JP2014116267A - Air battery, air battery system and method for charging/discharging air battery - Google Patents

Abstract

PROBLEM TO BE SOLVED: To solve such a problem that, when an air battery has a configuration suitable for increased capacity, reduction in prolonged charging time is difficult.SOLUTION: An air battery of the present invention includes: a positive electrode collector including an air electrode where a positive electrode reaction of oxygen is performed; a negative electrode collector to which metal particles comprising negative electrode metal adhere; a separator separating the air electrode from the negative electrode collector; and a circulation structure circulating a mixed liquid between the positive electrode collector and the negative electrode collector, the mixed liquid including negative electrode particles which contain the negative electrode metal and are dispersed in an electrolyte.

Description

  The present invention relates to an air battery, an air battery system, and a charge / discharge method for an air battery, and more particularly to an air battery, an air battery system, and a charge / discharge method for an air battery suitable for increasing the capacity.

  An air battery is a chargeable / dischargeable battery using oxygen in the air as a positive electrode active material and using a single metal or a metal compound as a negative electrode active material. Since the air battery does not need to be filled with the positive electrode active material in the battery container, the majority of the area in the battery container can be filled with the negative electrode active material. As a result, there are advantages such as high energy density and easy reduction in size and weight. Therefore, it attracts attention as a high-capacity secondary battery that is superior to the lithium secondary batteries that are currently widely used. In particular, lithium air batteries, which have a high energy density among air batteries, are expected to be applied to next-generation electric vehicles and the like, and research and development have been actively conducted in recent years.

  An example of such an air battery is described in Patent Document 1. As shown in FIG. 8, the related air battery 1 described in Patent Document 1 includes a negative electrode 17, a separator 6, a positive electrode 13 having a positive electrode catalyst layer 4 and a positive electrode current collector 3, an oxygen diffusion film 2, and the like. Has a laminate 19 arranged in this order. In addition, a power generation body 20 including an electrolyte 9 in contact with the negative electrode 17, the separator 6, and the positive electrode 13 is provided. Here, one of the main surfaces of the oxygen diffusion film 2 is disposed to face one of the main surfaces of the positive electrode current collector 3, and at least a part of the peripheral edge of the oxygen diffusion film 2 is in contact with air. Yes.

  In the related air battery 1, since at least a part of the peripheral edge portion of the oxygen diffusion film 2 is disposed so as to be in contact with air, the main surfaces can be stacked to be stacked. As a result, the capacity can be easily increased.

JP 2011-146339 A (paragraphs “0006” and “0007”) US Pat. No. 5,434,020 JP 2005-509262 A (paragraph "0054")

  Like the related air battery described above, a lithium air battery using lithium as a negative electrode active material is an attractive battery having an energy density of 10 times or more compared with an existing lithium ion battery. However, when a large capacity air battery is used for an electric vehicle, for example, there is a problem that the charging time is prolonged.

  Specifically, for example, currently popular electric vehicles have an energy capacity of around 20 kilowatt hours [kWh] per vehicle. On the other hand, when a lithium-air battery having an equivalent weight is mounted, it is possible to load an energy capacity of 200 kWh [kWh] or more, which is ideally ten times that. However, when a battery with an energy capacity of 200 kWh [kWh] is charged with 3 kW [kW], which is the charging power normally used for charging current electric vehicles, a charging time of about 70 hours is required. It becomes. Therefore, it is difficult to fully utilize the advantages of the high energy capacity of the lithium air battery.

  On the other hand, as a technique for solving such a prolonged charging time, a charging method using mechanical charging has been conventionally known for zinc-air batteries and the like. For example, in Patent Document 2, as shown in FIG. 9, the zinc pellet 44 as the negative electrode active material is filled between the two plates constituting the air electrode 56 and the negative electrode current collector 52, respectively, and the electrolyte is poured. A related zinc-air battery 40 is described. Further, in Patent Document 3, as shown in FIG. 10, a metal-air type related electrochemical cell in which an anode structure 32 made of a zinc metal plate supported by a support structure 34 is detachable in an electrolyte solution. A system 30 is described.

  However, it is difficult to use lithium metal or the like that is highly reactive in the air in the configuration of the related zinc-air battery described above.

  As described above, the related air battery has a problem that it is difficult to shorten the charging time which takes a long time if the configuration is suitable for increasing the capacity.

  An object of the present invention is an air battery that solves the problem described above, that is, it is difficult to shorten the charging time that takes a long time if the air battery has a configuration suitable for increasing the capacity. And an air battery system and an air battery charge / discharge method.

  The air battery of the present invention separates a positive electrode current collector having an air electrode in which a positive electrode reaction of oxygen is performed, a negative electrode current collector to which metal particles made of a negative electrode metal are attached, and an air electrode and a negative electrode current collector. A separator and a circulation structure in which a mixed liquid in which negative electrode particles containing a negative electrode metal are dispersed in an electrolytic solution is circulated between the positive electrode current collector and the negative electrode current collector.

  The charge / discharge method for an air battery according to the present invention creates a mixed liquid in which metal particles are dispersed by mixing metal particles and an electrolyte solution, and the mixed liquid is mixed with a positive electrode current collector and an negative electrode current collector each having an air electrode. It circulates between electrical conductors, supplies electrons to the oxygen molecules from the air electrode to generate oxygen ions, captures the metal particles by the negative electrode current collector, and releases the electrons released when the metal particles combine with the oxygen ions. It discharges by deriving, generates metal oxide by reacting metal particles and oxygen ions, circulates the metal oxide between the positive electrode current collector and the negative electrode current collector, and supplies electrons to the metal oxide Then, oxygen ions are generated and charged by depositing metal particles on the negative electrode current collector.

  According to the air battery, the air battery system, and the charge / discharge method of the air battery of the present invention, the charging time can be shortened even when the configuration is suitable for increasing the capacity.

It is sectional drawing which shows the structure of the air battery which concerns on the 1st Embodiment of this invention. It is a step view which shows the structure of the air battery which concerns on the 2nd Embodiment of this invention. It is a step view which shows the structure of the air battery which concerns on the 3rd Embodiment of this invention. It is a step view which shows the structure of the air battery which concerns on the 4th Embodiment of this invention. It is a step view which shows the structure of the air battery system which concerns on the 5th Embodiment of this invention. It is a step view which shows another structure of the air battery system which concerns on the 5th Embodiment of this invention. It is a step view which shows another structure of the air battery system which concerns on the 5th Embodiment of this invention. It is sectional drawing which shows the structure of a related air battery. It is sectional drawing which shows the structure of a related zinc air battery. It is sectional drawing which shows the structure of the related electrochemical cell system.

  Embodiments of the present invention will be described below with reference to the drawings.

[First Embodiment]
FIG. 1 is a cross-sectional view showing a configuration of an air battery 100 according to the first embodiment of the present invention. The air battery 100 includes a positive electrode current collector 110 including an air electrode 111 in which a positive electrode reaction of oxygen is performed, a negative electrode current collector 120, a separator 130 that separates the air electrode 111 and the negative electrode current collector 120, and a circulation structure 140. Have The negative electrode current collector 120 adheres metal particles made of a negative electrode metal. The circulation structure 140 circulates between the positive electrode current collector 110 and the negative electrode current collector 120 in a mixed liquid in which negative electrode particles containing a negative electrode metal are dispersed in an electrolytic solution.

