JP2013206872A - Metal-oxygen battery - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a metal-oxygen battery which can obtain a large charge/discharge capacity and also can obtain excellent cycle characteristics.SOLUTION: A metal-oxygen battery 1 comprises a cathode 2 including an oxygen storage material and using oxygen as an active material, an anode 3 using metal as an active material, and an electrolyte layer 4 held between the cathode 2 and the anode 3. The cathode 2, the anode 3 and the electrolyte layer 4 are hermetically housed in an enclosure 5. Cell reaction of the cathode 2 occurs on the surface of the oxygen storage material. Here, the oxygen storage material consists of a first oxygen storage material having the capability of chemically occluding and discharging oxygen to and from the inside or physically adsorbing and desorbing oxygen to and from the surface and a second oxygen storage material which is a porous material having the oxygen adsorption and desorption capability.

Description

  The present invention relates to a metal oxygen battery.

  Conventionally, a metal oxygen battery including a positive electrode using oxygen as an active material, a negative electrode using metal as an active material, and an electrolyte layer sandwiched between the positive electrode and the negative electrode is known.

  In the metal oxygen battery, during discharge, the metal is oxidized to generate metal ions at the negative electrode, and the metal ions move to the positive electrode side. On the other hand, in the positive electrode, oxygen is reduced to generate oxygen ions, and the oxygen ions are combined with the metal ions to generate a metal oxide. In the metal oxygen battery, the reverse reaction of the reaction occurs at the negative electrode and the positive electrode during charging.

  In the metal oxygen battery, when metal lithium is used as the metal, since the metal lithium has a high theoretical voltage and a large electrochemical equivalent, a large charge / discharge capacity can be obtained. In addition, when oxygen in the air is used as oxygen, it is not necessary to fill the positive electrode active material in the battery, so that the energy density per mass of the battery can be increased.

  However, when the positive electrode is opened to the atmosphere in order to use oxygen in the air as the positive electrode active material, there is a problem that moisture, carbon dioxide, etc. in the air enter the battery and the electrolyte layer, the negative electrode, and the like deteriorate. Accordingly, in order to solve the above-described problem, a positive electrode including an oxygen storage material that releases oxygen by receiving light, a negative electrode made of metallic lithium, an electrolyte layer sandwiched between the positive electrode and the negative electrode, and the oxygen storage There is known a metal oxygen battery in which the positive electrode, the negative electrode, and the electrolyte layer are sealed and accommodated in a housing having a light transmission portion that guides light to the material. (For example, refer to Patent Document 1).

  Further, as the positive electrode material of the metal oxygen battery, instead of using the oxygen storage material that needs to receive light, it does not require light reception, and chemically stores and releases oxygen inside or physically releases oxygen. The use of oxygen storage materials that can be adsorbed to and desorbed from the surface has been studied.

JP 2009-230985 A

  However, the metal oxygen battery using the oxygen storage material as the positive electrode material cannot obtain a sufficient charge / discharge capacity with respect to the theoretical value of the oxygen storage material, and can obtain a sufficient cycle performance. There is an inconvenience that it cannot be done.

  An object of the present invention is to provide a metal oxygen battery capable of solving such inconvenience and obtaining a large charge / discharge capacity and an excellent cycle performance.

  As a result of intensive studies by the present inventors, in the metal oxygen battery using the oxygen storage material, the reason why a sufficient charge / discharge capacity with respect to the theoretical value of the oxygen storage material cannot be obtained is that the oxygen storage during discharge This is probably because the amount of oxygen released from the material is lower than the theoretical value. In addition, in the metal oxygen battery using the oxygen storage material, it is considered that a sufficient cycle performance cannot be obtained because part of oxygen is not re-stored in the oxygen storage material during charging.

  That is, in the metal oxygen battery using the oxygen storage material, during discharge, the metal is oxidized in the negative electrode to generate metal ions, and the generated metal ions pass through the electrolyte layer and move to the positive electrode side. On the other hand, in the positive electrode, oxygen released from the oxygen storage material is reduced to generate oxygen ions, and the generated oxygen ions are combined with the metal ions to generate metal oxides.

