JP6588228B2 - Battery system and charging tank - Google Patents

Description

The present invention relates to a battery system, an electrode cartridge, a discharge tank, a battery, and a charging tank. More specifically, the present invention relates to a mechanical charging system battery system, and an electrode cartridge, a discharge tank, a battery, and a charging tank constituting the battery system.

A metal-air battery is an example of a battery in which a positive electrode and a negative electrode are provided in the electrolytic solution. A metal-air battery is a battery in which a negative electrode (anode) is composed of a metal electrode, and a positive electrode (cathode) is composed of an air electrode. Since it has a high energy density, development and research for practical use are being promoted. ing.

An example of the metal-air battery is a zinc-air battery. FIG. 18 is a schematic cross-sectional view showing an example of the structure of a conventional zinc-air battery, and FIG. 19 is a schematic cross-sectional view for explaining a battery reaction in the zinc-air battery. The zinc-air battery 121 has a structure in which a zinc electrode (negative electrode) 111 is provided in an alkaline electrolyte 115 and an air electrode (positive electrode) 112 is provided between the air flow path 113 and the electrolyte 115, Electric power is output from the zinc electrode 111 and the air electrode 112 as the battery reaction (discharge reaction) proceeds.

In the battery reaction of the zinc-air battery 121, metallic zinc constituting the zinc electrode 111 reacts with hydroxide ions in the electrolytic solution 115 to form tetrahydroxozinate ions, and electrons are released into the zinc electrode 111. In addition, the tetrahydroxozincate ion is decomposed and zinc oxide or zinc hydroxide is precipitated in the electrolytic solution 115. Further, hydroxide ions are generated by the reaction of electrons, water, and oxygen in the air electrode 112, and these hydroxide ions move to the electrolytic solution 115. When such a battery reaction proceeds, the zinc metal of the zinc electrode 111 is consumed, and zinc oxide and zinc hydroxide accumulate in the electrolytic solution 115. Therefore, in order to maintain the power output from the zinc-air battery 121, it is necessary to supply metallic zinc to the zinc electrode 111.

As exemplified by the zinc-air battery, in the metal-air battery, the negative electrode active material is consumed together with the discharge. On the other hand, the zinc-air battery cell which can be recharged mechanically is proposed (for example, refer patent document 1). In the zinc-air battery cell of Patent Document 1, a battery is formed by putting a zinc anode (negative electrode) in a housing containing an electrolytic solution. When the active zinc is consumed, the anode is removed from the housing and replaced with a new anode.

JP 7-45270 A

As described above, in the metal-air battery, a mechanical charging method in which the discharged negative electrode is replaced with a new negative electrode can be adopted. Here, after the discharged negative electrode is taken out from the discharge tank, it is charged by reducing the electrode active material oxidized by the discharge reaction in a charging tank different from the discharge tank, and discharged in the discharge tank. Regenerated to a possible negative electrode. In the case of a metal zinc battery, the discharged negative electrode is a zinc electrode in which zinc as an electrode active material is oxidized by a discharge reaction, and the zinc oxide is reduced to zinc in a charging tank.

In this specification, the discharge tank means an electrolytic cell that is provided with a positive electrode and is used for discharge containing an electrolytic solution, and the charging tank is used for charging that is provided with a positive electrode and contains an electrolytic solution. This means an electrolytic cell. The positive electrode can be formed as part of the wall of the discharge tank or the charging tank.

In a metal-air battery that employs a mechanical charging method, only the negative electrode needs to be replaceable. As the negative electrode, generally, an electrode active material and a current collector can be used as long as they have an electrode active material and a current collector. For example, in the case of a zinc electrode constituting the negative electrode of a zinc-air battery, it can be manufactured relatively easily by electrodeposition of zinc or the like. Moreover, if the metal which can become an electrode active material is contained, even if it is a metal rod containing an impurity, it can be discharged if immersed in electrolyte solution.

However, if the negative electrode charged under appropriate conditions is not used, the discharge capacity of the metal-air battery may be reduced, or the device life of the metal-air battery may be shortened. This is because if the negative electrode contains impurities such as Fe ions, the negative electrode may be subject to self-corrosion due to the impurities, or the reaction of the air electrode may be hindered.

Based on the above, as cartridge-type negative electrodes (electrode cartridges) used in mechanical charging battery systems, inferior or counterfeit products containing impurities other than electrode active materials are distributed on the market or illegally used by users. Or it was required to prevent misuse.

The present invention has been made in view of the above situation, and a mechanical charging system battery system capable of preventing the use of a non-genuine electrode cartridge, as well as an electrode cartridge, a discharge tank, and the like constituting the battery system, The object is to provide a battery and a charging tank.

As a result of examining a mechanical charging system battery system that can prevent the use of non-genuine electrode cartridges, the present inventors have provided an authentication mechanism for determining whether an electrode cartridge is a conforming product or a non-conforming product. I found it. When the electrode cartridge is provided with a storage unit for storing authentication information, the discharge tank reads the authentication information, and discharge is permitted when the authentication information is in a discharge-permitted state, and discharge is not permitted. The present inventors have arrived at the present invention by conceiving that the above-mentioned problem can be solved by providing an authentication unit for executing a process for preventing discharge.

That is, one aspect of the present invention is an electrode cartridge that can be reused by charging, a discharge tank that discharges with the electrode cartridge attached, and a charging tank that charges with the electrode cartridge after discharge attached The electrode cartridge has a storage unit that stores authentication information indicating a discharge permission state or a discharge non-permission state, and the discharge tank reads the authentication information stored in the storage unit, The battery system may include a first authentication unit that performs a process of permitting discharge when the discharge is permitted and preventing discharge when the discharge is not permitted.

Moreover, the electrode cartridge, the discharge tank, the battery, and the charging tank that constitute the battery system are also one embodiment of the present invention. That is, one embodiment of the present invention is an electrode cartridge that can be reused by charging, and includes an electrode cartridge that includes a metal electrode and a storage unit that stores authentication information indicating a discharge permission state or a discharge permission state. Also good. One aspect of the present invention is a discharge tank that discharges with an electrode cartridge attached thereto, wherein the discharge tank reads authentication information stored in the electrode cartridge, and the authentication information is in a discharge-permitted state. It may be a discharge tank having an authentication unit that performs a process of permitting discharge and preventing discharge when the discharge is not permitted. One embodiment of the present invention may be a battery in which the electrode cartridge is attached to the discharge tank. One aspect of the present invention is a charging tank that performs charging with a discharged electrode cartridge attached, wherein the charging tank reads authentication information stored in the electrode cartridge, and the authentication information does not permit discharge. It may be a charging tank having an authentication unit that executes processing for permitting charging when in a state and blocking charging when in a discharging permitted state.

Since the battery system, electrode cartridge, discharge tank, battery, and charging tank of the present invention have the above-described configuration, it is possible to prevent the use of electrode cartridges that are not genuine products.

It is a block diagram which shows the whole structure of the battery system of Embodiment 1. It is the flowchart which showed the authentication flow (discharge tank processing flow) when the charged electrode cartridge in Embodiment 1 is attached to the discharge tank. It is the flowchart which showed the authentication flow (charge tank processing flow) when the electrode cartridge which has been discharged in Embodiment 1 is attached to the charge tank. It is the cross-sectional schematic diagram which showed an example of the structure of the discharge tank (at the time of discharge of a metal air battery) to which the electrode cartridge was attached. It is the cross-sectional schematic diagram which showed an example of the structure of the charging tank (at the time of charge) to which the electrode cartridge was attached. It is a block diagram which shows the whole structure of the battery system of Embodiment 2. 6 is a flowchart illustrating a charging tank processing flow in the second embodiment. It is the flowchart which showed the discharge tank process flow in Embodiment 3. 10 is a flowchart illustrating a charging tank processing flow according to Embodiment 3. It is a block diagram which shows the whole structure of the battery system of Embodiment 4. 6 is a flowchart showing a discharge tank processing flow in Embodiment 4. 6 is a flowchart showing a charging tank processing flow in Embodiment 4. 10 is a flowchart showing a discharge tank processing flow in Embodiment 5. 10 is a flowchart showing a charging tank processing flow in Embodiment 5. It is the schematic diagram explaining the method of measuring the electric potential difference between a negative electrode and a positive electrode. It is the model explaining the method of measuring the water surface level of electrolyte solution, and shows the case where a detector is mounted in the electrode cartridge (the left figure shows the state after mounting, and the right figure shows the state after mounting). It is the model explaining the method of measuring the water surface level of electrolyte solution, and shows the case where a detector is mounted in the discharge tank (the left figure shows the state before mounting, and the right figure shows the state after mounting). It is the schematic cross section which showed an example of the structure of the conventional zinc air battery. It is typical sectional drawing for demonstrating the battery reaction in a zinc air battery.