  As described above, the air battery 100 according to the present embodiment includes the power generation unit / charging unit including the negative electrode current collector 120 and the air electrode 111 and the mixed liquid in which the negative electrode particles are dispersed (hereinafter, also referred to as “slurry liquid”). Is a completely separated configuration. Therefore, it is possible to perform mechanical charging in a short time (typically several seconds to several minutes) by exchanging the mixed liquid with a new mixed liquid (slurry liquid) after discharging the air battery 100. It becomes.

  In addition, even when a plurality of power generation units / charging units are electrically connected in series or in parallel to increase the capacity, it is possible to perform mechanical charging only by parallelizing the transport path of the mixed liquid. . Therefore, it is not necessary to have a complicated configuration for increasing the capacity, and complicated operation is not necessary. Furthermore, according to the air battery 100 of the present embodiment, the capacity of the air battery 100 can be determined only by the capacity of the mixed liquid. Therefore, it is not necessary to add a power generation part even when using a large capacity. Therefore, it is possible to achieve higher energy density than a sealed air battery.

  In addition, since the air battery 100 according to the present embodiment can have a configuration in which the power generation unit / charging unit and the storage unit for storing the mixed liquid are separated as described above, the storage unit is enlarged and the energy density of the entire system is increased. It is possible to use with improved In addition, since the negative electrode is in powder form, the interface between the negative electrode and the electrolyte solution has a large area. Therefore, since the design of large current discharge is easy, the air battery 100 according to the present embodiment is particularly suitable for use as a power source for a device including an actuator such as a moving body that requires a large capacity and a large output.

  As described above, according to the air battery 100 of the present embodiment, the charging time can be shortened even when the configuration is suitable for increasing the capacity.

[Second Embodiment]
Next, a second embodiment of the present invention will be described. FIG. 2 is a step view showing a configuration of an air battery 200 according to the second embodiment of the present invention. The air battery 200 according to the present embodiment has a configuration suitable for the case where the air battery 100 of the first embodiment is used as a discharge battery. The same components as those in the first embodiment are denoted by the same reference numerals, and the description thereof may be omitted.

  The air electrode 111 provided in the positive electrode current collector 110 of the air battery 200 supplies electrons to oxygen molecules and introduces oxygen ions into the mixed liquid in which the negative electrode particles are dispersed. The negative electrode current collector 120 includes a discharge negative electrode current collector 220 made of a porous conductor. The circulation structure 140 circulates the mixed liquid in which the metal particles as the negative electrode particles are dispersed so as to pass through the negative electrode current collector 220 for discharge. Then, the discharge negative electrode current collector 220 captures the metal particles and derives electrons that are emitted when the metal particles are combined with oxygen ions.

  The configuration of the air battery 200 according to the present embodiment will be described in more detail with reference to FIG.

  The air electrode 111 has oxygen permeability, water repellency, and conductivity, and supports a catalyst. The discharge negative electrode current collector 220 is made of a porous material having an opening smaller than the diameter of the metal particles and having electrical conductivity through which the electrolytic solution passes. Here, lithium can be used as the negative electrode metal, and the metal particles can be mainly composed of lithium.

  The separator 130 is made of a porous resin or the like, and is disposed between the discharge negative electrode current collector 220 and the air electrode 111. The separator can be configured to be supported by the discharge negative electrode current collector 220 and the separator support. The positive electrode current collector 110 is supported by a support 240 that covers a portion of the air electrode 111 excluding the reaction surface.

  The support 240 has a mixed liquid inflow port 241 for introducing a mixed liquid in the vicinity of the discharge negative electrode current collector 220 and a reaction liquid flow for discharging the discharged electrolytic solution between the separator and the air electrode 111. An outlet 242 is provided to constitute the circulation structure 140. The support 240 may have a cylindrical shape or a plate shape as long as the electrolyte solution can be held between the air electrode 111 and the discharge negative electrode current collector 220. The shape may be sufficient.

  It is desirable to connect electrode terminals 212 and 222 for extracting power to the positive electrode current collector 110 and the discharge negative electrode current collector 220, respectively. Note that at least the contact between the air electrode 111 and the discharge negative electrode current collector 220 needs to be formed of an insulator. Further, the gas diffusion permeable membrane 213 may be provided on the surface of the air electrode 111.

  Next, the operation of the air battery 200 according to the present embodiment will be described.

  First, the mixed liquid (slurry liquid) is introduced from the mixed liquid inlet 241 provided at the lower part of the support 240 by the operation of a pump or the like as a transport device. Here, the case where lithium is used as the negative electrode metal will be described as an example. The slurry liquid composed of the electrolytic solution and the metal lithium particles reaches the negative electrode current collector 220 for discharge. At this time, since the metal lithium particles have a size of about several μm to several hundred μm, they are trapped by the porous material constituting the discharge negative electrode current collector 220. On the other hand, the anions and cations (for example, lithium ions and bis (fluorosulfonyl) imide) that constitute the electrolyte solution and the supporting salt are about several nanometers in size, so that they pass through the porous mesh. Is possible. Therefore, only metallic lithium particles are trapped in the discharge negative electrode current collector 220, and the electrolyte fills between the discharge negative electrode current collector 220 and the air electrode 111, and flows out from the reaction solution outlet 242.

  The trapped lithium metal particles send electrons to the air electrode 111 through an external load, and after ionization, pass through the separator and move to the air electrode 111. On the other hand, in the vicinity of the air electrode 111, oxygen in the atmosphere receives electrons and combines with lithium ions to become lithium oxide and flows out from the reaction solution outlet 242. That is, metallic lithium particles are accumulated on the negative electrode current collector, and a negative electrode reaction proceeds to form a lithium-air battery having an electrolyte between the negative electrode current collector and the air electrode. When the metal lithium particles are dissolved by the discharge, a new liquid electrolyte and a mixed liquid containing the metal lithium particles are sequentially supplied by the transport device, and the discharge is continued.

  As described above, the air battery 200 according to the present embodiment has a configuration in which the power generation unit / charging unit including the discharge negative electrode current collector 220 and the air electrode 111 and the mixed liquid in which the negative electrode particles are dispersed are completely separated. . Therefore, after discharging the air battery 200, it is possible to perform mechanical charging in a short time by exchanging the mixed liquid with a new mixed liquid. Therefore, according to the air battery 200 of the present embodiment, the charging time can be shortened even when the configuration is suitable for increasing the capacity.

[Third Embodiment]
Next, a third embodiment of the present invention will be described. FIG. 3 is a step view showing a configuration of an air battery 300 according to the third embodiment of the present invention. The air battery 300 according to the present embodiment has a configuration suitable for the case where the air battery 100 of the first embodiment is used as a charging battery. The same components as those in the first embodiment are denoted by the same reference numerals, and the description thereof may be omitted.