  Further, at the time of charging, in the positive electrode, the metal oxide is decomposed to generate metal ions and oxygen ions, and the generated oxygen ions are oxidized and stored as oxygen in the oxygen storage material. On the other hand, the metal ions permeate the electrolyte layer and move to the negative electrode side, and are reduced to the metal by the negative electrode. Of the battery reactions described above, the surface of the oxygen storage material serves as a reaction field for the reaction occurring at the positive electrode.

  However, when the metal oxide is generated at the positive electrode during discharge and the surface of the oxygen storage material is completely covered with the metal oxide, and there is no exposed portion on the surface of the oxygen storage material, the reaction field disappears. To do. As a result, even when oxygen remains stored in the oxygen storage material, the release of the oxygen from the oxygen storage material stops, and the battery reaction does not proceed any more. From the above, it is considered that the metal oxygen battery using the oxygen storage material cannot obtain a sufficient discharge capacity.

  Also, as described above, during discharge, a part of oxygen remains stored in the oxygen storage material, and when the amount of oxygen released from the oxygen storage material decreases, the amount of metal oxide generated decreases. As a result, according to the metal oxygen battery using the oxygen storage material, it is considered that a battery reaction accompanied by decomposition of the metal oxide does not occur sufficiently during charging, and a sufficient charge capacity cannot be obtained.

  Furthermore, when a part of oxygen ions generated by the decomposition of the metal oxide is not re-stored in the oxygen storage material at the time of charging, the amount of oxygen available for the battery reaction at the next discharge decreases. As a result, according to the metal oxygen battery using the oxygen storage material, it is considered that sufficient cycle performance cannot be obtained.

  The present invention has been made based on the above consideration, and in order to achieve the above object, a positive electrode containing an oxygen storage material and containing oxygen as an active material, a negative electrode containing a metal as an active material, the positive electrode and In the metal oxygen battery, the positive electrode, the negative electrode, and the electrolyte layer are sealed and accommodated in a casing, and the battery reaction of the positive electrode occurs on the surface of the oxygen storage material. The oxygen storage material comprises: a first oxygen storage material having an oxygen storage / release capacity for chemically storing and releasing oxygen therein, or an oxygen storage / release capacity for physically adsorbing and desorbing oxygen on the surface; It consists of the 2nd oxygen storage material which is a porous body provided with oxygen adsorption / desorption ability.

  Here, the first oxygen storage material may have only one or both of the oxygen storage / release ability and the oxygen absorption / desorption ability.

  According to the metal oxygen battery of the present invention, since the positive electrode includes the first oxygen storage material and the second oxygen storage material having different performances, only one kind of oxygen storage material is contained in the first oxygen storage material. Compared with the case where the same amount as the total mass of the storage material and the second oxygen storage material is included, a large charge / discharge capacity can be obtained and excellent cycle performance can be obtained.

  In the metal oxygen battery of the present invention, a large charge / discharge capacity and an excellent cycle performance can be obtained for the following reason.

  In other words, in the metal oxygen battery of the present invention, the first oxygen storage material and the second oxygen storage material have different performances from each other, so that the battery reaction occurs on the surface of one oxygen storage material. It happens preferentially. For this reason, even when the surface of one oxygen storage material is completely covered during discharge and there is no exposed portion on the surface of the oxygen storage material, there is an exposed portion on the surface of the other oxygen storage material. The cell reaction can be continued by the oxygen released from the other oxygen storage material. As a result, according to the metal oxygen battery of the present invention, a large discharge capacity can be obtained.

  In addition, as described above, the amount of oxygen released from both the first oxygen storage material and the second oxygen storage material during discharge increases, resulting in an increase in the amount of metal oxide generated. As a result, since the battery reaction accompanied by the decomposition of the metal oxide can be sufficiently advanced during charging, a large charge capacity can be obtained according to the metal oxygen battery of the present invention.

  Furthermore, even when part of the oxygen ions generated by the decomposition of the metal oxide is not re-stored in the oxygen storage material during charging, both can be stored in the other oxygen storage material. The reduction in the amount of oxygen stored in the oxygen storage material can be suppressed. As a result, according to the metal oxygen battery of the present invention, a large amount of oxygen can be released from both oxygen storage materials at the next discharge, so that sufficient cycle performance can be obtained.

  By the way, in the metal oxygen battery of the present invention, it is desired that the oxygen storage material constituting the positive electrode not only has the ability to store oxygen, but also has catalytic ability for cell reaction and electronic conductivity. In the metal oxygen battery of the present invention, it is considered that by using an oxygen storage material having both the catalytic ability and the electronic conductivity, the battery reaction can be further promoted to further improve the charge / discharge capacity. However, there is no known oxygen storage material having both the catalytic ability and the electronic conductivity.