Embodiments will be described below, and the present invention will be described in more detail with reference to the drawings. However, the present invention is not limited only to these embodiments. Note that in the following description, the same portions or portions having similar functions are denoted by the same reference numerals in different drawings, and description thereof is not repeated.
In addition, the configurations of the respective embodiments may be appropriately combined or changed within a range not departing from the gist of the present invention.

[Embodiment 1]
The battery system according to the first embodiment includes an electrode cartridge that can be reused by charging, a discharge tank that discharges with the electrode cartridge attached, and a charging tank that charges with the electrode cartridge after discharge attached The electrode cartridge has a storage unit that stores authentication information indicating a discharge permission state or a discharge non-permission state, and the discharge tank reads the authentication information stored in the storage unit, It has the 1st certification | authentication part which performs the process which permits discharge when it is a discharge permission state, and blocks | disconnects discharge when it is the said discharge disapproval state, It is characterized by the above-mentioned.

Hereinafter, the battery system according to Embodiment 1 will be described with reference to the drawings. First, an outline of the battery system will be described, and then, a configuration when applied to a mechanically charged metal-air battery as an example of the battery system will be described in detail. Note that the battery system of the present invention is preferably applied to a battery that uses a recyclable / replaceable consumable, and can be applied to a fuel cell or the like in addition to a metal-air battery.

<Outline of battery system>
FIG. 1 is a block diagram illustrating the overall configuration of the battery system according to the first embodiment. The battery system of this embodiment includes an electrode cartridge, a discharge tank that attaches the electrode cartridge to perform discharge, and a charge tank that attaches and discharges the electrode cartridge after discharge.

The electrode cartridge is a replaceable member including at least an electrode active material that functions as a negative electrode of a battery, and can be attached to a discharge tank and a charging tank, respectively. When the electrode cartridge is attached to the discharge tank in which the electrolytic solution is placed, the battery is configured and can be discharged. The negative electrode active material is oxidized by the discharge. When the discharged electrode cartridge is removed from the discharge tank and attached to the charge tank, the oxidized electrode active material is reduced, that is, charged. The charged electrode cartridge can be attached to the discharge tank again and discharged. The electrode cartridge may include a current collector. As the electrode active material and the current collector, those used for general batteries can be used.

The electrode cartridge further includes a storage unit that stores authentication information indicating a discharge permission state (OK) or a discharge non-permission state (NG). The authentication information is electronic information that identifies a discharge permission state or a discharge disapproval state and can be processed by a computer. The storage unit is configured by hardware resources capable of storing electronic information. In the battery system of the first embodiment, if the authentication information is in the discharge permitted state, discharge in the discharge tank is permitted, and if the authentication information is in the discharge not permitted state, discharge in the discharge tank is blocked. Also, by identifying the discharge permission state or the discharge non-permission state, it is possible not only to control the discharge in the discharge tank, but also to control the charge in the charge tank. If charging in the charging tank is prevented and discharging is not permitted, charging in the charging tank may be permitted. That is, the use of the electrode cartridge can be managed by transitioning the authentication information stored in the storage unit between the discharge permission state and the discharge non-permission state.

The authentication information is not particularly limited as long as the discharge permission state or the discharge non-permission state can be identified. For example, the authentication information may be binary information such as “OK” and “NG”. Alternatively, it may be a log file that records the history of the electrode cartridge. As a method using a log file, when discharge (use) or charge is completed, the status information (“discharge (use)” or “charged”) is recorded at the end of the log file. A method for detecting the end information of the. As an advantage of using the log file, it is possible to know the timing of discarding the negative electrode when a certain number of charge-discharge cycles are repeated and the number of times that the reproduction cannot be performed is reached.

The discharge tank includes a positive electrode, and an electrolytic solution is held in the tank. By attaching an unused or charged electrode cartridge to the discharge tank containing the electrolytic solution, it functions as a battery (becomes a dischargeable state).

The discharge tank further includes a first authentication unit that authenticates authentication information stored in the storage unit of the electrode cartridge. The first authenticating unit executes a process of permitting discharge when the authentication information is in a discharge permitted state and blocking discharge when the authentication information is in a discharge not permitted state. The first authentication unit is configured by hardware resources that can process electronic information. As a result, the discharge can be started only when it is confirmed that the electrode cartridge inserted into the discharge tank is usable, such as a genuine product.

In addition, the discharge tank stores a first detection unit that detects information such as the electrode cartridge being inserted into the discharge tank and the completion of the discharge, and the information detected by the first detection unit. A first input unit that sends a command to rewrite the authentication information of the unit. The configuration of the first detection unit will be described in detail later. The first input unit is configured by hardware resources capable of processing electronic information. The first detection unit and / or the first input unit may be provided in the electrode cartridge. Furthermore, the discharge tank includes an insulating mechanism, an error notification sound generating mechanism such as a buzzer or a sound output device, and an error display unit such as a liquid crystal display or an LED lamp, which function when the first authentication unit determines that discharging is impossible. May be.

The charging tank includes a positive electrode (charging electrode), and an electrolytic solution is held in the tank. Charging (reduction of the negative electrode) is performed by attaching the discharged electrode cartridge to the charging tank containing the electrolytic solution. The charged electrode cartridge becomes reusable as the negative electrode of the battery.

The charging tank stores a second detection unit that detects information such as that the electrode cartridge has been inserted into the charging tank and that charging has been completed, and information detected by the second detection unit. A second input unit for sending a command to rewrite the authentication information of the unit. The configuration of the second detection unit will be described in detail later. The second input unit is configured by hardware resources capable of processing electronic information. The second detection unit and / or the second input unit may be provided in the electrode cartridge. Furthermore, the charging tank may have a second authentication unit (not shown in FIG. 1) for authenticating authentication information stored in the storage unit of the electrode cartridge. The second authentication unit is composed of hardware resources that can process electronic information. In addition, the charging tank includes an insulating mechanism, an error notification sound generating mechanism such as a buzzer or a sound output device, an error display unit such as a liquid crystal display or an LED lamp, which functions when the second authentication unit determines that charging is not possible. May be.

In addition, it is preferable that an electrode cartridge, a discharge tank, and a charging tank are provided with a wireless communication means. By wireless communication means, electronic information can be referred to, rewritten, etc. between the electrode cartridge, the discharge tank, and the charging tank.

<Battery system operation flow>
Next, the operation flow of the battery system of Embodiment 1 will be described with reference to the flowcharts of FIGS.

FIG. 2 is a flowchart showing an authentication flow (discharge tank treatment flow) when the charged electrode cartridge is attached to the discharge tank in the first embodiment. The discharge tank processing flow starts when the first detection unit detects that the electrode cartridge has been inserted into the discharge tank. The detection method by the first detection unit will be described in detail later. When the electrode cartridge is inserted into the discharge tank, the negative electrode of the electrode cartridge comes into contact with the electrolyte contained in the discharge tank. Further, the first authentication unit of the discharge tank and the storage unit of the electrode cartridge are connected for communication (step S11). The discharge tank refers to the authentication information stored in the storage unit of the electrode cartridge by the first authentication unit and confirms the authentication information (step S12). If the authentication information confirmed by the first authentication unit is in the discharge permission state (OK), the electrode cartridge is determined to be a compatible product, and discharge is started (step S13). Normally, the authentication information is in a discharge permission state when the electrode cartridge is a legitimate product and is in a charged or unused usable state. On the other hand, if the authentication information is in a discharge disapproval state (NG) or the authentication information cannot be confirmed, it is determined as a non-conforming product, and the discharge tank cannot be discharged so that the electrode cartridge cannot be used (step) S14). There are no particular limitations on the method for making the discharge impossible, and examples thereof include a method in which the air electrode of the discharge tank is insulated from the negative electrode of the electrode cartridge, and the electrolytic solution is discharged from the discharge tank. In addition, when it is determined that the discharge tank is a non-conforming product, it is preferable to make a notification such as making a buzzer sound with an alarm provided in the discharge tank or displaying on the screen that discharge is impossible.