  The air electrode 111 provided in the positive electrode current collector 110 of the air battery 300 supplies electrons to the metal oxide generated by the reaction between the metal particles and oxygen to generate oxygen ions in the electric field liquid. The negative electrode current collector 120 includes a charging negative electrode current collector 320 having a concavo-convex structure on the surface. The circulation structure 140 circulates a mixed liquid in which metal oxides as negative electrode particles are dispersed between the positive electrode current collector 110 and the negative electrode current collector 320 for charging. Then, the negative electrode current collector 320 for charging deposits metal particles and acquires electrons from oxygen ions.

  The configuration of the air battery 300 according to the present embodiment will be described in more detail with reference to FIG.

  The air electrode 111 has oxygen permeability, water repellency, and conductivity, and supports a catalyst. The charging negative electrode current collector 320 preferably has a shape obtained by processing the inner surface of the power generation unit into a groove shape.

  The separator 130 is made of a porous resin or the like, and is disposed between the charging negative electrode current collector 320 and the air electrode 111. The positive electrode current collector 110 is supported by a support 340 that covers the peripheral portion of the air electrode 111 excluding the reaction surface.

  The support 340 leads the reaction liquid inlet 341 for introducing the electrolytic solution after discharge between the air electrode 111 and the separator 130, and the mixed liquid between the negative electrode current collector 320 for charging and the separator 130. The mixed liquid outlet 342 is provided. Note that the shape of the support 340 may be a columnar shape, a plate shape, or the like as long as the electrolyte solution can be held between the air electrode 111 and the negative electrode current collector 320 for charging. The shape may be sufficient.

  Further, the transport device 350 that circulates the mixed liquid can be disposed at a position where the vibration of the transport device 350 is transmitted to the negative electrode current collector 320 for charging. In this case, the transport device 350 and the support 340 constitute the circulation structure 140. Specifically, for example, as shown in FIG. 3, one surface of the piezo pump as the transport device 350 may be fixed to the back surface side of the charging negative electrode current collector 320.

  It is desirable to connect electrode terminals 312 and 322 for extracting electric power to the positive electrode current collector 110 and the charging negative electrode current collector 320, respectively. Note that at least the contact between the air electrode 111 and the charging negative electrode current collector 320 needs to be formed of an insulator. Further, the gas diffusion permeable membrane 213 may be provided on the surface of the air electrode 111.

  Next, the operation of the air battery 300 according to the present embodiment will be described.

  First, a mixed liquid of an electrolytic solution and a metal oxide is introduced from a reaction liquid inflow port 341 provided at an upper portion of the support 340 by an operation of a pump as the transport device 350. Here, a case where lithium is used as the negative electrode metal will be described as an example. The lithium oxide as the metal oxide is trapped by the separator 130. On the other hand, the electrolytic solution fills between the charging negative electrode current collector 320 and the air electrode 111 and flows out from the mixed liquid outlet 342 provided at the lower portion of the support 340.

  When power is supplied between the air electrode 111 and the charging negative electrode current collector 320, lithium oxide in the vicinity of the air electrode 111 is decomposed and lithium is deposited on the charging negative electrode current collector 320. Lithium deposited on the surface of the current collector having a concavo-convex structure of the negative electrode current collector 320 for charging is deposited in a dendrite shape due to an internal pressure difference inside the lithium metal and vibration by a pump. Here, when a weak discharge is performed between the air electrode 111 and the negative electrode current collector 320 for charging, the root portion of the dendrite crystal is melted, and the powder of the dendrite crystal is released into the electrolytic solution. Thereafter, the air is discharged outside the air battery 300 by a pump.

Here, the deposition of metallic lithium will be described in more detail. As described above, metallic lithium is deposited from the electrolytic solution containing lithium oxide (LiO, LiO _2, etc.) as a reaction product on the current collector surface of the negative electrode current collector 320 for charging.

  Regarding the deposition of lithium metal, it is known that when a lithium-based battery such as a lithium ion battery is charged, lithium needle crystals (dendrites) are deposited on the negative electrode. Regarding the mechanism of the dendrite generation, when lithium plated on the electrode surface is deposited non-uniformly, an internal pressure difference occurs, and the surface of the locally high pressure portion becomes a structurally stable dendrite crystal. ,It is believed that. Further, when a weak current is discharged in a state where dendrites are generated, dissolution starts from the root portion of the dendrites where the interaction between lithium is small, and lithium on the electrode surface is cut off.

  Lithium deposits over the surface of the negative electrode current collector. However, when the surface of the negative electrode current collector has an uneven structure, or when the negative electrode current collector is vibrated, the pressure balance inside the lithium is suddenly broken. Dendrite crystals are formed. At this time, the dendrite crystal can be forcibly detached from the surface of the negative electrode current collector by periodically performing weak discharge.

  As described above, according to the air battery 300 according to the present embodiment, even a lithium metal air battery using metal particles, for example, lithium particles, can regenerate a mixed liquid (slurry liquid) in which lithium oxide is dispersed. It can be done electrically. That is, the lithium metal air battery can be charged electrically. For this reason, it is possible to selectively use electric charging that requires a long charging time and rapid mechanical charging by liquid exchange.

  For example, when the air battery 300 according to the present embodiment is used for an electric vehicle or the like, mechanical charging is performed in a short time of several minutes, and the mixed liquid in which lithium oxide is dispersed is lithium over a long time inside a charging device such as a power stand. A system that reduces to particles can be constructed. Alternatively, it is possible to construct a system that performs charging for a long time inside an electric vehicle without using a power stand.

  As described above, the air battery 300 according to the present embodiment has a configuration in which the power generation unit / charging unit including the charging negative electrode current collector 320 and the air electrode 111 and the mixed liquid in which the negative electrode particles are dispersed are completely separated. . Therefore, after discharging the air battery 300, it is possible to perform mechanical charging in a short time by exchanging the mixed liquid with a new mixed liquid. Therefore, according to the air battery 300 of the present embodiment, the charging time can be shortened even when the configuration is suitable for increasing the capacity.

[Fourth Embodiment]
Next, a fourth embodiment of the present invention will be described. FIG. 4 is a step view showing a configuration of an air battery 400 according to the fourth embodiment of the present invention. The air battery 400 according to the present embodiment has a configuration suitable when the air battery 100 of the first embodiment is used as a discharge battery and a charge battery. The same components as those in the first embodiment are denoted by the same reference numerals, and the description thereof may be omitted.

  The air electrode 111 provided in the positive electrode current collector 110 of the air battery 400 supplies electrons to oxygen molecules to introduce oxygen ions into the mixed liquid in which the negative electrode particles are dispersed. The air electrode 111 supplies electrons to the metal oxide generated by the reaction between the metal particles and oxygen to generate oxygen ions in the electrolysis solution.

  The negative electrode current collector 120 includes a discharge negative electrode current collector 220 made of a porous conductor, and a charging negative electrode current collector 320 having a concavo-convex structure on the surface.

