JP2017084551A - Metal-air battery - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a metal-air battery capable of securely reducing a passive film.SOLUTION: The metal-air battery includes a passive film suppression circuit 41, in which a metal electrode 22 is made of a material on a surface of which a passive film is formed by an oxidation reaction, including a conduction path 42 that generates a permanent conduction state between a pair of terminals 11A, 11B connected to the metal electrode 22 and the air electrode 23, respectively and a current regulator 43 that is provided on the conduction path 42 and regulates the value of a current flowing through the conduction path 42.SELECTED DRAWING: Figure 1

Description

  The present invention relates to a metal-air battery including a metal electrode made of a material having a passive film formed on the surface by an oxidation reaction.

  There is known a metal-air battery including a metal electrode made of a material on which a passive film is formed on the surface by an oxidation reaction. This type of metal-air battery has a circuit that selectively forms a closed circuit including a metal electrode and an air electrode in a state where a load is not connected in order to remove a passive film (also referred to as a passive film). The provided structure is disclosed (for example, refer patent documents 1 and 2).

In addition, the lithium battery inspection device “closes the switch on the drive circuit at regular intervals and supplies power to the inspection load on the drive circuit from the battery by closing the switch, thereby energizing the drive circuit. The voltage drop is inspected based on the terminal voltage of the battery obtained by the operation, and energization for disassembling the protective film generated on the surface of the battery terminal during opening of the switch is performed to close the switch. The configuration performed on the driving circuit ”is disclosed (for example, see Patent Document 3).
According to the configuration of Patent Document 3, an increase in the internal impedance of the battery due to the protective film generated and accumulated on the surface of the battery terminal by an amount corresponding to a period in which no energization is performed is caused by the voltage of the battery. It is described that it is possible to accurately perform a battery voltage drop test while suppressing an adverse effect on the periodic test for a drop.

Japanese Patent No. 5684929 JP 2014-22345 A JP 2001-264399 A

However, in the configurations of Patent Documents 1 and 2, the passive film formed by the oxidation reaction may not be sufficiently removed. In addition, when a passive film is generated in a no-load state, it takes a considerable time to supply power to the load even if the passive film can be removed.
By the way, when the spread of the metal-air battery is taken into consideration, the state of the metal-air battery is detected based on the battery voltage. However, according to the study by the inventors, when a passive film is formed on a metal-air battery, for example, a magnesium-air battery, it is difficult to extract current but voltage is easily generated. It has been difficult to determine whether or not power can be supplied to the load by forming a film, and whether or not a simple metal electrode has reached the battery life due to exhaustion or depletion of the electrolyte. Even if the configuration of Patent Document 3 is applied to a metal-air battery, it is difficult for the metal-air battery to determine the state of the battery from the battery voltage. For this reason, it is also required to determine the state of the metal-air battery where the battery voltage tends to be high.

  This invention is made | formed in view of the situation mentioned above, and it aims at providing the metal air battery which can reduce a passive film more reliably.

  In order to solve the above-described problems, the present invention provides a metal-air battery including a metal electrode made of a material on which a passive film is formed by an oxidation reaction, and an air electrode. It is characterized by comprising a conduction path that always conducts between a pair of terminal portions connected to each other, and a current adjusting element that is provided in the conduction path and adjusts the value of a current flowing through the conduction path.

In the above configuration, the current adjusting element may be connected in parallel to a battery body having the metal electrode and the air electrode.
Further, in the above configuration, a closed circuit including the metal electrode and the air electrode is formed with a time interval in a state where a load is not connected to the metal-air battery, and the passive circuit is removed from the closed circuit. A passive film removal circuit for flowing the current may be provided.