After the start of discharge, the first detection unit detects whether or not the negative electrode has come into contact with the electrolytic solution (step S15). If the detection is not successful, the process returns to the confirmation of the authentication information in step S12. On the other hand, when the detection is successful, the first input unit rewrites the authentication information from the discharge permission state to the discharge non-permission state (step S16). In addition, the implementation timing of said step S16 is not specifically limited, For example, it may be simultaneous with the start of discharge, and may be the timing which extracts an electrode cartridge from electrolyte solution. When the discharge is completed, the electrode cartridge is taken out from the discharge tank and carried to the charge tank (step S17).

FIG. 3 is a flowchart showing an authentication flow (charging tank processing flow) when the discharged electrode cartridge is attached to the charging tank in the first embodiment. The charging tank processing flow starts when the second detection unit detects that the discharged electrode cartridge recovered from the discharging tank is inserted into the charging tank after the discharge tank processing flow is completed. At this time, the negative electrode of the electrode cartridge is in contact with the electrolytic solution accommodated in the charging tank. In addition, the second input unit of the charging tank and the storage unit of the electrode cartridge are connected for communication (step S21). Subsequently, charging of the discharged electrode cartridge is started (step S22). When the second detection unit detects charging of the negative electrode, the second input unit rewrites the authentication information stored in the storage unit of the electrode cartridge from the discharge non-permitted state to the discharge permitted state (step S23). Thereby, it becomes possible to discharge in the next discharge tank processing flow. The execution timing of step S23 is not particularly limited. For example, it may be simultaneous with the start of charging, or may be a timing for extracting the electrode cartridge from the electrolytic solution. When the charging is completed, the electrode cartridge is taken out from the charging tank and carried to the discharging tank (step S24). In addition, although a 2nd detection part and a 2nd input part may be provided in a charging tank, it is also possible to provide in an electrode cartridge.

According to the battery system of the present embodiment described above, it is possible to exclude electrode cartridges (pirated products) manufactured or regenerated by a pirated manufacturer (unauthorized company). By preventing the use of nonconforming products, the battery life can be extended. Moreover, the discharge capacity as designed can be obtained.

<Metal-air battery>
Since the battery system of this embodiment includes a combination of an electrode cartridge, a discharge tank, and a charging tank, it is suitable for, for example, a mechanically charged metal-air battery. A metal-air battery is a battery having an electrolytic solution, an air electrode as a positive electrode of the battery, and a metal electrode (electrode active material) as a negative electrode of the battery. In the mechanical charging method, the negative electrode of the battery is formed into a cartridge. In the metal-air battery after discharge, the electrode cartridge is removed from the discharge tank, and the removed electrode cartridge is regenerated (reduced) in the charge tank. FIG. 4 is a schematic cross-sectional view showing an example of the configuration of the discharge tank (when discharging the metal-air battery) to which the electrode cartridge is attached, and FIG. 5 is a diagram of the charging tank (when charging) to which the electrode cartridge is attached. It is the cross-sectional schematic diagram which showed an example of the structure. Hereinafter, the metal-air battery of the mechanical charging method will be described with reference to FIGS. 4 and 5.

(Electrode cartridge)
The electrode cartridge is a replaceable member provided with a metal electrode 11a. When the metal-air battery 21 is used, it is attached to a discharge tank (battery casing).

The metal electrode 11a contains at least an electrode active material that functions as the negative electrode of the metal-air battery 21, and may contain a current collector (current collection structure). Examples of the electrode active material include metals such as zinc, lithium, sodium, calcium, magnesium, aluminum, iron, cobalt, cadmium, and palladium, alloys of these metals, or mixtures containing these metals and alloys. Among these, zinc is preferably used as the electrode active material. The metal electrode 11a may include an oxide of an electrode active material. However, the oxide of the electrode active material does not contribute to the discharge.

An additive may be added to the metal electrode 11a as necessary. For example, when the metal electrode 11a mainly composed of zinc is used, it is possible to prevent the metal electrode 11a from self-corrosion by adding an additive such as indium, bismuth, aluminum, or calcium.

The metal electrode 11a may be in direct contact with the electrolytic solution 15 in the discharge tank, but an ion conductive separator may be provided between the metal electrode 11a and the electrolytic solution 15. That is, the electrode cartridge may have a separator that covers the metal electrode 11a. The separator only needs to have resistance to electrolytic solution and ion conductivity, and a solid electrolyte, a porous resin film, or a nonwoven fabric can be used. Examples of the solid electrolyte include an ion conductive ceramic and an ion conductive glass. Examples of the porous resin include polyethylene, polypropylene, nylon 6, nylon 66, polyolefin, polyvinyl acetate, polyvinyl alcohol-based material, and polytetrafluoroethylene (PTFE). The separator is preferably hydrophilized so that the flow of the electrolytic solution 15 is improved. Ion conductivity may be improved by dispersing an electrolyte salt such as a zinc salt or a lithium salt in the porous resin.

The electrode active material emits electrons by the discharge reaction of the metal-air battery 21 and dissolves in the electrolytic solution 15, and then deposits as a metal compound such as a metal oxide or metal hydroxide. For example, when the electrode active material is zinc, zinc is oxidized as the battery reaction proceeds, and zinc oxide that does not contribute to discharge is generated. Therefore, the electrode cartridge that has passed the expiration date is replaced with a new electrode cartridge. Thereby, the metal air battery 21 can be operated continuously.

The electrode cartridge after discharge is charged in the charging tank 31 for reuse. That is, the electrode cartridge is suitable for both the discharge tank (battery casing) and the charging tank 31. The charging process is a process for reducing the oxidized electrode active material of the electrode cartridge and returning it to a state in which discharge in the discharge tank is possible. Specifically, the electrolytic solution 17 is put in the charging tank 31, and the charging electrode (positive electrode) 16 formed of a metal suitable for reduction of the electrode active material, and the electrode cartridge after discharging (the negative electrode 11b during charging) Is immersed in the electrolytic solution 17 to cause a reduction reaction. The electrode cartridge regenerated by the charging process is reused in the discharge tank.

(Discharge tank)
The metal-air battery 21 is in a dischargeable state with the charged electrode cartridge attached to the discharge tank (battery casing). The negative electrode (anode) of the metal-air battery 21 is a metal electrode (electrode active material) 11a provided in the electrode cartridge. The positive electrode (cathode) of the metal-air battery 21 is the air electrode 12 provided in the discharge tank.

The discharge tank is a container that holds the electrolytic solution 15 and includes the air electrode 12. The discharge tank is preferably made of a material having corrosion resistance to the electrolyte solution 15. The electrolytic solution 15 is a liquid having an ionic conductivity in which an electrolyte is dissolved in a solvent. The type of the electrolytic solution 15 may be selected according to the type of the electrode active material constituting the metal electrode 11a, and may be an electrolytic solution (aqueous electrolyte solution) using an aqueous solvent, or an electrolytic solution (organic) using an organic solvent. Electrolyte solution).

For example, in the case of a zinc-air battery, an aluminum-air battery, or an iron-air battery, an alkaline aqueous solution such as an aqueous sodium hydroxide solution or an aqueous potassium hydroxide solution can be used as the electrolyte solution 15. In the case of a magnesium air battery, the electrolyte solution 15 can be a neutral aqueous solution such as a sodium chloride aqueous solution. In the case of a lithium metal battery, a sodium air battery, or a calcium air battery, an organic electrolyte can be used.

Moreover, the discharge tank may be provided with a mechanism for discharging the electrolyte solution 15 such as a valve. For example, the electrolytic solution 15 in the discharge tank is held in the discharge tank when the bulb is closed, and is discharged from the discharge tank when the bulb is opened.

A partition wall may be provided in the discharge tank. Due to the partition walls, a reaction region where the metal electrode 11a and the air electrode 12 face each other and a groove region separated from the reaction region by the partition walls are provided in the discharge tank. The partition wall does not reach the upper end in the discharge vessel, and the reaction region and the groove region communicate with each other above the discharge vessel. Further, a mechanism for discharging the electrolytic solution 15 is provided in the groove region. With such a configuration, when the liquid level of the electrolytic solution 15 exceeds the upper end of the partition wall in the reaction region, the electrolytic solution 15 is discharged, so that the inflow amount and the outflow amount of the electrolytic solution 15 into the discharge tank are reduced. Even if it does not make it correspond, it can prevent that the electrolyte solution 15 overflows from the upper part of a discharge tank.