  The circulation structure 140 circulates the mixed liquid in which the metal particles as the negative electrode particles are dispersed so as to pass through the negative electrode current collector 220 for discharge. At this time, the discharge negative electrode current collector 220 captures the metal particles and derives electrons to be emitted when the metal particles are combined with oxygen ions.

  The circulation structure 140 circulates the mixed liquid in which the metal oxide as the negative electrode particles is dispersed between the positive electrode current collector 110 and the charging negative electrode current collector 320. At this time, the negative electrode current collector 320 for charging deposits metal particles and acquires electrons from oxygen ions.

  The configuration of the air battery 400 according to the present embodiment will be described in more detail with reference to FIG.

  The air electrode 111 has oxygen permeability, water repellency, and conductivity, and supports a catalyst. The discharge negative electrode current collector 220 is made of a porous material having an opening smaller than the diameter of the metal particles and having electrical conductivity through which the electrolytic solution passes. On the other hand, the charging negative electrode current collector 320 preferably has a shape obtained by processing the inner surface of the power generation unit into a groove shape.

  The separator 130 is made of a porous resin or the like, and is disposed between the discharge negative electrode current collector 220 and the air electrode 111 in the vicinity of the discharge negative electrode current collector 220. Further, the positive electrode current collector 110 is supported by a support body 440 that covers a peripheral portion of the air electrode 111 excluding the reaction surface.

  The support 440 includes a reaction solution inflow / outflow port 441 for introducing and deriving the electrolytic solution after discharge between the air electrode 111 and the separator 130. Furthermore, a mixed liquid inflow / outflow port 442 for introducing and deriving the mixed liquid between the discharge negative electrode current collector 220 and the charge negative electrode current collector 320 is provided. Note that the shape of the support 440 may be a columnar shape, a plate shape, or the like as long as the electrolyte solution can be held between the air electrode 111 and the negative electrode current collector 320 for charging. It may be a shape.

  Further, the transport device 350 that circulates the mixed liquid can be disposed at a position where the vibration of the transport device 350 is transmitted to the negative electrode current collector 320 for charging. In this case, the transport device 350 and the support body 440 constitute the circulation structure 140.

  It is desirable to connect electrode terminals 412, 222, and 322 for extracting power to the positive electrode current collector 110, the discharge negative electrode current collector 220, and the charge negative electrode current collector 320, respectively. Note that at least the contacts between the air electrode 111 and the discharging negative electrode current collector 220 and between the air electrode 111 and the charging negative electrode current collector 320 need to be made of an insulator. Further, the gas diffusion permeable membrane 213 may be provided on the surface of the air electrode 111.

  Next, the operation of the air battery 400 according to the present embodiment will be described.

  The air battery 400 of the present embodiment introduces the mixed liquid from the mixed liquid inflow / outflow port 442 provided at the lower part of the support 440 during discharge. On the other hand, at the time of charging, a mixed liquid of an electrolytic solution and a metal oxide is introduced from a reaction solution inflow / outflow port 441 provided at the upper part of the support 440, contrary to the time of discharging.

  More specifically, the air battery 400 according to the present embodiment is a mixed liquid in which a negative electrode metal having a fine particle structure such as powder, granule, or filler is mixed with an electrolyte inactive to the negative electrode metal and oxygen. Circulate (slurry liquid). At the time of discharging, power is generated by reaction with oxygen by trapping the negative electrode metal in the slurry liquid. On the other hand, at the time of charging, negative electrode metal and oxygen having a fine particle structure such as powder, granule, or filler are generated from the product after reaction. With such a configuration, charge / discharge can be realized only by the slurry liquid circulation system, and high-speed mechanical charging can be realized by exchanging the slurry liquid.

  The air battery 400 according to the present embodiment will be described by taking a case where lithium is used as the negative electrode metal as an example. The air battery 400 may be configured to use a slurry liquid in which the negative electrode lithium has a fine particle structure and is mixed with a nonaqueous electrolytic solution. In the discharging process, the negative electrode current collector having a porous structure traps the negative electrode lithium from the slurry liquid, thereby forming a chemical battery structure and performing a discharging operation.

  In order to achieve both electrical charging and discharging and mechanical charging, the air battery 400 according to the present embodiment uses a negative electrode current collector having a non-uniform surface for charging separately from the porous negative electrode current collector used for discharging. The configuration was provided. The negative electrode current collector having a non-uniform surface promotes the growth of fine needle crystals (dendrites) with respect to a soft metal such as lithium, and the needle crystals are detached into the electrolytic solution. Thereby, it becomes possible to reproduce | regenerate the slurry liquid which is a mixture of a negative electrode metal and electrolyte solution from the electrolyte solution after reaction.

  As described above, the air battery 400 according to the present embodiment includes the power generation unit / charging unit including the discharge negative electrode current collector 220, the charge negative electrode current collector 320, the air electrode 111, and the like, and a mixture in which the negative electrode particles are dispersed. The liquid is completely separated from the liquid. Therefore, after discharging the air battery 400, it is possible to perform mechanical charging in a short time by exchanging the mixed liquid with a new mixed liquid. Therefore, according to the air battery 400 of the present embodiment, the charging time can be shortened even when the configuration is suitable for increasing the capacity.

  Next, the charging / discharging method of the air battery according to the present embodiment will be described.

  According to the charge / discharge method of the air battery of this embodiment, first, a mixed liquid in which metal particles are dispersed is prepared by mixing metal particles and an electrolytic solution. And this mixed liquid is circulated between the positive electrode collector provided with the air electrode, and the negative electrode collector. Further, electrons are supplied from the air electrode to oxygen molecules to generate oxygen ions. At this time, the metal particles are captured by the negative electrode current collector and discharged by deriving electrons emitted when the metal particles are combined with oxygen ions.

  Further, a metal oxide is generated by reacting metal particles with oxygen ions, and the metal oxide is circulated between the positive electrode current collector and the negative electrode current collector. At this time, charging is performed by supplying electrons to the metal oxide to generate oxygen ions and depositing metal particles on the negative electrode current collector.

  With the above-described configuration, according to the charge / discharge method of the air battery according to the present embodiment, the discharge and charging process and the supply process of the metal particles are separated. However, the charging time can be shortened.

  Moreover, in the charge / discharge method of the air battery of this embodiment, after depositing metal particles on the negative electrode current collector to create a deposited metal structure, the deposited metal particles are created from the deposited metal structure, and the deposited metal particles are electrolyzed. It is good also as making a liquid mixture by making it mix with. In addition, when producing the deposited metal particles from the deposited metal structure, a step of adding vibration to the deposited metal structure can be performed. At this time, discharge may be performed using the deposited metal structure as an electrode.

[Fifth Embodiment]
Next, a fifth embodiment of the present invention will be described. FIG. 5 is a step view showing a configuration of an air battery system 1000 according to the fifth embodiment of the present invention. The air battery system 1000 according to this embodiment includes an air battery 1100 that is one of the air batteries according to the first to fourth embodiments described above.

  The air battery system 1000 of the present embodiment includes a container 1110 that houses the air battery 1100, a mixed liquid container 1200, and a reaction liquid container 1300.