  The present invention also provides a metal-air battery comprising a metal electrode made of a material having a passive film formed on the surface by an oxidation reaction, and an air electrode. The first closed circuit includes the metal electrode and the air electrode. And a passive film suppression circuit that constantly discharges the metal-air battery to suppress the formation of a passive film, and the metal-air battery is not connected to a load, and the metal is separated with a time interval. Forming a second closed circuit including a pole and the air electrode, forming a passive film removal circuit for passing a current for removing the passive film to the second closed circuit, and forming the second closed circuit. And a state determination unit that determines the state of the metal-air battery based on the generated power voltage.

  In the above configuration, the state determination unit includes a notifying unit that determines at least one of the initial stage of power generation, the middle period of power generation, and the end of discharge, and notifies the state based on a determination result of the state determination unit. May be.

Further, in the above configuration, the converter includes a converter that converts and outputs DC power of the battery main body having the metal electrode and the air electrode, and the state determination unit until the battery main body determines that the power generation is in the middle of power generation. The converter may be held in an operation stop state.
The metal electrode may be made of a magnesium alloy containing zinc.

  The present invention is provided with a conduction path that always connects a pair of terminal portions respectively connected to a metal electrode and an air electrode made of a material on which a passive film is formed on the surface by an oxidation reaction, and the conduction path. And a current adjusting element that adjusts the value of the current flowing through the conduction path, so that the current adjusted by the current adjusting element can always flow to suppress the formation of the passive film, It can be reduced more reliably.

It is the figure which showed the structure of the metal air battery system which concerns on embodiment of this invention. It is the flowchart which showed the operation | movement of a microcomputer.

Hereinafter, an embodiment of the present invention will be described with reference to the drawings.
FIG. 1 is a diagram showing a configuration of a metal-air battery system 10 according to an embodiment of the present invention.
The metal-air battery system 10 includes a battery body 11 and a connection unit 12 connected to the battery body 11. The battery body 11 is configured by connecting a plurality of unit cells 21 in series. Each unit cell 21 includes a pair of metal electrodes 22 and an air electrode 23, and oxygen in the air is injected by injecting an electrolyte solution. It is comprised in the metal air battery which generates electric power using an electrochemical reaction. During power generation, the metal electrode 22 functions as a negative electrode, and the air electrode 23 functions as a positive electrode. The entire metal-air battery system 10 is also referred to as a metal-air battery.

  The metal electrode 22 is formed of a magnesium alloy and is disposed to face the air electrode 23. More specifically, the metal electrode 22 is formed as a magnesium electrode made of ASTM standard AZ31, AZ61, AZ91, or the like, which is 96% magnesium, 3% aluminum, and 1% zinc. In addition, you may use not only what is based on an ASTM specification but a well-known Mg-Al-Zn type alloy. Further, elements other than aluminum and zinc may be added. For example, other elements such as Si, Cu, Li, Na, K, Fe, Ni, Ti, and Zr may be added.

  The electrolytic solution is an electrolytic solution capable of eluting magnesium ions from the metal electrode 22. More specifically, the electrolytic solution contains chloride ions as anions, alkali metal ions (Li, Na, K, Rb, Cs, Fr) as cations, and alkaline earth metal ions (Be, Mg, Ca, Sr). , Ba, Ra). In the present embodiment, a sodium chloride aqueous solution containing sodium ions is used as the electrolytic solution in terms of safety and high conductivity.

  That is, the battery body 11 is a magnesium air battery. The magnesium-air battery can easily procure the electrolyte because seawater can be used as the electrolyte or a liquid in which salt is mixed with tap water can be used. In addition, you may comprise so that the bag body which accommodated the sodium chloride which is electrolyte may be previously arrange | positioned inside the battery main body 11, and it generate | occur | produces electricity only by injecting water, such as tap water.

  The air electrode 23 is a component having air permeability that allows external air to pass through the battery body 11 and non-liquid permeability that does not leak electrolyte. The air electrode 23 is formed by integrating a catalyst sheet constituting a catalyst layer on both sides of a rectangular copper mesh constituting a current collector by pressing (pressing) or the like. In addition, about a liquid non-permeable property, you may ensure by providing the sheet | seat which has a liquid non-permeable property separately. Further, the air electrode 23 is not limited to the above-described configuration, and a known configuration can be widely applied.