In addition, a recovery tank in which the electrolytic solution 15 discharged from the discharge tank is stored, and a supply tank in which the electrolytic solution 15 put into the discharge tank is stored may be connected to the discharge tank.

The air electrode 12 is an electrode that generates hydroxide ions (OH ⁻ ) from oxygen gas, water, and electrons in the atmosphere. As with the metal electrode 11a, it is preferable that the electrode surface be provided in the discharge tank so as to be parallel to the direction of gravity. The electrode surface of the metal electrode 11a and the electrode surface of the air electrode 12 are preferably opposed to each other.

The air electrode 12 includes, for example, a configuration including a conductive porous carrier and an air electrode catalyst supported on the porous carrier. According to such a configuration, oxygen gas, water, and electrons can coexist on the air electrode catalyst, and the electrode reaction can proceed efficiently. The air electrode catalyst is preferably supported in the form of fine particles and supported on a porous carrier. The water used for the electrode reaction may be supplied from the atmosphere or may be supplied from the electrolytic solution 15.

Examples of porous carriers include carbon black such as acetylene black, furnace black, channel black, and ketjen black; conductive carbon particles such as graphite and activated carbon; vapor grown carbon fiber (VGCF), carbon nanotube, and carbon nanowire. Carbon fibers such as can be used. For example, Denka Black (registered trademark) manufactured by Denki Kagaku Kogyo Co., Ltd. can be used as acetylene black.
The porous carrier may be surface-treated so that a cationic group exists as a fixed ion on the surface thereof. As a result, hydroxide ions can be conducted on the surface of the porous carrier, so that the hydroxide ions generated on the air electrode catalyst can easily move.
The air electrode 12 may have an anion exchange resin supported on a porous carrier. Thereby, since hydroxide ions can be conducted through the anion exchange resin, the hydroxide ions generated on the air electrode catalyst are easily moved.

Examples of the air electrode catalyst include metals such as platinum, iron, cobalt, nickel, palladium, silver, ruthenium, iridium, molybdenum and manganese; metal compounds containing these metal atoms; alloys containing two or more of these metals Can be used. As the metal compound, a manganese oxide can be preferably used. The alloy is preferably an alloy containing at least two of platinum, iron, cobalt, and nickel. For example, platinum-iron alloy, platinum-cobalt alloy, iron-cobalt alloy, cobalt-nickel alloy, iron-nickel An alloy and an iron-cobalt-nickel alloy can be preferably used.

The air electrode 12 may be provided in direct contact with the atmosphere or may be provided in contact with the air flow path 13. When the air flow path 13 is provided, not only oxygen gas but also water can be supplied to the air electrode 12 by flowing humidified air through the air flow path 13. The installation method of the air flow path 13 is not particularly limited. For example, a current collecting member (not shown) is disposed on the opposite side of the air electrode 12 from the side in contact with the electrolyte solution 15 and formed on the current collecting member. Also good. If the air electrode 12 and the external load are electrically connected via the current collecting member, the power of the metal-air battery 21 can be efficiently output to the external load.

The air electrode 12 only needs to be able to conduct ions with the electrolytic solution 15, and the air electrode 12 may be provided so as to be in contact with the electrolytic solution 15 in the discharge tank, or the air electrode 12, the electrolytic solution 15, A separator may be provided between the two. When the air electrode 12 and the electrolytic solution 15 are in direct contact with each other, hydroxide ions generated at the air electrode 12 can easily move to the electrolytic solution 15. Further, water necessary for the electrode reaction in the air electrode 12 is easily supplied from the electrolytic solution 15 to the air electrode 12. On the other hand, by providing the separator, the ion species moving between the air electrode 12 and the electrolyte solution 15 can be limited. The separator may be an anion exchange membrane. As a result, hydroxide ions generated in the air electrode 12 can be transferred to the electrolyte solution 15 through the anion exchange membrane, and the cations in the electrolyte solution 15 can be prevented from moving to the air electrode 12. can do.

The discharge tank is preferably provided with a battery remaining amount detection unit for monitoring the remaining amount of the metal-air battery 21. The battery remaining amount detection unit may be integrated with the metal-air battery 21, and may be separately provided outside the metal-air battery 21, for example, as HEMS (Home Energy Management System). Further, the battery remaining amount detection unit may be operated by electric power generated by the power generation by the metal-air battery 21, or operated by electric power supplied from another power source instead of electric power generated by the electric power generation by the metal-air battery 21. May be. Even when the power generation of the metal-air battery 21 is stopped, the metal-air battery 21 can operate, and therefore, it is preferable to operate with power supplied from another power source. Another power source may be an external commercial power source or a storage battery. A storage battery is preferably used as another power source because it can operate even during a power failure. The storage battery may be charged with electric power from an external commercial power source, or may be charged with electric power generated by the metal-air battery 21.

(Charging tank)
The charging tank 31 is in a chargeable state with the discharged electrode cartridge attached. The charging tank 31 is a container that holds the electrolytic solution 17, and includes a charging electrode (positive electrode) 16. The electrolytic solution 17 put into the charging tank 31 may be the same type as the electrolytic solution 15 put into the discharge tank, or may be of a different type. The charging electrode 16 is not particularly limited as long as it is a material that causes an oxidation reaction paired with the reduction reaction of the electrode active material that functions as the negative electrode 11b during charging. For example, nickel, stainless steel, or the like can be used. In the electrode cartridge after discharge, the material generated by oxidizing the electrode active material during discharge becomes the electrode active material of the negative electrode 11b during charging (electrode active material during charging). As the electrode active material during charging, zinc oxide is preferably used. The negative electrode 11b during charging may include an electrode active material that is not oxidized.

[Embodiment 2]
The battery system according to the second embodiment is characterized in that authentication is performed in the charging tank using a release signal for releasing the discharge disapproval state. Hereinafter, features of the battery system of the second embodiment will be described, and descriptions of matters common to the battery system of the first embodiment will be omitted.

FIG. 6 is a block diagram illustrating an overall configuration of the battery system according to the second embodiment. As shown in FIG. 6, in the second embodiment, a third authentication unit for authenticating the release signal (key information) is provided in the charging tank. The third authentication unit is preferably configured by hardware resources capable of processing electronic information, and is configured integrally with the hardware resources configuring the second authentication unit. In FIG. 6, the second authentication unit also serves as the third authentication unit. The release signal (key information) is electronic information that can be processed by a computer, and examples thereof include the following.
(1) Identification information stored in each electrode cartridge.
(2) A user who has purchased a charging tank properly has a license key given by the seller (password stored by the user performing charging, key information that can be read using a physical key, and stored in memory. Key information).

When the license key (2) is used, a license key connection slot and a key information reading device in the memory may be provided. Moreover, when using a password, the input device for a user to input a password may be provided in the charging tank, and a password may be input from an external device.

The discharge tank processing flow in the second embodiment is the same as that in the first embodiment, but the charging tank processing flow in the second embodiment is different from that in the first embodiment. FIG. 7 is a flowchart showing a charging tank processing flow in the second embodiment. As shown in FIG. 7, the charging tank processing flow of the second embodiment is added to the charging tank processing flow of the first embodiment in which a step of determining the presence / absence of a release signal (key information) is added.

The charging tank processing flow of Embodiment 2 starts when the second detection unit detects that the discharged electrode cartridge (negative electrode) collected from the discharging tank is inserted into the charging tank. In addition, the storage unit of the electrode cartridge and the third authentication unit of the charging tank are connected for communication (step S31).

Subsequently, the third authentication unit determines whether or not there is key information (step S32). When it is determined that there is no key information or the key information is incompatible, the authentication information in the storage unit is maintained in the discharge non-permitted state (NG), and cannot be charged (step S33). There are no particular limitations on the method of making the battery unchargeable, and examples include a method of insulating the charging electrode of the charging tank and the negative electrode of the electrode cartridge, and draining the electrolyte from the charging tank. On the other hand, when it is determined that the key information is suitable, the charging start (step S34), the rewriting of the authentication information by the second input unit (step S35), and the charging completion, as in the charging tank processing flow of the first embodiment. The flow of (Step S36) is performed.