  The mixed liquid container 1200 contains a mixed liquid 1210 in which metal particles as negative electrode particles are dispersed. The reaction liquid container 1300 contains a reaction liquid 1310 that is a mixed liquid in which metal oxides generated by the reaction between metal particles and oxygen are dispersed. Here, the mixed liquid container 1200 is connected in the vicinity of the container 1110 and the negative electrode current collector 120, and the reaction liquid container 1300 is connected in the vicinity of the container 1110 and the positive electrode current collector 110.

  The configuration of the air battery system 1000 according to the present embodiment will be described in more detail with reference to FIG.

  The mixed liquid 1210 is a slurry liquid obtained by mixing metal particles having a fine particle structure such as powder, granule, or filler, for example, lithium metal particles and an organic electrolyte. The mixed liquid container 1200 is made of a material having corrosion resistance to the electrolytic solution. The reaction liquid container 1300 is also formed of a material having corrosion resistance with respect to the reaction liquid 1310 that is the electrolytic solution after discharge.

  In addition, the air battery system 1000 may include a transport device 1400 that circulates the mixed liquid, and may include a connection pipe 1500 that connects the container 1110, the mixed liquid container 1200, and the reaction liquid container 1300, respectively. In addition, it is desirable to take measures such as sealing with nitrogen gas so that the mixed liquid does not come into contact with oxygen in the atmosphere in a region other than the air battery 1100 and water molecules are not dissolved.

  Furthermore, the air battery system 1000 may include a control device 1600 that controls a transport device 1400 by measuring a current or voltage drop during discharge. Alternatively, power storage device 1700 may be connected to stabilize the discharge current. Control device 1600 and air battery 1100, transport device 1400, and power storage device 1700 are each connected by power line 1800.

  As the transport device 1400 described above, a general pump such as a tube pump or a piezo pump can be used. It is good also as not only this but transporting passively using gas pressure or gravity. What is necessary is just to arrange | position in the transport route by the connection pipe 1500, when transporting using a pump. However, in order to promote the precipitation of the metal particles, it is more desirable to arrange the metal particles at a position where the vibration of the transport device 1400 is transmitted to the negative electrode current collector 120.

  The material constituting the container 1110, the connecting pipe 1500, and the transport device 1400 described above may be an insulating material that does not cause a chemical reaction with the electrolytic solution or the negative electrode metal. For example, polytetrafluoroethylene (PTFE), polyvinylidene fluoride (PVDF), fluorine-containing resins such as fluorine rubber, or thermoplastic resins such as polypropylene and polyethylene, ethylene / propylene / diene monomer / monomers (EPDM), sulfonated EPDM, Natural butyl rubber (NBR) or the like can be used alone or as a mixture of two or more.

  Moreover, the support body which comprises the container 1110, the connection pipe 1500, and the air battery 1100 does not necessarily need to be formed separately, and a part or all of them can be integrally molded. Moreover, those shapes and arrangement methods are not particularly limited.

  In the above description, the case where the air battery system 1000 includes only one air battery 1100 has been described. However, as shown in FIG. 6, a plurality of air batteries 1100 may be electrically connected in series or in parallel. . The air battery system 2000 shown in FIG. 6 has a configuration in which three air batteries 1100 are electrically connected in series, and a connecting tube 2500 is connected so that a mixed liquid flows in parallel through the three air batteries 1100. did. With such a configuration, the air battery system 2000 can increase the current and voltage with a simple configuration, and can further increase the capacity.

  Moreover, it is good also as a structure which has the liquid container 3250 which integrated the liquid mixture container and the reaction liquid container like the air battery system 3000 shown in FIG. Here, the liquid container 3250 includes a filter 3300 made of a porous material. The filter 3300 can separate the mixed liquid 1210 and the reaction liquid 1310 and circulate only the electrolytic solution.

  As described above, according to the air battery system of the present embodiment, the charging time can be shortened even when the configuration is suitable for increasing the capacity.

  Examples of the present invention will be described below.

  First, materials that can be used to carry out the present invention will be described.

  As the electrolytic solution, a known nonaqueous electrolytic solution such as an organic electrolytic solution or an ionic liquid (molten salt) may be used as long as it does not directly react with metallic lithium and functions as an electrolytic solution. Can do. The viscosity of the electrolytic solution can be adjusted so that metallic lithium is dispersed with high efficiency in the electrolytic solution.

Examples of the organic electrolyte include well-known LiPF ₆ , LiClO ₄ , LiAsF ₆ , LiBF ₄ , Li (CF ₃ SO ₂ ) ₂ N, Li (CF ₃ SO ₃ ), LiN (C ₂ F ₅ SO ₂ ) _{2 and the} like. Can be used in which the supporting salt is dissolved in an aprotic organic solvent having no chain structure.

  Examples of such organic solvents include cyclic carbonates, chain carbonates, cyclic esters, cyclic ethers, chain ethers, and the like. Examples of the cyclic carbonate include ethylene carbonate (EC), propylene carbonate, butylene carbonate, and vinyl carbonate. Examples of the chain carbonate include dimethyl carbonate, diethyl carbonate (DEC), and methyl ethyl carbonate. Examples of the cyclic ester carbonate include gamma butyrolactone and gamma valerolactone. Examples of the cyclic ether include tetrahydrofuran and 2-methyltetrahydrofuran. Examples of the chain ether include dimethoxyethane and ethylene glycol dimethyl ether. These may be used alone or in combination. In addition, as the ionic conductor, an ionic liquid or the like may be used, or a plurality of these may be used in combination.

  As an air electrode, for example, a catalyst, a conductive material, and a binder can be mixed, and an appropriate solvent can be added to form a paste-like positive electrode material. The positive electrode material may be applied to the surface of the positive electrode current collector and dried, and may be compressed to increase the electrode density as necessary. Different material groups may be used for the charging cell and the discharging cell.

  The conductive material used for the air electrode is not particularly limited as long as it is an electron conductive material that does not adversely affect the battery performance of the positive electrode. A mixture of one or more of black, carbon black, ketjen black, carbon whisker, needle coke, carbon fiber, metal (steel, copper, nickel, silver, gold, etc.) can be used.

  The binder used for the air electrode plays a role of connecting the active material particles and the conductive material particles. For example, a fluorine-containing resin such as polytetrafluoroethylene (PTFE), polyvinylidene fluoride (PVDF), or fluororubber. Alternatively, thermoplastic resins such as polypropylene and polyethylene, ethylene / propylene / dienema (EPDM), sulfonated EPDM, and natural butyl rubber (NBR) can be used alone or as a mixture of two or more. In addition, an aqueous dispersion of cellulose or styrene butadiene rubber (SBR), which is an aqueous binder, can also be used.

  The catalyst for promoting the reaction of the air electrode is not particularly limited as long as oxygen in the air is reduced to oxygen ions during discharge. For example, as a catalyst, in addition to noble metal powder such as platinum, manganese, nickel Various metal oxides (including complex oxides) such as cobalt can be used. Alternatively, an organometallic complex such as metal porphyrin or metal phthalocyanine may be used.