The battery body 11 has a pair of terminal portions 11A and 11B constituting a positive electrode terminal and a negative electrode terminal. The connection unit 12 is detachably connected to the terminal portions 11 </ b> A and 11 </ b> B of the battery body 11, and the generated power of the battery body 11 is supplied to the connection unit 12.
The connection unit 12 includes a pair of power supply lines 31 and 32 connected to the terminal portions 11A and 11B, and a plurality (two in this configuration) of converters 34 that function as power conversion units that convert generated power into predetermined power. A plurality of (two in this configuration) USB (Universal Serial Bus) ports 36 that function as power output units that output the converted power, and a microcomputer 38 that functions as a control unit that controls each unit of the connection unit 12. I have.

Each converter 34 is a DC / DC converter, converts generated power supplied via a pair of power supply lines 31 and 32 into predetermined DC power, and is associated with each converter 34 on a one-to-one basis. Output to port 36. Each converter 34 can be switched between an operation state and an operation stop state by a signal SA from the microcomputer 38.
The converter 34 and the USB port 36 are not limited to two, but may be three or more or one. Further, not only the USB port but also a power output unit other than the USB port may be applied. Further, when a device other than the USB port is used, the converter 34 may be a DC / AC converter.

  By the way, in the metal air battery system 10 of this structure, each reaction of the air electrode 23 and the metal electrode 22 is as follows.

(Air electrode) O ₂ + 2H ₂ O + 4e ⁻ → 4OH ⁻
(Metal pole)
Power generation reaction of magnesium: Mg + 2OH ⁻ → Mg (OH) ₂ + 2e ⁻
Magnesium self-discharge: Mg + 2H ₂ O → Mg (OH) ₂ + H ₂
Power generation reaction of zinc: Zn + 4OH ⁻ → Zn (OH) ₄ ²⁻ + 2e ⁻
In electrolytic solution: Zn (OH) ₄ ²⁻ → ZnO + H ₂ O + 2OH ⁻
Power generation reaction of aluminum: Al + 3OH ⁻ → Al (OH) ₃ + 3e ⁻

In general, since magnesium is a highly reactive material, self-discharge tends to occur as described above.
In this configuration, by using the magnesium alloy, the oxide (for example, zinc oxide) generated by the oxidation reaction functions as a protective coating that inhibits self-discharge on the surface of the metal electrode 22 and suppresses generation of hydrogen. The self-discharge reaction can be suppressed by forming a passive film.

  However, according to studies by the inventors, when a passive film is formed on the surface of the metal electrode 22 by an oxidation reaction, the passive film may inhibit the battery reaction (power generation reaction). For example, when the discharge is stopped after the discharge is stopped, the battery reaction may not be sufficiently restarted, and a necessary current may not be taken out.

Therefore, in this embodiment, in order to reduce the inhibition of the battery reaction by the passive film, the connection unit 12 includes the passive film suppression circuit 41 that suppresses the generation of the passive film, and the passive film that removes the passive film. And a removal circuit 51.
Furthermore, in this embodiment, the connection unit 12 includes a notification unit 61 that notifies the battery state, and notifies the state of the battery main body 11 based on the determination result of the microcomputer 38.

The passive film suppression circuit 41 is a resistive discharge that includes a conduction path 42 (also referred to as a conduction line) that always conducts between the pair of terminal portions 11A and 11B, and a current adjusting element 43 provided in the conduction path 42. Formed in the circuit. The conduction path 42 is formed as a line connecting the pair of power supply lines 31 and 32 on the battery main body 11 side.
By this conduction path 42, a first closed circuit 41K including the metal electrode 22 and the air electrode 23 is always formed. The current adjusting element 43 is a resistance element that adjusts the value of the current flowing through the conduction path 42 to a predetermined set current value.