In the flow shown in FIG. 7, charging is not performed after step S33. However, after step S33, the authentication information in the storage unit is maintained in a discharge non-permitted state (NG), and charging is performed. The process may proceed to the start (step S34), and the flow up to the completion of charging (step 36) may be performed without going through the rewriting of the authentication information (step S35). In this case, even if the negative electrode is charged, the authentication information in the storage unit is maintained in the discharge non-permitted state (NG), so even if the charged electrode cartridge is attached to the discharge tank, it is incompatible with the discharge tank processing flow. Since it is judged as a product, it cannot be used. Therefore, it is possible to exclude a remanufactured product (pirated product) by a pirated manufacturer who does not have a release signal (key information).

According to the battery system of the second embodiment described above, for example, even if the pirated manufacturer regenerates the discharged negative electrode to a charged state, the pirated copy manufacturer has no release signal (key information) suitable for the charging tank. The authentication information cannot be updated from the discharge disapproval state (NG) to the discharge permission state (OK). Therefore, the negative electrode regenerated by the pirated copy manufacturer in the discharge tank processing flow can be recognized as a non-conforming product, and the pirated product can be eliminated.

[Embodiment 3]
The battery system of Embodiment 3 monitors the communication connection state between the electrode cartridge and the discharge tank, detects the completion of charging before rewriting authentication information in the charge tank, and the second in the charge tank. The battery system is the same as that of the first embodiment except that authentication information is checked by an authentication unit.

FIG. 8 is a flowchart showing a discharge tank treatment flow in the third embodiment. The discharge tank processing flow in the third embodiment starts when the first detection unit detects that the electrode cartridge has been inserted into the discharge tank (step S41). Subsequently, communication connection is performed between the storage unit and the first authentication unit, between the storage unit and the first input unit, and between the first input unit and the first detection unit ( Step S42). It is determined whether or not each communication connection performed in step S42 is possible (step S43). If any communication connection is not established, an error message indicating that the electrode cartridge attached to the discharge tank is a nonconforming product is displayed, and discharge is disabled (step S44). On the other hand, when all communication connections are established, authentication information is confirmed (step S45). If the authentication information is in a discharge disapproval state (NG) or if the authentication information cannot be confirmed, an error message indicating that the electrode cartridge attached to the discharge tank is a nonconforming product is displayed, and discharge is disabled (step S46). ). On the other hand, if the authentication information confirmed by the first authentication unit is in the discharge permission state (OK), the electrode cartridge is determined to be a compatible product, and discharge is started (step S47).

Each communication connection between the storage unit and the first authentication unit, between the storage unit and the first input unit, and between the first input unit and the first detection unit again after the start of discharge. Is determined (step S48). If any communication connection is not established, an error message indicating that the electrode cartridge attached to the discharge tank is incompatible is displayed, and discharge is disabled (step S49). On the other hand, when all the communication connections are established, the first detection unit detects whether or not the negative electrode is in contact with the electrolytic solution (step S50). If the detection is not successful, the process returns to step S43 for determining whether or not the communication connection is possible. On the other hand, when the detection is successful, the first input unit rewrites the authentication information from the discharge permission state to the discharge non-permission state (step S51). In addition, the implementation timing of said step S51 is not specifically limited, For example, it may be simultaneous with the start of discharge, and may be the timing which extracts an electrode cartridge from electrolyte solution. When the discharge is completed, the electrode cartridge is taken out from the discharge tank and carried to the charge tank (step S52). Note that the determination of whether or not communication connection is possible in step S48 may be performed a plurality of times or continuously after the start of discharge.

FIG. 9 is a flowchart showing a charging tank processing flow in the third embodiment. The charging tank processing flow of the third embodiment starts when the second detection unit detects that the discharged electrode cartridge recovered from the discharging tank is inserted into the charging tank (step S61). First, the storage unit of the electrode cartridge and the second input unit of the charging tank are connected for communication (step S62). Subsequently, the charging tank refers to the authentication information stored in the storage unit of the electrode cartridge by the second authentication unit, and confirms the authentication information (step S63). If the authentication information confirmed by the second authentication unit is in the discharge permission state (OK), or if the authentication information cannot be confirmed, it is determined as a non-conforming product and cannot be charged (step S64). On the other hand, when the authentication information is in the discharge non-permitted state (NG), charging of the discharged electrode cartridge is started (step S65). Subsequently, the second detection unit detects charging of the negative electrode (step S66). When charging is detected, the second input unit rewrites the authentication information stored in the storage unit of the electrode cartridge from the discharge non-permitted state to the discharge permitted state (step S67). In addition, the implementation timing of said step S67 is not specifically limited, For example, it may be simultaneous with the start of charge, and may be the timing which extracts an electrode cartridge from electrolyte solution. When the charging is completed, the electrode cartridge is taken out from the charging tank and carried to the discharging tank (step S68).

In the battery system of the third embodiment, the communication connection state is monitored in the discharge tank processing flow. However, in the present invention, the communication connection state is monitored in both the discharge tank processing flow and the charging tank processing flow. The communication connection state may be monitored only by the charging tank processing flow. In the battery system according to the third embodiment, the communication connection state in the discharge tank processing flow is monitored between the storage unit and the first authentication unit, between the storage unit and the first input unit, and first. However, in the present invention, only one of them may be used, or any two of them may be used in combination.

In the battery system of the third embodiment described above, in order to update the authentication information from the discharge permission state (OK) to the discharge non-permission state (NG), a communication connection needs to be established and maintained. Therefore, when the pirated manufacturer intentionally disconnects the communication connection, the authentication information is not updated, and the discharge permission state (OK) is maintained even after the discharge. If such a used electrode cartridge is obtained and charged by a pirated manufacturer, a charged electrode cartridge whose authentication information is in a discharge permission state (OK) is manufactured. However, by providing the second authentication unit in the charging tank, charging of the used electrode cartridge maintained in the discharge permission state (OK) is prevented in the charging tank processing flow. Therefore, the pirated manufacturer cannot manufacture a charged electrode cartridge whose authentication information is maintained in the discharge permission state (OK).

[Embodiment 4]
The battery system of the fourth embodiment is characterized in that the electrode cartridge is authenticated using the version number (a kind of identification information) of the electrode cartridge in addition to the authentication information. Hereinafter, the features of the battery system of the fourth embodiment will be described, and descriptions of matters common to the battery system of the first embodiment will be omitted.

FIG. 10 is a block diagram illustrating an overall configuration of the battery system according to the fourth embodiment. As shown in FIG. 10, in the fourth embodiment, in addition to the authentication information defining either the discharge permission state (OK) or the discharge non-permission state (NG) in the storage unit of the electrode cartridge, A unique version number is stored, and in the discharge tank processing flow, the first authentication unit of the discharge tank authenticates the electrode cartridge using both the recognition information and the version number. An example of the identification information in which the version number is recorded is the information table shown in Table 1 below. The identification information is electronic information that can be processed by a computer. In addition to the information shown in Table 1 below, for example, the discharge time, the charge time, the number of insertions in the discharge tank, or the charge tank may be used. Good.

Regarding the version number, the authentication unit determines whether or not it matches the latest information, and determines whether or not discharge is possible. In this case, the discharge tank may include an input device for updating to the latest version number and a storage device for storing the version number.

The method for counting the number of times of discharging and the number of times of charging is not particularly limited. For example, the method of adding +1 times at the time of starting discharge and the time of starting charging, the electrode cartridge was taken out of the state immersed in the electrolyte There is a method of adding +1 time at the time. Further, the version number may be updated when a certain number of discharges or charge is exceeded. For example, the version number may be updated to prevent subsequent charging / discharging, and a means for notifying that the negative electrode has reached the end of its life (cannot be reused) may be used.

FIG. 11 is a flowchart showing a discharge tank processing flow in the fourth embodiment. The discharge tank process flow in the fourth embodiment starts when the first detection unit detects that the electrode cartridge is inserted into the discharge tank. Then, communication connection is performed between the storage unit and the first authentication unit, between the storage unit and the first input unit, and between the first input unit and the first detection unit (step). S71). The discharge tank refers to the authentication information stored in the storage unit of the electrode cartridge by the first authentication unit and confirms the authentication information (step S72). If the authentication information is in a discharge disapproval state (NG) or the authentication information cannot be confirmed, an error message indicating that the electrode cartridge attached to the discharge tank is a non-conforming product is displayed, and discharge is not possible ( Step S73). On the other hand, if the authentication information is in a discharge permission state (OK), the discharge tank refers to the identification information stored in the storage unit of the electrode cartridge by the first authentication unit, and the version number is the same as that of the storage unit. It is determined whether or not it matches with one authentication unit (step S74).