  Examples of the solvent for dispersing the catalyst material, the conductive material and the binder include N-methylpyrrolidone, dimethylformamide, dimethylacetamide, methyl ethyl ketone, cyclohexanone, methyl acetate, methyl acrylate, diethyltriamine, N, N-dimethylaminopropyl. Organic solvents such as amine, ethylene oxide, and tetrahydrofuran can be used. Further, a dispersant, a thickener, or the like may be added to water, and the active material may be slurried with a latex such as a latex mainly composed of styrene and butadiene (SBR latex). As the thickener, for example, polysaccharides such as carboxymethyl cellulose and methyl cellulose can be used alone or as a mixture of two or more. Examples of the application method include roller coating such as applicator roll, screen coating, doctor blade method, spin coating, bar coater, and the like, and any of these can be used to obtain an arbitrary thickness and shape.

  As the positive electrode current collector, a porous body such as a mesh or mesh is preferably used in order to cause oxygen to diffuse quickly, and a porous metal plate such as stainless steel, nickel, or copper can be used. In order to suppress the oxidation of the current collector, the surface thereof may be coated with an oxidation resistant metal or alloy film. In addition, a water-repellent porous membrane such as polytetrafluoroethylene (PTFE) is pressure-bonded to the surface of the positive electrode current collector on the atmosphere side in order to prevent the evaporation of the electrolyte and the infiltration of water, and selectively pass only oxygen. Is possible. When the positive electrode current collector is covered with a non-conductor such as a water repellent porous film, a conductor such as a nickel ribbon is previously connected to the positive electrode current collector to expose the terminal to the outside.

  As the negative electrode current collector material, a conductive material that does not directly affect the battery reaction can be used. For example, stainless steel, copper, nickel, or titanium can be used. These metals alone or alloys thereof may be used, or the surface may be coated with other metals or alloys. In addition to these metals, oxide conductors and carbon can also be used.

  Further, when the negative electrode current collector structure is used as a discharge cell, a porous structure such as a network structure, a mesh structure, or a sponge structure that can trap the negative electrode metal powder and permeate the electrolytic solution can be used. In order to fully utilize the negative electrode metal, it is preferable that the opening and the hole diameter of the negative electrode current collector be as small as possible. Specifically, for example, titanium mesh, nichrome mesh, stainless steel mesh, carbon mesh, carbon felt, and the like can be used. When used as a charging cell, a concavo-convex structure or a groove structure is created by subjecting a plate-like electrode surface to chemical treatment or mechanical treatment.

  The separator is not particularly limited as long as it is a non-conductive porous film that allows the electrolytic solution to pass therethrough and exhibits corrosion resistance to the electrolytic solution. For example, a polytetrafluoroethylene (PTFE) porous film or a polyethylene non-woven fabric can be used.

  The support may be any material that has the strength to maintain the internal shape and does not directly affect the battery reaction and insulates the air electrode and the negative electrode current collector. For example, a resin material such as a fluorine-containing resin such as polytetrafluoroethylene (PTFE) or a thermoplastic resin such as polyethylene can be used. Alternatively, a metal material such as stainless steel, copper, nickel, or titanium, or a conductive material such as graphite that is entirely or partially coated with a resin material, or a material that has a multilayer structure of a plurality of materials may be used. In addition, only the insulating part between the air electrode and the negative electrode current collector is made of the above material, and other parts may be made of a metal such as stainless steel, copper, nickel, or titanium, or a conductive material such as graphite. Good.

[Example 1]
This example corresponds to the air battery 200 according to the second embodiment described above. The air battery of this example is composed of a support, a liquid channel, carbon paper, a PTFE porous membrane, a liquid channel, an air electrode, and a gas permselective membrane in this order. Sealed with a support molded into a mold and silicone.

As the electrolytic solution, one using a mixed solvent of ethylene carbonate (EC) and diethyl carbonate (DEC) and a Li (CF ₃ SO ₂ ) ₂ N (LiTFSI) supporting salt was used. The electrolyte solution was mixed with lithium wire cut into a fine powder to form a slurry liquid for discharge used for the first time.

  At the time of discharge, the pump is operated so that the mixed liquid flows from the lower part to the upper part of the air battery, and lithium metal is accumulated in the discharge negative electrode porous body to generate electric power. The electrode is a nickel ribbon taken out from the air electrode as a positive electrode and carbon paper as a negative electrode current collector.

[Example 2]
This example corresponds to the air battery 300 according to the third embodiment described above. The air battery of this example is composed of a copper plate, a slurry liquid path, a PTFE porous membrane, a slurry liquid path, an air electrode, and a gas permselective membrane in this order, and a support formed by molding polyether ketone ketone (PEEK) into a square shape. Seal with body and silicone.

  A negative electrode current collector for charging is obtained by performing groove processing with a width of about 50 μm and an interval of about 100 μm on the surface of the copper plate that contacts the slurry liquid. Also, the bottom of the pump that causes the slurry liquid to flow is bonded to the opposite surface of the copper plate.

As the electrolytic solution, one using a mixed solvent of ethylene carbonate (EC) and diethyl carbonate (DEC) and a Li (CF ₃ SO ₂ ) ₂ N (LiTFSI) supporting salt was used. The electrolyte solution was mixed with lithium wire cut into a fine powder to form a slurry liquid for discharge used for the first time.

  At the time of charging, the pump is operated so that the mixed liquid flows from the upper part to the lower part of the air battery, and charging is performed with the reaction product accumulated in the vicinity of the air electrode. The electrode is a nickel ribbon taken out from the air electrode as a positive electrode, and a copper plate as a negative electrode current collector.

Example 3
This example corresponds to the air battery 400 according to the fourth embodiment described above. The air battery of this example is composed of a copper plate, a slurry liquid path, carbon paper, a PTFE porous membrane, a slurry liquid path, an air electrode, and a gas permselective membrane in this order. Polyetherketone ketone (PEEK) is square. Sealed with molded support and silicone.

  A negative electrode current collector for charging is obtained by performing groove processing with a width of about 50 μm and an interval of about 100 μm on the surface of the copper plate that contacts the slurry liquid. Also, the bottom of the pump that causes the slurry liquid to flow is bonded to the opposite surface of the copper plate. A pump that can change the flow direction in both directions is used.

As the electrolytic solution, one using a mixed solvent of ethylene carbonate (EC) and diethyl carbonate (DEC) and a Li (CF ₃ SO ₂ ) ₂ N (LiTFSI) supporting salt was used. The electrolyte solution was mixed with lithium wire cut into a fine powder to form a slurry liquid for discharge used for the first time.

  At the time of discharge, the pump is operated so that the mixed liquid flows from the lower part to the upper part of the air battery, and lithium metal is accumulated in the discharge negative electrode porous body to generate electric power. The electrode is a nickel ribbon taken out from the air electrode as a positive electrode and carbon paper as a negative electrode current collector.