  According to the passive film suppression circuit 41, the first closed circuit 41K including the metal electrode 22 and the air electrode 23 is always formed. Since the current adjusted by the current adjustment element 43 always flows through the closed circuit 41K, the battery main body 11 continues to be discharged. Thereby, the production | generation of a passive film is suppressed compared with the time of discharge stop.

  If the current value adjusted by the current adjusting element 43 is too large, the power generation time is shortened, and the power generation time (for example, 5 days) required for the metal-air battery system 10 is not satisfied. On the other hand, if the current value adjusted by the current adjusting element 43 is too small, the passive film cannot be sufficiently suppressed. If the passive film cannot be sufficiently suppressed, it will be difficult to remove the passive film even if the passive film removal circuit 51 is used.

  Therefore, the inventors set the current value adjusted by the current adjusting element 43 to the minimum current value necessary for a device (power consuming device) connected to the USB port 36, or a value close thereto. The generation of the passive film is suppressed to a level that can be sufficiently removed by the passive film removal circuit 51 described later while sufficiently securing the power generation time.

  More specifically, the inventors changed the current value adjusted by the current adjusting element 43 to various values, and as a result, good results were obtained at 100 mA or more, more preferably 150 mA. By setting this range, a practically sufficient performance can be obtained, and a mobile phone as an example of a device connected to the USB port 36 can be charged. Further, the passive film is removed by the passive film removing circuit 51. The passive film could be suppressed as much as possible.

  In the present embodiment, the case where a resistance element is used as the current adjusting element 43 has been described. However, the present invention is not limited to this, and other elements having a resistance component such as a diode may be used. In addition, since the current adjusting element 43 is connected in parallel to the battery body 11, the influence on the converter 34 and the passive film removing circuit 51 is suppressed, and the current is always supplied with a simple configuration. can do.

Next, the passive film removal circuit 51 will be described.
The passive film removal circuit 51 is an open / close type that includes another conduction path 52 that connects the pair of terminal portions 11A and 11B, and a current adjustment element 53 and a switching element 54 that are connected in series to the conduction path 52. The resistor discharge circuit is formed. The switching element 54 is a field effect transistor (FET), and its opening and closing is controlled by a signal SB from the microcomputer 38. The current adjusting element 53 is a resistance element that adjusts the value of the current flowing through the conduction path 52 to a current that removes the passive film. In this embodiment, a resistance value that allows a current of 1 A to flow is selected.

  The microcomputer 38 is an MPU that operates with extremely low power consumption, and controls the passive film removal circuit 51 to temporarily switch the switching element 54 from open to closed with a time interval. Thereby, the passive film removal circuit 51 forms the 2nd closed circuit 51K containing the metal electrode 22 and the air electrode 23, and connects the element 53 for electric current adjustment as a forced load. Therefore, a large current is forced to flow temporarily through the second closed circuit 51K, and the passive film formed on the surface of the metal electrode 22 is dissolved in the electrolytic solution to expose the fresh metal surface. it can.

  In this configuration, the microcomputer 38 temporarily switches the switching element 54 from open to closed when a power consuming device serving as a load is not connected to the USB port 36. As a result, the second closed circuit 51K is formed when the power generation voltage of the battery body 11 is higher than when the power consuming device is connected, and the current value flowing through the second closed circuit 51K can be efficiently increased. it can. Therefore, it is advantageous for removing the passive film.

Next, the notification unit 61 will be described.
The notification unit 61 includes an LED element 62 that functions as a light source, and a switching element 63 (in this embodiment, a field effect transistor (FET)) that turns on and off power supply to the LED element 62. A pair of LED elements 62 and switching elements 63 are provided for each USB port 36. Note that the driving power of the LED element 62 is the output power of the converter 34.