If the version numbers do not match or the version number cannot be confirmed, an error message indicating that the electrode cartridge attached to the discharge tank is a nonconforming product is displayed, and discharge is disabled (step S75). On the other hand, if the version numbers match, it is determined that the electrode cartridge is a compatible product, and discharge is started (step S76).

After the start of discharge, the first detection unit detects whether or not the negative electrode has come into contact with the electrolytic solution (step S77). If the detection is not successful, the process returns to the confirmation of the authentication information in step S72. On the other hand, when the detection is successful, the first input unit rewrites the authentication information from the discharge permission state to the discharge non-permission state, and updates the number of discharges of the identification information stored in the storage unit of the electrode cartridge ( Step S78). At this time, the version number stored in the storage unit of the electrode cartridge may be updated simultaneously when a certain number of discharges is exceeded. The update of the version number stored in the storage unit of the electrode cartridge does not necessarily have to be performed in the flow of FIG. 11, may be performed during transportation of the electrode cartridge, and may be performed at any timing. . As an update method of the version number stored in the storage device of the discharge tank, the update number of the version number and the updated version number are notified through the communication line, and the input device at the notified update timing, For example, the version number stored in the storage device may be updated. Further, the execution timing of step S78 is not particularly limited. For example, it may be simultaneous with the start of discharge or may be the timing of extracting the electrode cartridge from the electrolyte. When the discharge is completed, the electrode cartridge is taken out of the discharge tank and carried to the charge tank (step S79).

FIG. 12 is a flowchart showing a charging tank processing flow in the fourth embodiment. The charging tank processing flow of Embodiment 4 starts when the second detection unit detects that the discharged electrode cartridge recovered from the discharging tank is inserted into the charging tank. Further, the storage unit of the electrode cartridge and the second input unit of the charging tank are connected for communication (step S81). Subsequently, charging of the discharged electrode cartridge is started (step S82). Prior to step S82, authentication information and / or identification information may be authenticated by the second authentication unit in the same manner as in the discharge tank processing flow, and it may be determined whether or not to start charging. Next, when the second detection unit detects charging of the negative electrode, the second input unit rewrites the authentication information stored in the storage unit of the electrode cartridge from the discharge non-permitted state to the discharge permitted state (step S83). . Further, the number of charging times of the identification information stored in the storage unit of the electrode cartridge is added once (step S84). At this time, the version number stored in the storage unit of the electrode cartridge may be updated at the same time when a certain number of times of charging is exceeded. In addition, the execution timing of said step S83 and step S84 is not specifically limited, For example, it may be simultaneous with the start of charge, and may be the timing which extracts an electrode cartridge from electrolyte solution. When the charging is completed, the electrode cartridge is taken out from the charging tank and carried to the discharging tank (step S85).

According to the battery systems of the first to third embodiments, it is possible to take measures against a pirated manufacturer who collects and charges a discharged electrode cartridge, but the pirated manufacturer provides the authentication information of the electrode cartridge without discharging. If the permitted state can be rewritten to the discharge permitted state, the pirated product may not be eliminated. On the other hand, in the battery system of the fourth embodiment, the version number of the electrode cartridge is used in addition to the authentication information. If the version information cannot be updated as well as the electrode cartridge authentication information, the discharge is performed. Sometimes electrode cartridges cannot be authenticated. Therefore, according to the battery system of Embodiment 4, it can prevent more reliably that the electrode cartridge reproduced | regenerated by the pirated manufacturer is used in a discharge tank.

[Embodiment 5]
The battery system of Embodiment 5 includes history information (a type of identification information) relating to a history unique to the electrode cartridge stored in the discharge tank, and history information (identification information) relating to a history unique to the electrode cartridge stored in the electrode cartridge. It is characterized in that the electrode cartridge is authenticated by comparing with the above. Hereinafter, features of the battery system of the fifth embodiment will be described, and description of matters common to the battery system of the first embodiment will be omitted.

The block diagram showing the overall configuration of the battery system of the fifth embodiment is the same as FIG. 10 according to the fourth embodiment. In Embodiment 5, the storage unit of the electrode cartridge includes the version number and ID number of the electrode cartridge as identification information in addition to the authentication information that defines either the discharge permission state (OK) or the discharge non-permission state (NG). And history information such as the number of discharges and the number of charges. On the other hand, the storage device of the discharge tank stores a version number and an ID number associated with each electrode cartridge, and the number of discharges and / or the number of charges of each electrode cartridge. In the discharge tank processing flow, the authentication unit of the discharge tank authenticates the electrode cartridge using both authentication information and identification information. An example of the identification information is the information table shown in Table 2 below.

With regard to the version number, the first authentication unit determines whether or not it matches the latest information, and determines whether or not discharge is possible. The discharge tank may include an input device for updating to the latest version number.

The method for counting the number of times of discharging and the number of times of charging is not particularly limited. For example, the method of adding +1 times at the time of starting discharge and the time of starting charging, the electrode cartridge was taken out of the state immersed in the electrolyte There is a method of adding +1 time at the time. Further, the version number may be updated when a certain number of discharges or charge is exceeded. For example, the version number may be updated to prevent subsequent charging / discharging, and a means for notifying that the negative electrode has reached the end of its life (cannot be reused) may be used.

FIG. 13 is a flowchart showing a discharge tank processing flow in the fifth embodiment. The discharge tank processing flow in the fifth embodiment starts when the first detection unit detects that the electrode cartridge has been inserted into the discharge tank. Then, communication connection is performed between the storage unit and the first authentication unit, between the storage unit and the first input unit, and between the first input unit and the first detection unit (step). S91). The discharge tank refers to the authentication information stored in the storage unit of the electrode cartridge by the first authentication unit and confirms the authentication information (step S92). If the authentication information is in a discharge disapproval state (NG) or the authentication information cannot be confirmed, an error message indicating that the electrode cartridge attached to the discharge tank is a non-conforming product is displayed, and discharge is not possible ( Step S93). On the other hand, if the authentication information is in a discharge permission state (OK), then the discharge tank refers to the identification information stored in the storage unit of the electrode cartridge and the storage device of the discharge tank by the first authentication unit, respectively. It is determined whether or not the identification information corresponds (step S94). The identification information is determined for at least one of the version number, the number of times of charging, and the number of times of discharging associated with the ID number of the electrode cartridge. The correspondence of the identification information is determined by whether or not the values stored in the storage unit of the electrode cartridge and the storage device of the discharge tank match when the confirmation target is a version number or the number of discharges. When the confirmation target is the number of times of charging, it is determined whether or not (number of times of charging stored in the storage unit of the electrode cartridge) −1 matches the number of times of charging stored in the storage device of the discharge tank.

If at least one of the identification information does not correspond or the identification information cannot be confirmed, discharging is disabled (step S95). At this time, an error display may be made to the effect that the electrode cartridge attached to the discharge tank is incompatible. In this case, the authentication information is not rewritten from the discharge permission state to the discharge non-permission state. On the other hand, if all the identification information matches, it is determined that the electrode cartridge is a compatible product, and discharge is started (step S96).

After the start of discharge, the first detection unit detects whether or not the negative electrode is in contact with the electrolytic solution (step S97). If the detection is not successful, the process returns to the confirmation of the authentication information in step S92. On the other hand, when the detection is successful, the first input unit rewrites the authentication information from the discharge permission state to the discharge non-permission state, and the identification information (the number of discharges, the version number, etc.) stored in the storage unit of the electrode cartridge Update and update the identification information (discharge count, charge count, version number, etc.) stored in the storage device of the discharge tank (step S98). The version number may not necessarily be updated in the flow of FIG. 13, may be performed during the transportation of the electrode cartridge, and the version number of the storage device may be updated at any timing. Good. As a method for updating the version number stored in the storage device, the update timing of the version number and the version number after the update are notified via the communication line, and the storage device is notified by the input device at the notified update timing. A method such as updating the version number stored in the. In addition, the execution timing of step S98 is not particularly limited, and may be, for example, simultaneous with the start of discharge or may be the timing of extracting the electrode cartridge from the electrolytic solution. When the discharge is completed, the electrode cartridge is taken out of the discharge tank and carried to the charge tank (step S99).