  At the time of charging, the pump is operated so that the mixed liquid flows from the upper part to the lower part of the air battery, and charging is performed with the reaction product accumulated in the vicinity of the air electrode. The electrode is a nickel ribbon taken out from the air electrode as a positive electrode, and a copper plate as a negative electrode current collector.

Example 4
In this example, a metal-air battery using aluminum powder instead of lithium as the negative electrode metal was used. An air battery system corresponding to the air battery system 1000 according to the fifth embodiment described above was configured using this aluminum air battery.

  A commercially available polytetrafluoroethylene (PTFE) container was used as the container, and a commercially available silicone tube was used as the connecting pipe. In addition, a piezo pump having chemical resistance was used as a transport device.

  The aluminum air battery of this example is configured to correspond to the air battery 200 according to the second embodiment described above. As the slurry liquid, a mixed liquid obtained by mixing an aqueous potassium hydroxide (KOH) solution and aluminum powder was used.

  To the air electrode, a nickel ribbon cathode electrode is ultrasonically bonded to a stainless steel mesh, and then a mixture of carbon black, platinum catalyst, and PTFE dispersion is thinly applied and dried, and a PTEF gas permeable membrane is pressed. Used. The air electrode was bonded to the support using an epoxy resin. The support was prepared by processing polyether ketone ketone (PEEK).

  Untreated carbon paper was used as the negative electrode current collector, and the carbon paper and the anode electrode of the nickel ribbon were sandwiched between the supports.

  The contacts of these parts were sealed with silicone rubber to prevent liquid leakage.

  The pump was operated so that the mixed liquid flowed from the lower part to the upper part of the aluminum air battery of this example, and it was confirmed that the power generation was performed between the electrodes and the aluminum powder was sequentially supplied.

  The present invention is not limited to the above-described embodiments and examples, and various modifications are possible within the scope of the invention described in the claims, and these are also included in the scope of the present invention. Needless to say.

  Part or all of the above embodiments and examples can be described as in the following supplementary notes, but are not limited thereto.

  (Additional remark 1) The positive electrode collector provided with the air electrode in which the positive electrode reaction of oxygen is performed, the negative electrode collector which adheres the metal particle which consists of negative electrode metals, and the separator which isolate | separates the said air electrode and the said negative electrode collector And an air battery having a circulating structure in which a mixed liquid in which negative electrode particles containing the negative electrode metal are dispersed in an electrolytic solution is circulated between the positive electrode current collector and the negative electrode current collector.

  (Supplementary note 2) The air electrode supplies electrons to oxygen molecules to introduce oxygen ions into the mixed liquid, and the negative electrode current collector includes a negative electrode current collector for discharge made of a porous conductor, The circulation structure circulates the mixed liquid in which the metal particles as the negative electrode particles are dispersed so as to pass through the discharge negative electrode current collector, and the discharge negative electrode current collector captures the metal particles. The air battery according to appendix 1, wherein electrons emitted when the metal particles are combined with the oxygen ions are derived.

  (Supplementary Note 3) The air electrode supplies electrons to a metal oxide generated by a reaction between the metal particles and the oxygen to generate oxygen ions in the electric field liquid. The negative electrode current collector for charging having a concavo-convex structure, wherein the circulating structure is a mixture of the metal oxide as the negative electrode particles dispersed in the positive electrode current collector and the negative electrode current collector for charging. The air battery according to appendix 1, wherein the charging negative electrode current collector deposits the metal particles and acquires electrons from the oxygen ions.

  (Supplementary Note 4) The air electrode supplies electrons to oxygen molecules, introduces oxygen ions into the liquid mixture, supplies electrons to the metal oxide produced by the reaction between the metal particles and the oxygen, and Oxygen ions are generated in the electrolysis solution, and the negative electrode current collector includes a negative electrode current collector for discharge made of a porous conductor, and a negative electrode current collector for charging having a concavo-convex structure on the surface. The mixed liquid in which the metal particles as the negative electrode particles are dispersed is circulated so as to pass through the negative electrode current collector for discharge, and the mixed liquid in which the metal oxide as the negative electrode particles is dispersed is Circulating between a positive electrode current collector and the charging negative electrode current collector, the discharging negative electrode current collector captures the metal particles, and emits electrons emitted when the metal particles combine with the oxygen ions. Derived, and the negative electrode current collector for charging is Air battery described in Appendix 1, the metal particles to precipitate, to gain electrons from the oxygen ions.

  (Additional remark 5) The said metal particle is an air battery as described in any one of Additional remark 1 to 4 which has lithium as a main component.

  (Additional remark 6) The air battery as described in any one of additional remarks 1 to 5, the container which accommodates the said air battery, The mixed liquid container which accommodates the said mixed liquid in which the said metal particle as said negative electrode particle was disperse | distributed, A reaction liquid container containing the mixed liquid in which the metal oxide generated by the reaction between the metal particles and the oxygen is dispersed, and the mixed liquid container is in the vicinity of the container and the negative electrode current collector And the reaction solution container is connected in the vicinity of the container and the positive electrode current collector.

  (Supplementary Note 7) The negative electrode current collector includes a negative electrode current collector for charging having a concavo-convex structure on the surface, and the circulation structure includes a transport device, the container, the mixed liquid container, and the reaction liquid container, respectively. The air battery system according to appendix 6, including a connecting pipe to be connected, wherein the transport device is disposed at a position where vibration of the transport device is transmitted to the charging negative electrode current collector.

  (Appendix 8) A mixed liquid in which the metal particles are dispersed is prepared by mixing metal particles and an electrolytic solution, and the mixed liquid is placed between a positive electrode current collector and an negative electrode current collector each having an air electrode. Circulate, supply electrons from the air electrode to oxygen molecules to generate oxygen ions, capture the metal particles by the negative electrode current collector, and release electrons when the metal particles combine with the oxygen ions. A metal oxide is produced by reacting the metal particles with the oxygen ions, and the metal oxide is circulated between the positive electrode current collector and the negative electrode current collector. A charge / discharge method for an air battery in which an electron is supplied to an oxide to generate oxygen ions and the metal particles are deposited on the negative electrode current collector.

  (Appendix 9) After depositing the metal particles on the negative electrode current collector to create a deposited metal structure, the deposited metal particles are created from the deposited metal structure, and the deposited metal particles are mixed with the electrolytic solution. The charge / discharge method of an air battery according to appendix 8, wherein the mixed liquid is prepared.

  (Additional remark 10) At the time of producing the said precipitated metal particle from the said precipitated metal structure, it adds at least one of the process of adding a vibration with respect to the said precipitated metal structure, and the process of discharging using the said precipitated metal structure as an electrode. The charge / discharge method of the air battery described in 2.

  (Additional remark 11) The said circulation structure flows out the electrolyte solution after discharge between the liquid mixture inlet for introducing the said liquid mixture in the vicinity of the said negative electrode collector for discharge, and the said separator and the said air electrode. The air battery as described in appendix 2 or 4, including a support body provided with a reaction liquid outlet.