  The microcomputer 38 acquires the potential of the power supply line 31 via the built-in A / D conversion circuit, and based on this potential (hereinafter referred to as “power generation voltage V1”), the battery body 11 is in the initial power generation immediately after water injection, the power generation state. A process is performed to determine whether the battery is in a stable middle power generation state or a final discharge state, and depending on the determination result, the lighting / extinguishing control of each LED element 62 is varied to change the state to the user. Can be notified.

FIG. 2 is a flowchart showing the operation of the microcomputer 38.
In the initial state, each of the switching elements 54 and 63 is in an open state, and the converter 34 is in an operation stop state.
When the electrolytic solution is injected into the battery body 11 and the battery body 11 starts generating power, the microcomputer 38 is first activated, and a preset initial waiting time T0 (T0 = 10 seconds in the present embodiment) elapses. (Step S1). This initial waiting time T0 is a waiting time until the power generation state is stabilized to some extent after the battery main body 11 starts power generation (step S1).

When the initial waiting time T0 has elapsed, the microcomputer 38 proceeds to the process of step S2.
In the process of step S2, the microcomputer 38 temporarily switches the switching element 54 from open to closed, connects the current adjusting element 53 as a forced load, removes the passive film, and closes the switching element 54. The generated voltage V1 is measured. Then, the microcomputer 38 determines whether or not the measured power generation voltage V1 has reached a predetermined value VL that is a first predetermined value set in advance (in this embodiment, VL = 3.15V) ( Step S3).

  Here, in this configuration, since the first closed circuit 41K including the metal electrode 22 and the air electrode 23 is always formed by the passive film suppression circuit 41, the passive film simultaneously starts the battery body 11 and generates power. The suppression circuit 41 functions, and generation of a passive film on the metal electrode 22 can be suppressed from the initial stage of power generation.

The specified value VL is a threshold value for determining whether or not the battery body 11 is within a preset specified voltage range, and is set to, for example, a lower limit value of the specified voltage range or a value in the vicinity thereof.
As described above, since the microcomputer 38 acquires the voltage when the switching element 54 is closed as the generated voltage V1, the generated voltage V1 when the current adjusting element 53 acts as a forced load is measured. Therefore, even in the case of a metal-air battery that is relatively high in voltage, the power generation voltage V1 is less than the specified value VL at the initial stage of power generation, and it can be determined that the power generation is in the initial stage.

If it is determined in step S3 that the generated voltage V1 does not reach the specified value VL (step S3; No), the microcomputer 38 has a fixed time T1 that is the operation cycle of the passive film removal circuit 51 (T1 = in this embodiment). 30 seconds) (step S4), the process proceeds to step S2. As a result, the passive film removal circuit 51 repeatedly removes the passive film at time T1 intervals until the generated voltage V1 reaches the specified value VL.
If the microcomputer 38 determines that the power generation voltage V1 has reached the specified value VL in step S3 (step S3; Yes), the control from the initial power generation consisting of the above-described steps S1 to S4 to the middle power generation control after step S5. And migrate.

In the process of step S5, the microcomputer 38 opens the switching element 54 of the passive film removing circuit 51 to release the forced load, switches all the converters 34 to the operating state, and closes the switching element 63 of the notification unit 61. The LED element 62 is switched to the lighting state by switching to the state.
Thereby, when the power generation voltage V1 becomes equal to or higher than the specified value VL, power supply to all the USB ports 36 is started, and the LED element 62 is turned on to notify the user that the power generation is in the middle state.

Next, the microcomputer 38 waits until a certain time T2 (in this embodiment, T2 = 10 minutes), which is the operation cycle of the passive film removal circuit 51, has elapsed (step S6), and then generates the generated voltage V1. It is measured and it is determined whether or not the generated voltage V1 is in a no-load state range (step S7).
Here, the no-load state is a state in which no power consuming device as a load is connected to all the USB ports 36. The generated voltage V1 is relatively low in a loaded state in which a power consuming device serving as a load is connected to at least one of the USB ports 36, and is relatively high in a no-load state. Thereby, it can be determined whether it is a no-load state based on the generated voltage V1.
The determination of whether or not the range is in the no-load state may be made by using a threshold value that can discriminate between the generated voltage V1 in the loaded state and the no-load state.

