zinc air batteries, etc.) for the purpose of preventing electrolyte depletion.

1. First Embodiment FIG. 1 is a diagram schematically showing an entire air battery 100 according to a first embodiment. As shown in FIG. 1, the air battery 100 includes a positive electrode 10, a negative electrode 20, a power generation unit 40 having an electrolyte layer 30 interposed between the positive electrode 10 and the negative electrode 20, and a housing 50 that contains these. ing. In addition, a space 51 is provided between the housing 50 and the power generation unit 40, and the oxygen layer 11 is formed on the side surface opposite to the electrolyte layer 30 of the positive electrode 10 by filling the space 51 with an oxygen-containing gas. Yes. Oxygen is supplied to the positive electrode 10 from here, and is used for the battery reaction of the positive electrode 10. Moreover, the positive electrode 10 and the negative electrode 20 are each provided with an electrode terminal, and in the air battery 100, the electric energy generated by the battery reaction can be taken out through the electrode terminal. Furthermore, an electrolytic solution consumption calculating means 60 (hereinafter, also referred to as “calculating means 60”) is connected to each electrode terminal. On the other hand, an electrolytic solution amount adjusting unit 70 (hereinafter sometimes referred to as “adjusting unit 70”) is provided outside the housing 50, and the adjusting unit 70 includes an electrolytic solution in which an electrolytic solution 72 is accommodated. A tank 71, a supply pipe 73 extending from the electrolyte tank 71 into the housing 50, and an electromagnetic valve 74 provided in the supply pipe 73 are provided. The electromagnetic valve 74 is connected to the calculation means 60, and the opening / closing of the valve can be controlled by a signal sent from the calculation means 60. Hereinafter, each configuration of the air battery 100 will be described.

<Positive electrode 10>
The positive electrode 10 contains a conductive material, a catalyst, and a binder that binds these.

  The conductive material contained in the positive electrode 10 is not particularly limited as long as it can withstand the environment when the air battery 100 is used and has conductivity. Examples of the conductive material contained in the positive electrode 10 include carbon materials such as carbon black and mesoporous carbon. Further, from the viewpoint of suppressing a decrease in reaction field and a decrease in battery capacity, the content of the conductive material in the positive electrode 10 is preferably set to 10% by mass or more. Further, from the viewpoint of making the form capable of exhibiting a sufficient catalytic function, the content of the conductive material in the positive electrode 10 is preferably 99% by mass or less.

  Examples of the catalyst contained in the positive electrode 10 include cobalt phthalocyanine and manganese dioxide. From the standpoint of achieving a form capable of exhibiting a sufficient catalytic function, the content of the catalyst in the positive electrode 10 is preferably 1% by mass or more. Further, from the viewpoint of suppressing a decrease in reaction field and a decrease in battery capacity, the catalyst content in the positive electrode 10 is preferably 90% by mass or less.

  Examples of the binder contained in the positive electrode 10 include polyvinylidene fluoride (PVDF) and polytetrafluoroethylene (PTFE). The content of the binder in the positive electrode 10 is not particularly limited, but is preferably, for example, 10% by mass or less, and more preferably 1% by mass to 5% by mass.

  The positive electrode 10 can be produced, for example, by applying a paint composed of carbon black, a catalyst, and a binder to the surface of a positive electrode current collector described later by a doctor blade method. In addition, it can also be produced by hot pressing a mixed powder containing carbon black and a catalyst.

<Negative electrode 20>
The negative electrode 20 contains a metal that functions as a negative electrode active material. In addition, the negative electrode 20 is provided with a negative electrode current collector (not shown) that contacts the inside or the outer surface of the negative electrode 20 and collects the negative electrode 20.

  Examples of the metal that can be contained in the negative electrode 20 include Li, Na, K, Mg, Ca, Al, Fe, Zn, and alloys thereof. From the viewpoint of providing the air battery 100 that can easily increase the capacity, it is preferable that Li is contained.