  Therefore, in the metal oxygen battery of the present invention, it is preferable that the first oxygen storage material further has a catalytic ability with respect to a battery reaction, and the oxygen storage / release ability, the oxygen adsorption / desorption ability, and the catalytic ability are As the first oxygen storage material having both, a composite metal oxide containing Y and Mn can be given.

  In the metal oxygen battery of the present invention, the second oxygen storage material preferably further has electronic conductivity, and the second oxygen storage material having both the oxygen adsorption / desorption capability and the electron conductivity. Examples of the material include activated carbon.

  In the metal oxygen battery of the present invention, the negative electrode includes one metal selected from the group consisting of Li, Zn, Al, Mg, Fe, Ca, Na, and K, an alloy of the metal, and the metal. A compound made of either an organic metal compound or an organic complex of the metal can be used.

BRIEF DESCRIPTION OF THE DRAWINGS Explanatory sectional drawing which shows one structural example of the metal oxygen battery of this invention. The graph which shows the relationship between the discharge capacity density and cell voltage of the metal oxygen battery of a present Example.

  Next, embodiments of the present invention will be described in more detail with reference to the accompanying drawings.

  As shown in FIG. 1, the metal oxygen battery 1 of this embodiment includes an oxygen storage material and is sandwiched between a positive electrode 2 using oxygen as an active material, a negative electrode 3 using metal as an active material, and a positive electrode 2 and a negative electrode 3. The positive electrode 2, the negative electrode 3, and the electrolyte layer 4 are sealed and accommodated in a case 5.

  The case 5 includes a cup-shaped case main body 6 and a lid body 7 that closes the case main body 6, and a ring-shaped insulating resin 8 is interposed between the case main body 6 and the lid body 7. . The positive electrode 2 includes a positive electrode current collector 9 and a pressing member 10 between the top surface of the lid 7 and the negative electrode 3 includes a negative electrode current collector 11 between the bottom surface of the case body 6. . In the metal oxygen battery 1, the case body 6 functions as a negative electrode plate, and the lid body 7 functions as a positive electrode plate.

  In the metal oxygen battery 1, the positive electrode 2 includes a conductive additive and a binder in addition to the oxygen storage material, and has a void in the range of 0.1 to 200 μm.

  The oxygen storage material includes a first oxygen storage material and a second oxygen storage material having different performances. In the present embodiment, the oxygen storage material is composed of two types of oxygen storage materials, but may be composed of three or more types of oxygen storage materials as long as their performances are different from each other.

  Does the first oxygen storage material have only one of oxygen storage / release ability for chemically storing and releasing oxygen inside and oxygen storage / release capacity for physically adsorbing and desorbing oxygen on the surface? Or both. As a 1st oxygen storage material, the composite metal oxide containing Y and Mn can be mentioned, for example.

  A 2nd oxygen storage material is a porous body provided with the said oxygen adsorption / desorption capability, and is further provided with electronic conductivity. The porous body has pores of 0.4 to 100 nm and can adsorb and desorb oxygen on the surfaces of the pores. Examples of the second oxygen storage material include activated carbon.

  Examples of the conductive aid include carbon materials such as graphite, acetylene black, ketjen black, carbon nanotube, mesoporous carbon, and carbon fiber.

  Examples of the binder include polytetrafluoroethylene (PTFE), carboxymethylcellulose (CMC), polyvinyl alcohol (PVA), polyvinylidene fluoride (PVDF), styrene butadiene rubber (SBR), and polyimide (PI). it can.

  The positive electrode 2 is manufactured as follows. First, the second oxygen storage material, the conductive auxiliary agent, and the binder are mixed, and then the first oxygen storage material is further mixed. Next, the obtained positive electrode mixture is applied to one side of the positive electrode current collector 9 and dried.

  Next, after the cathode mixture applied to the cathode current collector 9 and dried is heated to a temperature of 200 ° C., it is cooled to room temperature while flowing oxygen gas through the cathode mixture, and further oxygen gas is allowed to flow at room temperature. As a result, oxygen is adsorbed to the first oxygen storage material and the second oxygen storage material contained in the dried positive electrode mixture. Thus, the positive electrode 2 can be obtained. In the obtained positive electrode 2, voids having an average pore diameter in the range of 0.1 to 200 μm are formed.