If it is determined that there is no load (step S7; Yes), the microcomputer 38 temporarily switches the switching element 54 from open to closed, connects the current adjusting element 53 as a forced load, and removes the passive film. Perform (step S8).
Further, the microcomputer 38 measures the generated voltage V1 when the switching element 54 is closed in the process of step S8, and determines whether or not it is the end of discharge based on the measured generated voltage V1 (step S9). More specifically, the microcomputer 38 determines that the state in which the measured power generation voltage V1 is equal to or lower than a predetermined value VE (3.0 V in this embodiment) that is a second predetermined value set in advance. When the number of times is confirmed continuously, it is determined that the state is at the end of discharge.
That is, the specified value VE is a determination reference value for determining whether or not it is the end of power generation, and is set to a value lower than a specified value VL that is a determination reference value for determining whether or not it is in the middle of power generation.

If it is determined that the state is not the end of discharge (step S9; No), the microcomputer 38 opens the switching element 54 of the passive film removal circuit 51 to release the forced load (step S10), and then performs the process of step S6. Migrate to As a result, the processes in steps S6 to S10 are repeatedly executed while it is not determined as the end-of-discharge state.
On the other hand, when the end-of-discharge state is reached, it is determined whether the generated voltage V1 is equal to or lower than the specified value VE continuously for a predetermined number of times, so that it is determined as the end-of-discharge state. With this determination method, it is possible to determine whether or not the discharge is at the end of discharge even in a metal-air battery with a relatively high voltage.

If it determines with the state of the last stage of discharge (step S9; Yes), the microcomputer 38 will open and close the switching element 63 of the alerting | reporting part 61 with a time interval as control of the last stage of discharge, and will switch the LED element 62 to a blinking state ( Step S11). Thereby, it can alert | report that it is the state of the end of discharge to a user by blinking of the LED element 62. FIG.
Note that the method for determining the end-of-discharge state is not limited to the above method. For example, in the case of a metal-air battery in which the generated voltage V1 greatly decreases when the end of discharge is reached, the end of discharge may be determined when the generated voltage V1 falls below a predetermined threshold.

Further, when it is determined in step S7 that the load is not in a no-load state (that is, a load is determined), the microcomputer 38 measures the generated voltage V1 and determines whether or not the end of discharge is based on the measured generated voltage V1. Is determined (step S12). More specifically, the microcomputer 38 determines that the state is at the end of the discharge when it is confirmed that the measured power generation voltage V1 is equal to or lower than the specified value VE or continuously for a predetermined specified number of times.
If the microcomputer 38 determines that it is not the end of discharge (step S12; No), the process proceeds to step S5. Therefore, while it is not in the end-of-discharge state, if it is a loaded state, the processes of steps S6, S7, and S12 are repeatedly executed.
Even when it is determined that the state is the end of discharge in the loaded state (step S12; Yes), the microcomputer 38 proceeds to the process of step S11 and is in the state of the end of discharge for the user by the blinking of the LED element 62. Is notified. The operation of the microcomputer 38 has been described above.

  As described above, in the metal-air battery system 10 (metal-air battery) of the present embodiment, the metal electrode 22 is made of a material in which a passive film is formed on the surface by an oxidation reaction, and the metal electrode 22 and the air electrode 23 are formed. And a pair of terminal portions 11A and 11B connected to each other, a conduction path 42 that is always in a conduction state, and a current adjustment element 43 that is provided in the conduction path 42 and adjusts the value of the current flowing through the conduction path 42. Since the passive film suppression circuit 41 is provided, the current adjusted by the current adjusting element 43 can always be supplied to suppress the generation of the passive film. Therefore, the passive film can be more reliably reduced as compared with a configuration in which only energization for decomposing the protective film is performed at regular intervals.