  The negative electrode 20 only needs to contain at least a negative electrode active material, and may further contain a conductive material that improves conductivity, or a binder that fixes the metal or the like. From the viewpoint of suppressing a decrease in reaction field and a decrease in battery capacity, the content of the conductive material in the negative electrode 20 is preferably 10% by mass or less. Further, the content of the binder in the negative electrode 20 is not particularly limited, but is preferably 10% by mass or less, and more preferably 1% by mass or more and 5% by mass or less. The type and amount of the conductive material and binder that can be contained in the negative electrode 20 can be the same as in the case of the positive electrode 10.

  In the air battery 100, a negative electrode current collector (not shown) is provided in contact with the inside or the outer surface of the negative electrode 20. The negative electrode current collector has a function of collecting the negative electrode 20. In the air battery 100, the material of the negative electrode current collector is not particularly limited as long as it is a conductive material. Examples of the material for the negative electrode current collector include copper, stainless steel, and nickel. Examples of the shape of the negative electrode current collector include a foil shape, a plate shape, and a mesh (grid) shape. In the air battery 100, the negative electrode 20 can be produced by the same method as that of the positive electrode 10, for example.

<Electrolyte layer 30>
The electrolyte layer 30 contains an electrolyte solution that conducts ions between the positive electrode 10 and the negative electrode 20.

The form of the electrolytic solution accommodated in the electrolyte layer 30 is not particularly limited as long as it has metal ion conductivity, and an aqueous electrolytic solution or a non-aqueous electrolytic solution is selected depending on the metal used for the negative electrode. In particular, a non-aqueous electrolyte is preferable. It is preferable that the type of the non-aqueous electrolyte used for the electrolyte layer 30 is appropriately selected according to the type of metal ions to be conducted. For example, the non-aqueous electrolyte of a lithium air battery usually contains a lithium salt and an organic solvent. Examples of the lithium salt include LiPF ₆ , LiBF ₄ , LiClO _4, LiAsF _{6 and} other inorganic lithium salts, LiCF ₃ SO ₃ , LiN (CF ₃ SO ₂ ) ₂ , LiN (C ₂ F ₅ SO ₂ ) ₂ , LiC An organic lithium salt such as (CF ₃ SO ₂ ) ₃ can be exemplified. Examples of the organic solvent include propylene carbonate (PC), ethylene carbonate (EC), dimethyl carbonate (DMC), diethyl carbonate (DEC), ethyl methyl carbonate (EMC), butylene carbonate, γ-butyrolactone, sulfolane, acetonitrile, 1 , 2-dimethoxymethane, 1,3-dimethoxypropane, diethyl ether, tetrahydrofuran, 2-methyltetrahydrofuran, and mixtures thereof.

  Moreover, it is preferable that the electrolyte layer 30 has a configuration in which the electrolytic solution is held by the separator. Examples of such a separator include porous films such as polyethylene and polypropylene, and nonwoven fabrics such as resin nonwoven fabric and glass fiber nonwoven fabric.

<Oxygen layer 11>
The oxygen layer 11 has a function of guiding oxygen gas present in the housing 50 to the positive electrode 10. The oxygen layer 11 is a passage of air guided to the positive electrode 10. For example, the oxygen layer 11 includes holes provided in the positive electrode current collector that contacts the inside or the outer surface of the positive electrode 10 and collects the current of the positive electrode 10. Function as. That is, the oxygen layer 11 can also be expressed as the positive electrode current collector 11.

  In the air battery 100, the positive electrode current collector has a function of collecting the positive electrode 10. In the air battery 100, the material of the positive electrode current collector is not particularly limited as long as it is a conductive material. Examples of the material for the positive electrode current collector include stainless steel, nickel, aluminum, iron, titanium, and carbon. Examples of the shape of the positive electrode current collector include a mesh (grid) shape.

<Power generation unit 40>
In the air battery 100, the power generation unit 40 is a stacked body in which the positive electrode 10, the electrolyte layer 30, and the negative electrode 20 are stacked in this order. The method for laminating the positive electrode 10, the electrolyte layer 30, and the negative electrode 20 is not particularly limited. For example, after forming the positive electrode 10 on one side of the separator and the negative electrode 20 on the other side, the electrolyte is immersed in the separator. By using the electrolyte layer 30, the power generation unit 40 is obtained.