  (Additional remark 12) The said circulation structure is a reaction liquid inlet for introducing the electrolyte solution after discharge between the said air electrode and the said separator, and a liquid mixture between the said negative electrode collector for charging, and the said separator. The air battery according to appendix 3 or 4, further comprising a support having a mixed liquid outlet for leading out, and further including a transport device for circulating the mixed liquid.

  (Additional remark 13) The air battery system as described in additional remark 6 or 7 which has the transport apparatus which circulates the said liquid mixture, and the control apparatus which measures either the electric current drop at the time of discharge, and a voltage drop and controls the said transport apparatus .

  (Additional remark 14) The air battery system as described in additional remark 6 or 7 provided with the electrical storage apparatus for stabilizing discharge current.

  (Supplementary Note 15) A plurality of the air batteries according to any one of Supplementary Note 1 to Supplementary Note 5 are provided, and the plurality of air batteries are electrically connected by either serial connection or parallel connection, and the mixing The air battery system according to appendix 6 or 7, wherein the air battery system has a connection pipe configured to allow liquid to flow in parallel through a plurality of air batteries.

  (Additional remark 16) It has a liquid container provided with the filter which consists of porous materials, The said filter isolate | separates the reaction liquid which is the mixed liquid and the mixed liquid which the said metal oxide disperse | distributed, and circulates only the said electrolyte solution The air battery system described in Supplementary Note 6 or 7.

100, 200, 300, 400, 1100 Air battery 110 Positive electrode current collector 111 Air electrode 120 Negative electrode current collector 130 Separator 140 Circulation structure 212, 222, 312, 322, 412 Electrode terminal 213 Gas diffusion permeable film 220 Negative electrode current collector for discharge Electrode 240, 340, 440 Support 241 Mixed liquid inlet 242 Reaction liquid outlet 320 Charging negative electrode current collector 341 Reaction liquid inlet 342 Mixed liquid outlet 350, 1400 Transport device 441 Reaction liquid inlet / outlet 442 Mixed liquid Inflow / outflow port 1000, 2000, 3000 Air battery system 1110 Container 1200 Mixed liquid container 1210 Mixed liquid 1300 Reaction liquid container 1310 Reaction liquid 1500 2500 Connection pipe 1600 Controller 1700 Power storage device 1800 Power line 3250 Liquid container 3300 Luta 1 Relevant air battery 2 Oxygen diffusion membrane 3 Positive electrode current collector 4 Positive electrode catalyst layer 6 Separator 9 Electrolyte 13 Positive electrode 17 Negative electrode 19 Laminate 20 Power generator 30 Related electrochemical cell system 32 Anode structure 34 Support structure 40 Related zinc Air battery 44 Zinc pellet 52 Negative electrode current collector 56 Air electrode

Claims (10)

A positive electrode current collector having an air electrode in which a positive electrode reaction of oxygen is performed;
A negative electrode current collector to which metal particles made of a negative electrode metal are attached;
A separator for separating the air electrode and the negative electrode current collector;
An air battery comprising: a circulating structure in which a mixed liquid in which negative electrode particles including the negative electrode metal are dispersed in an electrolytic solution is circulated between the positive electrode current collector and the negative electrode current collector. The air electrode supplies electrons to oxygen molecules to introduce oxygen ions into the mixed liquid,
The negative electrode current collector includes a negative electrode current collector for discharge made of a porous conductor,
The circulation structure circulates the mixed liquid in which the metal particles as the negative electrode particles are dispersed so as to pass through the negative electrode current collector for discharge,
The air battery according to claim 1, wherein the discharge negative electrode current collector captures the metal particles and derives electrons emitted when the metal particles are combined with the oxygen ions. The air electrode supplies electrons to the metal oxide generated by the reaction between the metal particles and the oxygen to generate oxygen ions in the electrolysis solution,
The negative electrode current collector includes a charging negative electrode current collector having an uneven structure on the surface,
The circulating structure circulates the mixed liquid in which the metal oxide as the negative electrode particles is dispersed between the positive electrode current collector and the negative electrode current collector for charging,
The air battery according to claim 1, wherein the negative electrode current collector for charging deposits the metal particles and acquires electrons from the oxygen ions. The air electrode supplies electrons to oxygen molecules, introduces oxygen ions into the mixed liquid, supplies electrons to the metal oxide generated by the reaction between the metal particles and oxygen, and enters the electric field liquid. Generate oxygen ions,
The negative electrode current collector includes a negative electrode current collector for discharge made of a porous conductor, and a negative electrode current collector for charging having an uneven structure on the surface,
The circulation structure circulates the mixed liquid in which the metal particles as the negative electrode particles are dispersed so as to pass through the negative electrode current collector for discharge,
The mixed liquid in which the metal oxide as the negative electrode particles is dispersed is circulated between the positive electrode current collector and the charging negative electrode current collector,
The discharge negative electrode current collector captures the metal particles and derives electrons that are emitted when the metal particles are combined with the oxygen ions,
The air battery according to claim 1, wherein the negative electrode current collector for charging deposits the metal particles and acquires electrons from the oxygen ions. The air battery according to any one of claims 1 to 4, wherein the metal particles have lithium as a main component. An air battery according to any one of claims 1 to 5;
A container for housing the air battery;
A mixed liquid container containing the mixed liquid in which the metal particles as the negative electrode particles are dispersed;
A reaction liquid container containing the mixed liquid in which the metal oxide generated by the reaction between the metal particles and the oxygen is dispersed;
The mixed liquid container is connected in the vicinity of the container and the negative electrode current collector,
The reaction liquid container is connected in the vicinity of the container and the positive electrode current collector. The negative electrode current collector includes a charging negative electrode current collector having an uneven structure on the surface,
The circulation structure includes a transport device, a connecting pipe that connects the container, the mixed liquid container, and the reaction liquid container, respectively.
The air battery system according to claim 6, wherein the transport device is disposed at a position where vibration of the transport device is transmitted to the charging negative electrode current collector. Create a mixed liquid in which the metal particles are dispersed by mixing the metal particles and the electrolyte,
Circulating the mixed liquid between a positive electrode current collector and an negative electrode current collector each having an air electrode;
Supplying electrons from the air electrode to oxygen molecules to generate oxygen ions,
The metal particles are captured by the negative electrode current collector, and discharged by deriving electrons emitted when the metal particles are combined with the oxygen ions,
Producing a metal oxide by reacting the metal particles with the oxygen ions;
Circulating the metal oxide between the positive electrode current collector and the negative electrode current collector;
A method for charging and discharging an air battery, wherein charging is performed by supplying electrons to the metal oxide to generate oxygen ions and depositing the metal particles on the negative electrode current collector. After the metal particles are deposited on the negative electrode current collector to form a deposited metal structure, the deposited metal particles are created from the deposited metal structure, and the deposited metal particles are mixed with the electrolytic solution to form the mixed liquid. The charge / discharge method of the air battery according to claim 8 to be created. When creating the deposited metal particles from the deposited metal structure,
The charge / discharge method for an air battery according to claim 9, wherein at least one of a step of applying vibration to the deposited metal structure and a step of discharging using the deposited metal structure as an electrode is performed.