In addition, since the current adjusting element 43 is connected in parallel to the battery body 11 having the metal electrode 22 and the air electrode 23, while suppressing the influence on other circuits (for example, the passive film removal circuit 51), It is possible to maintain a state where a desired current is always passed with a simple configuration.
In addition, a second closed circuit 51K including the metal electrode 22 and the air electrode 23 is formed with a time interval in a state where a power consuming device as a load is not connected, and the second closed circuit 51K is passive. Since the passive film removal circuit 51 for supplying a current for film removal is provided, both suppression and removal of the passive film can be performed, and the passive film can be further reduced.

  Further, the metal air battery system 10 determines the state of the metal air battery system 10 (corresponding to the state of the battery body 11) based on the power generation voltage V1 when the second closed circuit 51K is formed. Since the microcomputer 38 functioning as a unit is provided, the battery voltage is determined based on the power generation voltage V1 when the timing of removing the passive film is used in a state where the passive film is more reliably reduced to improve the power generation state. It is possible to determine the state of the metal-air battery that tends to be high.

In this case, the microcomputer 38 determines whether the state is the initial stage of power generation, the middle stage of power generation, or the end stage of discharge based on the power generation voltage V1, and performs different notifications according to the determination result by the notification unit 61. In addition, it is possible to appropriately notify each state at the end of discharge.
In addition, although the case where all the initial stages of power generation, the middle period of power generation, and the end of discharge are determined and notified so that each state can be identified has been described, the present invention is not limited to this. Also good. That is, it is only necessary to determine at least one of the states in the initial stage of power generation, the middle period of power generation, and the end of discharge, and notify any of the determined states.

  Moreover, it has the converter 34 which converts and outputs the direct-current power of the battery main body 11 which has the metal electrode 22 and the air electrode 23, and the microcomputer 38 stops operation | movement of the converter 34 until the battery main body 11 determines with the electric power generation middle period Therefore, the activation of the metal-air battery can be promoted to promptly shift to the middle stage of power generation. Further, when the state of power generation is in the middle, the converter 34 is put into an operation state, so that stable power can be output from the converter 34.

  In the metal-air battery system 10, since the metal electrode 22 is made of a magnesium alloy containing zinc, a passive film is easily formed by zinc oxide generated by the battery reaction. Since the passive film suppression circuit 41 described above is provided under this configuration, it is possible to effectively suppress adverse effects due to the passive film while adopting the metal electrode 22 made of magnesium alloy containing zinc.

As mentioned above, although the form for implementing this invention was described, this invention is not limited to the above-mentioned embodiment, Based on the technical idea of this invention, various deformation | transformation and change are possible. For example, in the above-described embodiment, the case where the metal electrode 22 made of a magnesium alloy containing at least zinc is used is described. However, the present invention is not limited thereto, and a metal electrode made of a material that forms a passive film on the surface by an oxidation reaction is used. The present invention may be applied when used.
In the above-described embodiment, the case where the notification unit 61 notifies the state by turning off, turning on, and blinking the LED element 62 has been described. However, the state is notified by using a light source or a display device other than the LED element 62. Anyway. In addition, the notification unit 61 may be configured by a voice output device that reports the state by voice, or may be configured by a wireless transmission device that wirelessly transmits a signal indicating the state to a portable device carried by the user. good.

10 Metal-air battery system (metal-air battery)
DESCRIPTION OF SYMBOLS 11 Battery main body 11A, 11B Terminal part 12 Connection unit 22 Metal electrode 23 Air electrode 34 Converter 38 Microcomputer (state determination part)
41 Passive Film Suppression Circuit 41K First Closed Circuit 42 Conduction Path 43 Current Adjusting Element 51 Passive Film Removal Circuit 51K Second Closed Circuit 61 Notification Unit

In order to solve the above-described problems, the present invention provides a metal-air battery including a metal electrode made of a material on which a passive film is formed by an oxidation reaction, and an air electrode. a pair of the terminals portions connected respectively, always a conduction path to the conductive state in order to continue the discharge of the metal-air battery, Rutotomoni provided in series with the conduction path, the conductive path provided in the series A current adjusting element that adjusts the value of the flowing current to a current value that suppresses the generation of the passive film, and the current adjusting element includes a battery body having the metal electrode and the air electrode. Connected in parallel,
In a state where no load is connected to the metal-air battery, a closed circuit including the metal electrode and the air electrode is formed with a time interval, and a passive film is passed through the closed circuit to pass a current for removing a passive film. characterized Rukoto includes a film removal circuit.