  As the negative electrode 3, one metal selected from the group consisting of Li, Zn, Al, Mg, Fe, Ca, Na, and K, an alloy of the metal, an organometallic compound containing the metal, or an organic complex of the metal Any of the above can be used. In the present embodiment, a case where a lithium metal foil is used for the negative electrode 3 will be described as an example.

  The electrolyte layer 4 may be, for example, a nonaqueous electrolyte solution immersed in a separator, or a solid electrolyte.

  As the non-aqueous electrolyte solution, for example, a lithium salt dissolved in a non-aqueous solvent can be used. As said lithium salt, carbonate, nitrate, acetate etc. can be mentioned, for example. Examples of the non-aqueous solvent include a carbonate ester solvent, an ether solvent, and an ionic liquid.

  Examples of the carbonate ester solvent include ethylene carbonate, propylene carbonate, dimethyl carbonate, and diethyl carbonate. Two or more of the carbonate ester solvents can be used in combination.

  Examples of the ether solvent include dimethoxyethane, dimethyl trigram, polyethylene glycol, and the like. Two or more of the ether solvents can be used in combination.

  Examples of the ionic liquid include cations such as imidazolium, ammonium, pyridinium, and peridium, bis (trifluoromethylsulfonyl) imide (TTSI), bis (pentafluoroethylsulfonyl) imide (BETI), tetrafluoroborate, park, and the like. Examples thereof include salts with anions such as lorate and halogen anions.

  Examples of the separator include glass fiber, glass paper, polypropylene non-woven fabric, polyimide non-woven fabric, polyphenylene sulfide non-woven fabric, polyethylene porous film, and the like having a thickness of 40 to 1000 μm. Can do.

  Examples of the solid electrolyte include an oxide solid electrolyte and a sulfide solid electrolyte.

Examples of the oxide solid electrolyte include Li ₇ La ₃ Zr ₂ O ₁₂ , which is a composite oxide of lithium, lanthanum, and zirconium, glass ceramics mainly composed of lithium, aluminum, silicon, titanium, germanium, and phosphorus. Can be mentioned. In Li ₇ La ₃ Zr ₂ O ₁₂ , lithium, lanthanum, and zirconium were partially substituted with other metals such as strontium, barium, silver, yttrium, lead, tin, antimony, hafnium, tantalum, and niobium. It may be a thing.

  As the positive electrode current collector 9, foam metal, mesh, porous body, or metal foil made of Al, Ti, stainless steel, Ni, or the like can be used.

  Examples of the pressing member 10 include stainless steel.

  Examples of the negative electrode current collector 11 include a foam metal made of stainless steel, Cu, Ni, etc., a mesh made of Cu, stainless steel, a porous body, a metal foil made of Cu, a metal plate made of stainless steel, and the like.

  According to the metal oxygen battery 1 of the present embodiment, the positive electrode 2 includes the first oxygen storage material and the second oxygen storage material having different performances, so that only one type of oxygen storage material is contained in the first oxygen storage material. Compared with the case where the same mass as the total mass of the first oxygen storage material and the second oxygen storage material is included, a large charge / discharge capacity can be obtained and excellent cycle performance can be obtained.

  Further, since the positive electrode 2 is formed with voids having an average pore diameter in the range of 0.1 to 200 μm, the electrolytic solution can be infiltrated into the voids. It can be promoted, and a large charge / discharge capacity can be obtained reliably. Moreover, since the positive electrode 2 can accommodate the metal oxide produced at the time of discharge by forming the void, the expansion of the positive electrode 2 due to the metal oxide can be suppressed. it can.

  Next, examples and comparative examples of the present invention are shown.

〔Example〕
In this example, first, yttrium nitrate pentahydrate, manganese nitrate hexahydrate, and malic acid were pulverized and mixed at a molar ratio of 1: 1: 6 to obtain a mixture. . Next, the obtained mixture was reacted at a temperature of 250 ° C. for 30 minutes, and further reacted at a temperature of 300 ° C. for 30 minutes and at a temperature of 350 ° C. for 1 hour. Next, the mixture of reaction products was pulverized and mixed, and then fired at a temperature of 1000 ° C. for 1 hour to obtain a composite metal oxide represented by the chemical formula YMnO ₃ .