<Case 50>
The housing 50 accommodates at least the power generation unit 40, the oxygen layer 11, and the oxygen-containing gas. In the air battery 100, the shape of the housing 50 is not particularly limited. As a constituent material of the casing 50, a material that can be used for the casing of the air battery can be appropriately used. The oxygen-containing gas accommodated in the housing 50 (existing in the space 51) is not particularly limited as long as it contains oxygen, but air, preferably dry air, or a pressure of 1 is used. .01 × ¹⁰ 5 Pa, the oxygen concentration can be used such as 99.99% of the oxygen gas.

<Electrolyte consumption calculation means 60 (calculation means 60)>
The electrolytic solution consumption calculating means 60 is a means for calculating the electrolytic solution consumption of the air battery 100 based on information such as the number of times the air battery 100 is used (number of times of charging / discharging) and the electric capacity used. Specifically, for example, the electrolyte consumption is calculated based on the following formula (1).
y = a * x * n ... Formula (1)
In the formula (1), y is the electrolyte consumption, a is the electrolyte consumption coefficient, x is the electric capacity used, and n is the number of times the battery is charged and discharged.

  The electrolyte consumption coefficient a is a coefficient determined for each type of electrolyte used in the air battery 100. Specific examples will be described later. The electric capacity x used is the amount of electricity used during the discharge reaction (output). The used electric capacity x can be determined, for example, based on the time required to reach a preset lower limit voltage under a constant current. The charge / discharge number n means the number of charge / discharge cycles of the battery, and one charge / discharge cycle is counted as one time. The “number of times of charging / discharging n” can be measured and calculated by, for example, a known counter. The above equation (1) calculates the electrolyte consumption amount y by multiplying the cumulative capacitance value obtained when the electrical capacity x is obtained n times of charge / discharge times by the electrolytic solution consumption coefficient a. is there.

  Hereinafter, an air battery 100 using a propylene carbonate (PC) -based electrolyte will be described as a specific example of calculating the electrolyte consumption.

If the air battery 100 is discharged when the PC electrolyte is used, it is considered that PC is consumed and decomposition products are generated as shown in the following reaction formula.
Li ⁺ + e ⁻ + O ₂ + PC → R ¹ —O— (C═O) —O—R ²
(R ¹ and R ² are Li or an alkyl group)

That is, it is considered that 1 mol of decomposition product R ¹ —O— (C═O) —O—R ² is generated by consuming 1 mol of electrons (96500 coulomb) and 1 mol of PC per discharge. Since the molecular weight of PC is 102.09 g / mol and the specific gravity is 1.21 g / ml, when an electric capacity of x (coulomb) is obtained,
96500: 102.09 / 1.21 = x: y ₁
(Y ₁ is the amount of electrolyte consumed per discharge)
The following formula holds. Solving this for y ₁ ,
y ₁ = 0.000874 · x
It becomes. When this is repeated n times (the charge / discharge cycle is repeated n times), the electrolyte consumption amount y satisfies the relationship y = y ₁ · n.
y = 0.000874 · x · n
Is obtained. The coefficient 0.000874 in the formula is the electrolyte consumption coefficient a when a PC electrolyte is used as the electrolyte.

  In the calculation means 60, electrolyte consumption is calculated based on the above formula. For example, in an air battery 100 using a PC electrolyte, when an electric capacity of 100 coulombs is obtained and charging / discharging is repeated 100 times, the calculated electrolyte consumption is about 8.7 ml.

  The form of the calculating means 60 can calculate the electrolytic solution consumption from the electric capacity x and the number of times of charging / discharging n by the calculation as described above, and the control signal based on the calculated electrolytic solution consumption There is no particular limitation as long as it is sent to the liquid amount adjusting means 70 and the electrolyte amount adjusting means 70 is controlled. For example, it may be a device that combines a known arithmetic device and a control device.

In the above formula (1), instead of the used electric capacity x and the number of charge / discharge times n, the electrolytic solution consumption y is calculated by the following formula (2) using the cumulative electric capacity X obtained from the battery. It may be calculated.
y = a · X Equation (2)
In equation (2), y is the electrolyte consumption, a is the electrolyte consumption coefficient, and X is the cumulative electric capacity obtained from the battery. The “cumulative electric capacity obtained from the battery” is an electric capacity value obtained from the battery by discharge or obtained cumulatively from the battery by repeating charge and discharge of the battery, for example, Measurement, calculation, or determination can be made based on the accumulated time during which the battery is discharged under a constant current.