FIG. 14 is a flowchart illustrating a charging tank processing flow according to the fifth embodiment. The charging tank processing flow of the fifth embodiment starts when the second detection unit detects that the discharged electrode cartridge recovered from the discharging tank is inserted into the charging tank. Further, the storage unit of the electrode cartridge and the second input unit of the charging tank are connected for communication (step S101). Subsequently, charging of the discharged electrode cartridge is started (step S102). Prior to step S102, similarly to the discharge tank processing flow, authentication information and / or identification information may be authenticated by the second authentication unit to determine whether to start charging. Next, when the second detection unit detects charging of the negative electrode, the second input unit rewrites the authentication information stored in the storage unit of the electrode cartridge from the discharge non-permitted state to the discharge permitted state (step S103). . Further, the number of times of charging the storage unit of the electrode cartridge is added once (step S104). In addition, the implementation timing of said step S103 and step S104 is not specifically limited, For example, it may be simultaneous with the start of charge, and may be the timing which extracts an electrode cartridge from electrolyte solution. When the charging is completed, the electrode cartridge is taken out from the charging tank and carried to the discharging tank (step S105).

According to the battery systems of the first to third embodiments, it is possible to take measures against a pirated manufacturer who collects and charges a discharged electrode cartridge, but the pirated manufacturer provides the authentication information of the electrode cartridge without discharging. If the permitted state can be rewritten to the discharge permitted state, the pirated product may not be eliminated. On the other hand, in the battery system of the fifth embodiment, history information (identification information) is used in addition to the authentication information, and not only the identification information on the electrode cartridge side is updated, but also in the discharge tank (and the charging tank). The number of times of charging (and the number of times of discharging) is stored in a storage device and used for authentication of discharge permission. Accordingly, if the identification information on the discharge tank (and charge tank) side cannot be updated, the electrode cartridge cannot be authenticated, and the use of a pirated product can be effectively prevented. It is also possible to determine whether or not unauthorized charging / discharging has been performed while the electrode cartridge is being transported. Therefore, according to the battery system of the fifth embodiment, the electrode cartridge (recycled product) regenerated by the pirated manufacturer can be specified, and the use and distribution of the regenerated product can be more reliably prevented.

[Electrode cartridge detection method]
In the said Embodiments 1-5, it is detected by the 1st detection part of the discharge tank whether the negative electrode of the electrode cartridge contacted electrolyte solution (refer step S15, S50, S77, and S97). The specific method will be described below.

(1) Method for Measuring Potential Difference between Negative Electrode and Positive Electrode FIG. 15 is a schematic diagram illustrating a method for measuring a potential difference between negative electrode and positive electrode. When the negative electrode (metal electrode 11a) of the electrode cartridge is inserted into the discharge tank and comes into contact with the electrolytic solution 15, an electromotive force is generated between the positive electrode (air electrode 12) and the negative electrode. By measuring the electromotive force, it can be detected whether or not the negative electrode is in contact with the electrolytic solution 15. The detector can use a voltmeter that detects a potential difference between the positive electrode and the negative electrode, and may be mounted on an electrode cartridge or a discharge tank. As a criterion for determining whether or not there is a contact, for example, a criterion for determining that there is a contact when the potential difference between the positive electrode and the negative electrode reaches a desired set voltage range of the theoretical voltage of metal-air battery −0.5 V or more. Is mentioned. The desired set voltage range is preferably in the range of −0.5 to 0 V, more preferably in the range of −0.4 to 0 V, and still more preferably in the range of −0.5 to 0 V based on the theoretical voltage of the metal-air battery. It is in the range of 3V to 0V. If the set voltage range is narrowed, the probability of erroneous detection of whether or not the negative electrode of the electrode cartridge has come into contact with the electrolytic solution decreases. However, even when the negative electrode is not in contact with the electrolyte solution 15, the voltage may fluctuate and rarely reach the set voltage range. Therefore, a more preferable determination criterion is that the set voltage range is reached and stable. (For example, maintained within ± 5% for 1 minute or more).

(2) Method for Measuring Water Surface Level of Electrolyte Solution FIGS. 16 and 17 are schematic diagrams illustrating a method for measuring the liquid surface level of the electrolyte solution 15. FIG. 16 shows the case where the detector is mounted on the electrode cartridge, and FIG. 17 shows the case where the detector is mounted on the discharge tank (both the left figure shows the state before mounting, and the right figure shows the state after mounting). . When the negative electrode (metal electrode 11a) of the electrode cartridge is inserted into the discharge tank, it is measured at which position the liquid level of the electrolytic solution 15 is relative to the negative electrode. The detector 41 may be one in which two electrodes face each other and measure the resistance therebetween, and may be mounted on an electrode cartridge or a discharge tank. As a criterion for determining whether or not there is a contact, there is a criterion that a contact is made when a resistance value obtained by measurement reaches a desired set resistance value range. The desired set resistance value range is preferably within a range of ± 10%, more preferably ± 5 with respect to a theoretical value obtained by (specific resistance of electrolyte) × (distance between electrodes) ÷ (electrode area). % Is in the range. If the set voltage range is narrowed, the probability of erroneous detection of whether or not the negative electrode of the electrode cartridge has come into contact with the electrolytic solution decreases. However, even when the negative electrode is not in contact with the electrolyte solution 15, the voltage may fluctuate and rarely reach the set resistance value range. Therefore, as a more preferable determination criterion, the set resistance value range is reached. Criteria such as being stable (for example, maintained within ± 5% for 1 minute or more).

(3) Other methods There is a method for detecting the relative position between the negative electrode of the electrode cartridge and the discharge tank. For example, the button may be pushed by the operation of inserting the electrode cartridge into the discharge tank, and thereby the relative position may be detected.

According to each of the detection methods (1) to (3), it can be determined whether or not the negative electrode of the electrode cartridge is in contact with the electrolytic solution, but contact is made from a state in which the negative electrode is not in contact with the electrolytic solution. It is also possible to detect a transition to a completed state (complete insertion of the negative electrode) and a transition from a contact state to a non-contact state (desorption of the negative electrode). For example, regarding the completion of insertion of the negative electrode, in the case of the detection method of (1) above, the potential difference between the positive electrode and the negative electrode changes so as to be stable from outside the setting range to within the setting range. In the case of the method, the resistance value changes so as to be stable from outside the setting range to within the setting range, and in the case of the detection method of (3) above, the state where the button is not pressed is changed to the pressed state. Can be confirmed. In the detection mode of the transition from the contact state to the non-contact state, it may take time until the negative electrode is taken out of the electrolytic solution and then stabilized in a detectable state. The detection mode of the transition from the state to the contact state is suitable.

In addition, it is preferable to detect a transition between a non-contact state and a contact state rather than merely detecting a state in contact with the electrolytic solution. For example, when the detector is provided in the electrode cartridge, if the pirated manufacturer destroys the detector, an electrode cartridge in which the authentication information remains in the discharge-permitted state even if the detector has been discharged is manufactured. By regenerating (charging), electrode cartridges whose authentication information is in a discharge-permitted state in spite of non-conforming products will circulate. The problem of shortening arises.

[Appendix]
One embodiment of the present invention includes an electrode cartridge that can be reused by charging, a discharge tank that discharges with the electrode cartridge attached, and a charge tank that charges with the electrode cartridge after discharge attached. The electrode cartridge has a storage unit that stores authentication information indicating a discharge permission state or a discharge non-permission state, and the discharge tank reads the authentication information stored in the storage unit and discharges the discharge The battery system may include a first authentication unit that performs a process of permitting discharge when the battery is in a state and blocking discharge when the battery is in the discharge non-permitted state. According to the battery system of the above aspect, use of a non-genuine electrode cartridge (pirated product) can be prevented.

Even if the said electrode cartridge or the said discharge tank has a 1st input part which performs the process which changes the authentication information stored in the said memory | storage part from a discharge permission state to a discharge non-permission state after a discharge start Good. With such a configuration, it is possible to more effectively prevent the use of the electrode cartridge regenerated by the pirated manufacturer.

Even if the said electrode cartridge or the said charging tank has a 2nd input part which performs the process which changes the authentication information stored in the said memory | storage part from a discharge non-permission state to a discharge permission state after a charge start Good. With such a configuration, it is possible to more effectively prevent the use of the electrode cartridge regenerated by the pirated manufacturer.

The charging tank reads the authentication information stored in the storage unit, and executes a process of permitting charging when the authentication information is in a discharge not-permitted state and blocking charging when the authentication information is in a discharge-permitted state. You may have a 2nd authentication part. With this configuration, it is possible to prevent the electrode cartridge manufactured or collected by the pirated manufacturer from being charged in the charging tank.