  The composite metal oxide has an oxygen storage / release capability for chemically storing and releasing oxygen therein, or an oxygen storage / desorption capability for physically adsorbing and desorbing oxygen on the surface, and a catalytic capability for battery reaction. Yes. In this example, the composite metal oxide was used as the first oxygen storage material.

  Next, activated carbon (manufactured by Kuraray Co., Ltd., pore diameter 0.4 to 100 nm, pore volume 0.94 mL / g) was prepared. The activated carbon has the oxygen adsorption / desorption capability and electronic conductivity. In this example, the activated carbon was used as the second oxygen storage material.

  Next, an N-methyl-2-pyrrolidone solution (stock) containing 8% by mass of the activated carbon, ketjen black (manufactured by Lion Corporation) as a conductive additive, and polyvinylidene fluoride (PVDF) as a binder. (Manufactured by Kuraray Co., Ltd.), and the obtained composite metal oxide was further mixed. In the mixing, the mixed metal oxide as the first oxygen storage material, the activated carbon as the second oxygen storage material, the ketjen black, and the PVDF are 10: 60: 10: 20. The mass ratio was performed.

  Next, the obtained positive electrode mixture was applied to one side of a foamed aluminum sheet (manufactured by Mitsubishi Materials Corporation, thickness 400 μm, average bubble diameter 150 μm, porosity 75%) as the positive electrode current collector 9 and dried. .

  Next, the positive electrode mixture applied to the positive electrode current collector 9 and dried is heated to a temperature of 200 ° C., and then cooled to room temperature while flowing oxygen gas at a flow rate of 100 mL / min to the positive electrode mixture. Then, oxygen gas was allowed to adsorb to the first oxygen storage material and the second oxygen storage material contained in the dried positive electrode mixture by further flowing oxygen gas for 2 hours. Thus, the positive electrode 2 having a diameter of 15 mm and a thickness of 0.4 mm was formed. In the positive electrode 2, voids having an average pore diameter of 1 μm are formed.

  Next, a negative electrode current collector 11 made of stainless steel having a diameter of 15 mm is disposed inside a bottomed cylindrical SUS case body 6 having an inner diameter of 17 mm. The negative electrode current collector 11 has a diameter of 15 mm and a thickness of 0.1 mm. A negative electrode 3 made of 1 mm metal lithium foil was superposed.

  Next, a separator made of a microporous film having a diameter of 17 mm (manufactured by Asahi Kasei Corporation) was superposed on the negative electrode 3. Next, the positive electrode 2 and the positive electrode current collector 9 obtained as described above were superimposed on the separator so that the positive electrode 2 was in contact with the separator. Next, a non-aqueous electrolyte solution was injected into the separator to form an electrolyte layer 4.

As the non-aqueous electrolyte solution, lithium hexafluorophosphate (LiPF ₆ ) was dissolved as a supporting salt at a concentration of 1 mol / L in a mixed solution in which ethylene carbonate and diethyl carbonate were mixed at a mass ratio of 30:70. The solution (made by Kishida Chemical Co., Ltd.) was used.

  Next, the pressing member 10 made of stainless steel was disposed inside the bottomed cylindrical SUS lid body 7 having an inner diameter of 17 mm.

  Next, the laminate composed of the negative electrode current collector 11, the negative electrode 3, the electrolyte layer 4, the positive electrode 2, and the positive electrode current collector 9 housed in the case body 6 is closed with the lid body 7 on which the pressing member 10 is disposed. Covered. At this time, by disposing a ring-shaped insulating resin 8 made of polytetrafluoroethylene (PTFE) having an outer diameter of 32 mm, an inner diameter of 30 mm, and a thickness of 5 mm between the case body 6 and the lid body 7, FIG. A metal oxygen battery 1 shown in FIG. In the metal oxygen battery 1, the positive electrode 2, the negative electrode 3, and the electrolyte layer 4 are sealed and accommodated in a case 5.

Next, the metal oxygen battery 1 obtained in this example was mounted on an electrochemical measuring device (manufactured by Toho Giken Co., Ltd.), and a current of 0.025 mA / cm ² was applied between the negative electrode 3 and the positive electrode 2. This was applied and discharged until the cell voltage reached 2.0V. FIG. 2 shows the relationship between the discharge capacity (discharge capacity density) per unit mass of the obtained oxygen storage material and the cell voltage.