<Electrolytic solution amount adjusting means 70 (adjusting means 70)>
The electrolytic solution amount adjusting means 70 includes an electrolytic solution tank 71 in which the electrolytic solution 72 is accommodated, a supply pipe 73 extending from the electrolytic solution tank 71 into the housing 50, and an electromagnetic valve 74 provided in the supply pipe 73. ing. The adjusting means 70 is controlled based on the electrolytic solution consumption information obtained by the calculating means 60, and is a means for replenishing a necessary amount of electrolytic solution in the housing 50 and adjusting the amount of electrolytic solution in the housing. The electrolytic solution is the same as the electrolytic solution held in the electrolyte layer 30. In the adjusting means 70, the electromagnetic valve 74 is opened only at the time of adjusting the amount of electrolyte, and in other cases, the electromagnetic valve 74 is in a closed state. About each structure of the adjustment means 70, a well-known thing can be used without being specifically limited.

2. Steps for Adjusting Electrolyte Volume FIG. 2 shows each step performed when the amount of electrolyte in the housing 50 is adjusted. In the air battery 100, the calculation means 60 calculates the electrolyte consumption based on, for example, the electrolyte consumption coefficient a, the electric capacity x, and the charge / discharge frequency n, and the adjustment means 70 based on the electrolyte consumption. A signal is sent to and the operation of the adjusting means 70 is controlled, so that the amount of electrolyte in the housing 50 is adjusted. There is no particular limitation on when the operation control by the calculation means 60 and the adjustment means 70 is performed, and it is performed automatically or manually at a predetermined battery state, at a preset interval, or arbitrarily. Can be broken. For example, it can be performed at predetermined intervals during battery discharge. Hereinafter, with reference to FIGS. 1 and 2, each step related to the adjustment of the amount of electrolyte in the housing 50 performed by the calculation unit 60 and the adjustment unit 70 will be described.

<Electrolytic Solution Consumption Calculation Step S1>
Step S1 is a step of calculating the electrolyte consumption by the calculation means 60 and determining whether or not the calculated electrolyte consumption exceeds a preset threshold value. That is, based on the amount of electrolyte consumption calculated by the arithmetic unit of the calculation means 60, it is determined by the determination unit (control unit) in the calculation means 60 whether or not the amount of electrolyte consumption exceeds the set value. Is done. For example, when the electrolytic solution consumption amount y is calculated based on the electrolytic solution consumption coefficient a, the measured and calculated electric capacity x, and the number of times of charging / discharging n as in the above formula 1, the electrolytic solution consumption amount y is predetermined. When it is determined that the value has become equal to or greater than the value (it can also be said that the cumulative electric capacity value has been determined to be equal to or greater than the predetermined value), the process proceeds to the electrolyte amount adjustment step S2.

<Electrolytic solution amount adjusting step S2>
When it is determined that the amount of electrolyte consumption has reached a predetermined value or more and it is determined that it is necessary to replenish the casing 50 with the electrolyte, a control signal is sent to the adjusting means 70 and the solenoid valve 74 operates. Controlled, the solenoid valve 74 is opened. When the electromagnetic valve 74 is opened, the electrolytic solution 72 is replenished from the electrolytic solution tank 71 into the housing 50 through the supply pipe 73. At the time of replenishment, the supply amount of the electrolytic solution is appropriately controlled so that the necessary amount of electrolytic solution is replenished in the housing 50. For example, the operation of the adjusting unit 70 is controlled so that the electrolytic solution 72 is replenished into the housing 50 by an amount equivalent to the calculated electrolytic solution consumption. By performing Step S1 and Step S2 once, the electrolyte solution consumption amount may be replenished, or Step S1 and Step S2 may be repeated many times. In the case of repeatedly performing step S1 and step S2, for example, a difference between the amount of electrolyte consumption calculated in step S1 and the amount of electrolyte replenished in step S2 is calculated, and a new value is calculated based on the difference. It can be set as the form by which control of process S2 is made.

  In particular, when supplying the electrolytic solution at a time, when the step S2 is being performed, the electrolytic solution consumption information of the calculating means 60 may be reset in preparation for the next electrolytic solution adjustment. That is, after resetting the electrolyte consumption information, the air battery 100 may be charged and discharged again to calculate the electrolyte consumption.