The charging tank has a third authentication unit that authenticates a release signal used to release a discharge non-permitted state, and permits charging when the release signal matches, and charges when it does not match. It is also possible to execute a process for preventing the above. With this configuration, it is possible to prevent the electrode cartridge manufactured or collected by the pirated manufacturer from being charged in the charging tank.

The discharge tank performs communication connection with the electrode cartridge after the start of discharge, and transitions authentication information stored in the storage unit from a discharge permission state to a discharge non-permission state after the communication connection state is established. It may be. With such a configuration, when the pirated manufacturer intentionally disconnects the communication connection, the authentication information is not updated, and the electrode cartridge manufactured or reproduced by the pirated manufacturer is illegally used. It can be effectively prevented.

The battery system further includes a detector that detects contact between the electrode unit included in the electrode cartridge and the electrolytic solution placed in the discharge tank, and the contact is detected after the contact is detected by the detector. The authentication information stored in the storage unit may be changed from the discharge permission state to the discharge non-permission state. With such a configuration, the authentication information stored in the storage unit of the electrode cartridge can be appropriately updated. The detector may be a voltmeter that measures a potential difference between the metal electrode and a positive electrode provided in the discharge vessel.

The storage unit further stores identification information unique to the electrode cartridge, and the discharge tank and / or the charging tank permit discharge and / or charging when the identification information is matched. May be. By performing additional authentication using the identification information, the pirated product cannot be used simply by rewriting the authentication information, so that unauthorized use can be prevented more effectively.

The discharge tank may execute a process of updating the identification information after the start of discharge, and the charge tank may execute a process of updating the identification information after the start of charging. According to these configurations, since the pirated product cannot be used only by rewriting the identification information on the electrode cartridge side, unauthorized use can be more effectively prevented.

In addition, the electrode cartridge, the discharge tank, the battery, and the charging tank constituting the battery system of the above aspect are also one aspect of the present invention. That is, one embodiment of the present invention is an electrode cartridge that can be reused by charging, and includes an electrode cartridge that includes a metal electrode and a storage unit that stores authentication information indicating a discharge permission state or a discharge permission state. Also good. One aspect of the present invention is a discharge tank that discharges with the electrode cartridge attached, wherein the discharge tank reads authentication information stored in the electrode cartridge, and the authentication information is in a discharge-permitted state. In some cases, the discharge tank may include an authentication unit that performs a process of permitting discharge and preventing discharge when the discharge is not permitted. One embodiment of the present invention may be a battery in which the electrode cartridge is attached to the discharge tank, for example, a metal-air battery. One aspect of the present invention is a charging tank that performs charging with a discharged electrode cartridge attached, wherein the charging tank reads authentication information stored in the electrode cartridge, and the authentication information does not permit discharge. It may be a charging tank having an authentication unit that executes processing for permitting charging when in a state and blocking charging when in a discharging permitted state. The electrode cartridges, discharge tanks, batteries and charging tanks of these aspects are also useful in preventing the use of non-genuine electrode cartridges (pirated products).

11a: Metal electrode 11b: Negative electrode 12 during charging, 112: Air electrode 13, 113: Air flow path 15, 17, 115: Electrolytic solution 16: Charging electrode 21: Metal-air battery 31: Charging tank 41: Detector 111: Zinc electrode 121: Zinc-air battery

Claims (13)

An electrode cartridge comprising a metal electrode containing an electrode active material and reusable by charging;
A discharge tank that includes an air electrode and discharges with the electrode cartridge attached;
A charging tank that includes a positive electrode and performs charging in a state in which the electrode cartridge taken out from the discharge tank after discharge is attached;
The electrode cartridge has a storage unit for storing authentication information indicating a discharge permission state or a discharge non-permission state,
The discharge tank reads the authentication information stored in the storage unit, and executes a process of permitting discharge when the discharge is permitted and preventing discharge when the discharge is not permitted. With an authentication part of
The electrode cartridge or the discharge tank has a first input unit that executes a process of transitioning authentication information stored in the storage unit from a discharge permission state to a discharge non-permission state after the start of discharge,
The said charging tank has a 2nd input part which performs the process which changes the authentication information stored in the said memory | storage part from a discharge non-permission state to a discharge permission state after a charge start. An electrode cartridge comprising a metal electrode containing an electrode active material and reusable by charging;
A discharge tank that includes an air electrode and discharges with the electrode cartridge attached;
A charging tank that includes a positive electrode and performs charging in a state in which the electrode cartridge taken out from the discharge tank after discharge is attached;
The electrode cartridge has a storage unit for storing authentication information indicating a discharge permission state or a discharge non-permission state,
The discharge tank reads the authentication information stored in the storage unit, and executes a process of permitting discharge when the discharge is permitted and preventing discharge when the discharge is not permitted. With an authentication part of
The electrode cartridge or the discharge tank has a first input unit that executes a process of transitioning authentication information stored in the storage unit from a discharge permission state to a discharge non-permission state after the start of discharge,
The charging tank reads the authentication information stored in the storage unit, and executes a process of permitting charging when the authentication information is in a discharge not-permitted state and blocking charging when the authentication information is in a discharge-permitted state. A battery system comprising a second authentication unit. An electrode cartridge comprising a metal electrode containing an electrode active material and reusable by charging;
A discharge tank that includes an air electrode and discharges with the electrode cartridge attached;
A charging tank that includes a positive electrode and performs charging in a state in which the electrode cartridge taken out from the discharge tank after discharge is attached;
The electrode cartridge has a storage unit for storing authentication information indicating a discharge permission state or a discharge non-permission state,
The discharge tank reads the authentication information stored in the storage unit, and executes a process of permitting discharge when the discharge is permitted and preventing discharge when the discharge is not permitted. With an authentication part of
The electrode cartridge or the discharge tank has a first input unit that executes a process of transitioning authentication information stored in the storage unit from a discharge permission state to a discharge non-permission state after the start of discharge,
The charging tank has a third authentication unit that authenticates a release signal used to release a discharge non-permitted state, and permits charging when the release signal conforms, and charges when it does not conform. The battery system characterized by performing the process which blocks | prevents. The discharge tank performs communication connection with the electrode cartridge after the start of discharge,
The said 1st input part changes the authentication information stored in the said memory | storage part from a discharge permission state to a discharge non-permission state, after the said communication connection state is established. The battery system according to any one of the above. The battery system further includes a detector that detects contact between a metal electrode included in the electrode cartridge and an electrolytic solution placed in the discharge tank,
The first input unit transitions authentication information stored in the storage unit from a discharge permission state to a discharge non-permission state after the contact is detected by the detector. 5. The battery system according to any one of 4. The battery system according to claim 5, wherein the detector is a voltmeter that measures a potential difference between the metal electrode and a positive electrode provided in the discharge tank. The storage unit further stores identification information unique to the electrode cartridge,
The battery system according to claim 1, wherein the discharge tank and / or the charging tank permits discharge and / or charging when the identification information is matched. The battery system according to claim 7, wherein the discharge tank executes a process of updating the identification information after the start of discharge. The battery system according to claim 7 or 8, wherein the charging tank performs a process of updating the identification information after starting charging. The storage unit stores the number of times the electrode cartridge is charged,
Wherein the first authentication unit, based on the number of times the electrode cartridge is charged, the a discharge enable state or the discharge not permitted state, it is determined, according to any one of claims 1 to 9 Battery system. A charging tank equipped with a positive electrode and charged in a state where an electrode cartridge including a metal electrode containing an electrode active material after discharge is attached,
The charging tank is
An authentication unit that reads authentication information stored in a storage unit included in the electrode cartridge, and performs a process of permitting charging when the authentication information is in a discharge-not-permitted state and blocking charging when the authentication information is in a discharge-permitted state. The charging tank characterized by having. The charging tank is
The charging tank according to claim 11, further comprising an input unit that executes a process of transitioning the authentication information stored in the storage unit from a discharge non-permitted state to a discharge permitted state after the start of charging. The charging tank is
Furthermore, it has the 3rd certification | authentication part which authenticates the cancellation | release signal used in order to cancel | release a discharge non-permission state, charge is permitted when the said cancellation | release signal suits, and charge is blocked | prevented when it does not fit. The charging tank according to claim 11 or 12, wherein processing is executed.

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