In the above-described configuration, the state determination unit determines at least one of a power generation middle stage and a discharge end stage in which power generation voltage reaches a predetermined value set in advance after power generation is stable in the initial stage of power generation. A notification unit that notifies the state based on the determination result of the state determination unit may be provided.

Further, in the above configuration, a converter that converts and outputs DC power of a battery main body having the metal electrode and the air electrode is provided, and the state determination unit is configured to preliminarily generate a power generation voltage after the power generation initial state and power generation state is stabilized. It determines the state of at least the power generation middle of the power generation middle period and the end of discharge that has reached the set specified value, and holds the converter in an operation stopped state until the battery body determines the power generation middle period. May be.
The metal electrode may be made of a magnesium alloy containing zinc.

In order to solve the above-described problems, the present invention provides a metal-air battery including a metal electrode made of a material on which a passive film is formed by an oxidation reaction, and an air electrode. provided between the pair of terminal portions connected respectively to the always conductive state in order to continue the discharge of the metal-air battery, and the value of the current flowing in the path of the conductive state, it generates suppression of the passivation film a current adjustment element to adjust the current value, the current regulating element is a battery body having a said metal electrode the cathode, are connected in parallel, connecting the load to the metal-air battery A passive circuit removing circuit that forms a closed circuit including the metal electrode and the air electrode with a time interval in a state in which a current for removing the passive film is supplied to the closed circuit. To do.

Claims (7)

In a metal-air battery comprising a metal electrode made of a material that forms a passive film on the surface by an oxidation reaction, and an air electrode,
Between a pair of terminal portions respectively connected to the metal electrode and the air electrode, a conduction path that always conducts,
A current adjusting element that is provided in the conduction path and adjusts a value of a current flowing through the conduction path;
A metal-air battery comprising:   The metal-air battery according to claim 1, wherein the current adjusting element is connected in parallel to a battery body having the metal electrode and the air electrode.   In a state where no load is connected to the metal-air battery, a closed circuit including the metal electrode and the air electrode is formed with a time interval, and a passive film is passed through the closed circuit to pass a current for removing a passive film. The metal-air battery according to claim 1, further comprising a film removal circuit. In a metal-air battery comprising a metal electrode made of a material that forms a passive film on the surface by an oxidation reaction, and an air electrode,
A passive film suppression circuit that always forms a first closed circuit including the metal electrode and the air electrode, and that constantly discharges the metal-air battery to suppress generation of a passive film;
A second closed circuit including the metal electrode and the air electrode is formed with a time interval with no load connected to the metal-air battery, and a passive film is removed from the second closed circuit. A passive film removal circuit for passing current to
A state determination unit that determines the state of the metal-air battery based on the generated voltage when the second closed circuit is formed;
A metal-air battery comprising: The state determination unit determines at least one state among the initial stage of power generation, the middle period of power generation and the end stage of discharge,
The metal-air battery according to claim 4, further comprising a notification unit that notifies the state based on a determination result of the state determination unit. A converter that converts and outputs DC power of a battery body having the metal electrode and the air electrode;
6. The metal-air battery according to claim 4, wherein the state determination unit holds the converter in an operation stopped state until the battery main body determines that the power generation is in the middle of power generation.   The metal-air battery according to any one of claims 1 to 6, wherein the metal electrode is made of a magnesium alloy containing zinc.

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