  In the air battery 100, the amount of the electrolyte in the housing 50 is appropriately maintained by performing the steps S1 and S2. Therefore, depletion of the electrolytic solution is prevented, and a decrease in battery life can be suppressed.

3. 2nd Embodiment FIG. 3: is a figure which shows schematically the structure of the air battery 200 concerning 2nd Embodiment. Among the air batteries 200, those common to the air battery 100 are denoted by the same reference numerals and description thereof is omitted. The straight arrows in the figure indicate the flow direction of the electrolyte or oxygen-containing gas.

  The air battery 200 is electrolyzed based on a plurality of power generation units 40, 40,..., And an electrolytic solution housed in the housing 50, a cumulative electric capacity obtained from the air battery 200, and the number of times of charge / discharge of the air battery 200. A calculating means 60 for calculating the liquid consumption, and an adjusting means 70 for adjusting the amount of the electrolytic solution in the housing 50 by controlling the operation based on the information related to the electrolyte consumption calculated by the calculating means 60. An electrolytic solution tank 71, an electrolytic solution 72, an electrolytic solution supply pipe 73, and electromagnetic valves 74a to 74e), an electrolytic solution discharge pipe 75 and a valve 76 provided at the lower part of the casing 50, and a power generation unit from the lower part of the casing 50. Oxygen supply pipes 80 and 80 and valves 81 and 81 for supplying oxygen to the oxygen layers 11 and 11 of 40, 40,. A pipe 82 and a valve 83.

  The air battery 200 is different from the air battery 100 in that a plurality of power generation units 40, 40,... The power generation units 40, 40 are arranged so that the positive electrodes 10 face each other, and the oxygen layer 11 is provided between the positive electrodes 10, 10 to share the oxygen layer 11 (hereinafter referred to as “structure”). ). The form of the structure is not particularly limited as long as the positive electrode 10 is provided on the inner side and the negative electrode 20 is provided on the outer side so that the oxygen layer 11 can be shared. The two power generation units 40 and 40 face each other. In addition to the form installed in the cylinder, the cylindrical inner side surface is formed into a cylindrical shape in which one end and the other end of one power generation unit 40 are connected to each other. The form may be such that the portion is the oxygen layer 11.

  In addition, the air battery 200 includes the electrolyte layers 20 and 20 of the power generation units 40 and 40 from above the casing 50 (upper side in FIG. 3) via a plurality of branched electrolyte supply pipes 73 and electromagnetic valves 74 a to 74 e. ,... (Separator), the electrolytic solution 72 is supplied, and the electrolytic solution is discharged as necessary via the electrolytic solution discharge pipe 75 and the valve 76 provided at the lower part of the casing 50. Is different. The electrolyte solution supply pipe 73 is provided with electromagnetic valves 74 a to 74 e, and the valve opening / closing operation is controlled based on the electrolyte solution consumption calculated by the calculation means 60. By allowing the electrolytic solution 72 to permeate into the electrolyte layer 20 from above the casing 50, the electrolytic solution can be supplied without depending on the liquid retention of the separator. Therefore, the consumed electrolyte can be replenished easily and appropriately.

  Further, the air battery 200 is oxygenated from below the casing 50 (the lower side in FIG. 3) to the air layers 11 and 11 of the power generation units 40 and 40 through the oxygen supply pipes 80 and 80 and the valves 81 and 81. And oxygen that has not been subjected to the battery reaction is discharged to the outside together with other by-product gases and the like through the space 51 provided in the upper part of the housing 50, the oxygen discharge pipe 82, and the valve 83. Thus, it is different from the air battery 100. Oxygen can be evenly distributed into the air layer 11 by supplying oxygen from the lower part of the housing 50. In addition, a decrease in battery capacity can be suppressed by replacing oxygen and discharging by-product gas.