[Comparative Example 1]
In this comparative example, first, the composite metal oxide was obtained in exactly the same manner as in the example. In this comparative example, the composite metal oxide was used as an oxygen storage material.

  Next, except that the activated carbon is not used at all, the ketjen black and the N-methyl-2-pyrrolidone solution containing 8% by mass of the PVDF are mixed exactly as in the example, The obtained composite metal oxide was mixed. The mixing was performed such that the composite metal oxide as an oxygen storage material, the ketjen black, and the PVDF had a mass ratio of 70:10:20.

  Next, a positive electrode 2 was formed in the same manner as in the example except that the positive electrode mixture obtained in this comparative example was used.

  Next, a metal oxygen battery 1 was produced in the same manner as in the example except that the positive electrode 2 obtained in this comparative example was used.

  Next, discharging was performed in exactly the same manner as in the example except that the metal oxygen battery 1 obtained in this comparative example was used. The relationship between the obtained discharge capacity density and the cell voltage is shown in FIG.

[Comparative Example 2]
In this comparative example, first, the activated carbon was prepared in exactly the same manner as in the example. In this comparative example, the activated carbon was used as an oxygen storage material.

  Next, N-methyl-2-containing 8% by mass of the binder, the ketjen black, and the PVDF in exactly the same manner as in Examples except that the composite metal oxide is not used at all. The pyrrolidone solution was mixed. The mixing was performed such that the activated carbon as an oxygen storage material, the ketjen black, and the PVDF had a mass ratio of 70:10:20.

  Next, a positive electrode 2 was formed in the same manner as in the example except that the positive electrode mixture obtained in this comparative example was used.

  Next, a metal oxygen battery 1 was produced in the same manner as in the example except that the positive electrode 2 obtained in this comparative example was used.

  Next, discharging was performed in exactly the same manner as in the example except that the metal oxygen battery 1 obtained in this comparative example was used. The relationship between the obtained discharge capacity density and the cell voltage is shown in FIG.

  From FIG. 2, it is clear that the metal oxygen battery 1 of the example has a larger discharge capacity per unit mass than the metal oxygen batteries 1 of Comparative Examples 1 and 2. In addition, the metal oxygen battery 1 of the example has a wider discharge capacity per unit mass when in the steady state than the metal oxygen batteries 1 of Comparative Examples 1 and 2, and the steady state It is clear that the battery voltage is excellent because it has a large cell voltage.

  DESCRIPTION OF SYMBOLS 1 ... Metal oxygen battery, 2 ... Positive electrode, 3 ... Negative electrode, 4 ... Electrolyte layer, 5 ... Housing | casing.

Claims (6)

A positive electrode containing an oxygen storage material and containing oxygen as an active material, a negative electrode containing metal as an active material, an electrolyte layer sandwiched between the positive electrode and the negative electrode, and the positive electrode, the negative electrode and the electrolyte layer are In a metal oxygen battery that is hermetically sealed and accommodated in a casing, and the battery reaction of the positive electrode occurs on the surface of the oxygen storage material,
The oxygen storage material includes: a first oxygen storage material having an oxygen storage / release capability of chemically storing and releasing oxygen therein; or an oxygen storage / release capability of physically adsorbing and desorbing oxygen on the surface; A metal oxygen battery comprising a second oxygen storage material which is a porous body having adsorption / desorption capability. The metal oxygen battery according to claim 1, wherein
The metal oxygen battery, wherein the first oxygen storage material further has a catalytic ability for a battery reaction. The metal oxygen battery according to claim 2, wherein
The metal oxygen battery, wherein the first oxygen storage material is a composite metal oxide containing Y and Mn. The metal oxygen battery according to any one of claims 1 to 3,
The metal oxygen battery, wherein the second oxygen storage material further has electronic conductivity. The metal oxygen battery according to claim 4, wherein
The metal oxygen battery, wherein the second oxygen storage material is activated carbon. The metal oxygen battery according to any one of claims 1 to 5,
The negative electrode is made of one metal selected from the group consisting of Li, Zn, Al, Mg, Fe, Ca, Na, and K, an alloy of the metal, an organometallic compound containing the metal, or an organic complex of the metal. A metal oxygen battery comprising any of the above.

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