  In the air battery 200, as with the air battery 100, the opening / closing operation of the electromagnetic valves 74 a to 74 e of the adjusting means 70 is controlled based on the electrolyte consumption calculated by the calculating means 60, and the electrolyte supply from the electrolyte tank 71 is performed. By supplying or stopping supplying the electrolyte solution 72 to the electrolyte layers 20, 20,... In the housing 50 through the pipe 73, the amount of the electrolyte solution in the housing 50 is adjusted. The operations of the calculating means 60 and the adjusting means 70 are the same as those described for the air battery 100. Although the calculation means 60 is illustrated as being connected to the housing 50 and wiring and terminals are omitted, the calculation means 60 is electrically connected to the air battery 200 and It is in a state where the accumulated electric capacity value and the like can be measured and calculated. On the other hand, when the electrolyte in the housing 50 is unnecessary or excessive, or when it is determined that the electrolyte needs to be discharged to the outside, such as when the electrolyte is replaced, the valve 76 is opened. Then, the electrolytic solution is discharged through the electrolytic solution discharge pipe 75, and the amount of the electrolytic solution in the housing 50 is adjusted. About operation | movement of the valve 76, operation control is suitably carried out by using the control apparatus provided separately, or combining the control part in the calculation means 60. FIG. As described above, the air battery 200 adjusts the amount of electrolyte in the housing 50 by appropriately controlling the operation of the adjusting unit 70 based on the amount of electrolyte consumed calculated by the calculating unit 60. The amount of the electrolytic solution can be appropriately maintained. Therefore, according to the air battery 200, depletion of the electrolytic solution is prevented, and a reduction in battery life can be suppressed.

4). 3rd Embodiment FIG. 4: is a figure which shows schematically the structure of the air battery 300 concerning 3rd Embodiment. Among the air batteries 300, those common to the air batteries 100 and 200 are denoted by the same reference numerals, and description thereof is omitted. The straight arrows in the figure indicate the flow direction of the electrolyte or oxygen-containing gas. Moreover, FIG. 5 is a figure shown about the electrolyte solution amount adjustment in the housing | casing 50 in the air battery 300 concerning 3rd Embodiment.

  As shown in FIG. 4, the air battery 300 generally has the same configuration as the air battery 200 as a whole. However, the air battery 300 is different from the air battery 200 in that a detection unit 90 and a control unit 91 are provided instead of the calculation unit 60. In addition, as shown in FIG. 5, in the air battery 300, in order to adjust the amount of electrolyte in the housing 50 and make the state of the electrolyte in the housing 50 appropriate, the detection step S11 and the amount of electrolyte Adjustment process S12 is performed.

<Detection means 90, control means 91>
The detection means 90 is a means that is installed on the inner wall of the housing 50 and detects the state of the electrolyte in the housing 50. In the air battery 300, the state of the electrolytic solution is changed by repeatedly charging and discharging. As the detection means 90, for example, a liquid level sensor that detects the amount of the electrolytic solution in the housing 50, a metal wire that can measure the ionic conductivity of the electrolytic solution in the housing 50, or the electrolytic solution in the housing 50 A dissolved oxygen meter capable of measuring the dissolved oxygen concentration in the inside can be used. Further, the control means 91 is means for controlling the opening / closing operation of the valves 74 a to 74 e of the adjusting means 70 based on the electrolytic solution information (electrolytic solution amount, ion conductivity, oxygen dissolved degree, etc.) obtained by the detecting means 90. It is. A known control device can be used as the control means 91.

  When the detection means 90 is a liquid level sensor capable of detecting the amount of the electrolytic solution in the housing 50, for example, the liquid level sensor is installed at a predetermined water level on the inner wall of the housing 50, and the electrolytic solution is at the predetermined water level. When it becomes, the signal for replenishing electrolyte solution is transmitted to the following control means 91 (detection process S11). The control means 91 controls the operation of the electromagnetic valves 74a to 74e of the adjustment means 70 based on the signal from the liquid level sensor. As the control means, a known control device similar to the control device section of the calculation means 60 can be used. The electromagnetic valves 74a to 74e are opened by the control means 91 and the electrolyte solution 72 is supplied into the housing 50, whereby the amount of the electrolyte solution in the housing 50 can be adjusted appropriately (electrolyte solution). The amount adjusting step S12), the depletion of the electrolyte is prevented, and the decrease in battery life is suppressed.

  In addition, when the detection unit 90 is a metal wire (for example, two metal wires) that can measure the ionic conductivity of the electrolyte in the housing 50, the metal wire is connected to the electrolyte on the inner wall of the housing 50. When the ionic conductivity of the electrolytic solution is below a threshold value, it is installed in a place where it can be contacted, and a signal for replacing the electrolytic solution is sent to the control means 91 and the control device that controls the electrolytic solution discharge valve 76 (not (Shown in step S11). The shape and material of the metal wire are not particularly limited as long as the ionic conductivity of the electrolytic solution can be measured. As a result, the electrolyte discharge valve 76 is opened, and the deteriorated electrolyte is discharged to the outside. On the other hand, the electromagnetic valves 74a to 74e are opened, and the electrolytic solution 72 is supplied into the housing 50 (electrolytic solution amount adjusting step S12). When the electrolytic solution is deteriorated, it is considered that a considerable amount of the electrolytic solution is consumed at the same time, and the electrolytic solution can be replenished simultaneously by replacing the electrolytic solution. Accordingly, it is possible to prevent depletion of the electrolytic solution and to suppress a decrease in battery life. Moreover, since the electrolyte solution which has not deteriorated can be used for a battery reaction, battery performance can be maintained.

  Further, when the detection means 90 is a dissolved oxygen meter capable of measuring the dissolved oxygen concentration in the electrolyte solution in the housing 50, the dissolved oxygen meter is installed at a location where the dissolved oxygen meter can come into contact with the electrolyte solution on the inner wall of the housing 50. When the dissolved oxygen concentration of the electrolytic solution becomes equal to or lower than the threshold value, a signal for adjusting the amount of the electrolytic solution is transmitted to the control unit 91 and a control device (not shown) that controls the electrolytic solution discharge valve 76. In addition, a signal for adjusting the oxygen supply amount is transmitted to a control device (not shown) that controls the operation of the valves 81, 81 and 83 (detection step S11). The form of the dissolved oxygen meter is not particularly limited as long as the dissolved oxygen concentration in the electrolytic solution can be measured. Thereby, the electromagnetic valves 74a to 74e are opened / closed, or the valve 76 is opened / closed, and the amount of the electrolytic solution in the housing 50 is adjusted (electrolyte amount adjusting step S12). On the other hand, the valves 81, 81 and 83 are opened and closed to control the oxygen supply amount in the housing. In this way, the adjustment of the amount of electrolyte prevents the electrolyte from being depleted and suppresses the decrease in battery life. In addition, the dissolved oxygen concentration in the electrolyte can be appropriately controlled, and the battery performance is appropriately adjusted. Can be maintained. In addition, about control of dissolved oxygen concentration, it is more preferable to control so that dissolved oxygen concentration becomes high at the time of battery discharge, and dissolved oxygen concentration becomes low at the time of battery charge.

  Also with such an air battery 300, the amount of the electrolyte in the housing 50 can be adjusted appropriately, and a reduction in battery life can be suppressed.

  In the above description according to the first embodiment, the oxygen layer 11 is provided on the upper surface side in the casing 50, and the electrolyte solution supply pipe 73 is inserted from the side surface side of the casing 50 to replenish the separator 30 with the electrolyte solution. However, the present invention is not limited to this embodiment. As long as the amount of the electrolytic solution in the housing 50 can be adjusted appropriately, for example, the oxygen layer 11 may be provided on the lower surface side or the side surface side in the housing 50, and the electrolytic solution supply valve 73 is provided on the housing 50. It may be inserted from the upper surface side or the lower surface side.

  In the above description according to the first embodiment and the second embodiment, the calculation unit 60 calculates the electrolyte consumption, determines the calculated electrolyte consumption, and transmits the control signal to the adjustment unit. However, the present invention is not limited to this embodiment. You may provide a calculation means, a determination means, and a control means separately.

  In the above description according to the first embodiment and the second embodiment, the adjustment of the amount of the electrolytic solution in the housing 50 by the calculating unit 60 and the adjusting unit 70 is the consumption of the electrolytic solution calculated by the calculating unit 60. Although the description has been made centering on a mode that is performed only when the amount exceeds a predetermined value, the present invention is not limited to this mode. When the battery is in a state where the electrolyte is consumed (for example, during battery discharge), the steps S1 and S2 are performed intermittently or constantly so that the amount of the electrolyte in the housing 50 is always above a certain level. It is good also as a form controlled. At this time, it is not determined whether or not the electrolytic solution consumption exceeds the set value, and the electrolytic solution is supplied into the housing 50 by an amount corresponding to the calculated electrolytic solution consumption.

  In the above description according to the second embodiment, the configuration in which two structures including the power generation unit 40 are provided in the housing 50 has been described, but the present invention is not limited to this configuration. The form provided with three or more structures in the housing | casing 50 may be sufficient.

  In the above description according to the second embodiment, the mode in which the electrolytic solution is supplied from the upper surface side of the housing 50 and the oxygen-containing gas is supplied from the lower surface side of the housing 50 has been described, but the present invention is limited to this mode. Is not to be done. As long as the amount of the electrolytic solution in the housing 50 can be appropriately adjusted, the electrolyte and oxygen supply locations may be from any of the housings 50. However, from the viewpoint of uniformly distributing the electrolyte solution to the electrolyte layer 30 and uniformly distributing oxygen to the oxygen layer 11 without depending on the liquid retention of the separator, the electrolyte solution is from the upper surface side of the housing 50. It is preferable that the oxygen-containing gas is supplied from the lower surface side of the housing 50.

  Moreover, in this invention, it can also be used combining the structure of 1st-3rd embodiment. That is, the calculation means 60, the detection means 90, etc. may be used in combination.

  Although the present invention has been described with reference to the most practical and preferred embodiments at the present time, the invention is not limited to the embodiments disclosed herein. However, the present invention can be appropriately changed without departing from the spirit or concept of the invention that can be read from the claims and the entire specification, and an air battery with such a change is also understood to be included in the technical scope of the present invention. There must be.

  The present invention can be suitably used for portable device batteries, electric vehicle batteries, hybrid vehicle batteries, fuel cell vehicle batteries, and the like.

DESCRIPTION OF SYMBOLS 10 Positive electrode 11 Oxygen layer 20 Negative electrode 30 Electrolyte layer 40 Power generation part 50 Case 51 Space 60 Electrolyte consumption calculation means 70 Electrolyte amount adjustment means 71 Electrolyte tank 72 Electrolyte solution 73 Electrolyte supply pipe (electrolyte supply flow path)
74 Solenoid valve 75 Electrolyte discharge pipe 80 Oxygen supply pipe 82 Oxygen discharge pipe 90 Detection means 91 Control means 100 Air battery 200 Air battery 300 Air battery

Claims (4)

A casing, a power generation unit and an electrolyte provided in the casing, an electrolyte consumption calculation means for calculating consumption of the electrolyte, and an electrolyte consumption calculated by the electrolyte consumption calculation means An electrolyte amount adjusting means for adjusting the amount of the electrolyte in the casing based on
An air battery in which the electrolyte consumption is calculated by the following equation (1) in the electrolyte consumption calculation means.
y = a * x * n ... Formula (1)
In equation (1), y is the electrolyte consumption, a is the electrolyte consumption coefficient, x is the electric capacity obtained from the battery, and n is the number of charge / discharge cycles of the battery. A casing, a power generation unit and an electrolyte provided in the casing, an electrolyte consumption calculation means for calculating consumption of the electrolyte, and an electrolyte consumption calculated by the electrolyte consumption calculation means An electrolyte amount adjusting means for adjusting the amount of the electrolyte in the casing based on
In the electrolytic solution consumption calculation means, the electrolytic solution consumption is calculated by the following formula (2).
y = a · X Equation (2)
In equation (2), y is the electrolyte consumption, a is the electrolyte consumption coefficient, and X is the cumulative electric capacity obtained from the battery. The electrolyte amount adjusting means has an electrolyte tank containing an electrolyte, an electrolyte supply channel extending from the electrolyte tank to the housing, and a valve provided in the electrolyte supply channel;
3. The air battery according to claim 1, wherein opening and closing of the valve is controlled based on the calculated amount of electrolyte consumption, whereby the amount of the electrolyte in the casing is adjusted. The air battery according to any one of claims 1 to 3 , wherein the adjustment of the amount of the electrolyte in the casing is performed by supplying the electrolyte from the upper side surface of the casing into the casing.

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