WO2021111495A1 - 空気電池、および、空気電池の正極の製造方法 - Google Patents

空気電池、および、空気電池の正極の製造方法 Download PDF

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WO2021111495A1
WO2021111495A1 PCT/JP2019/046987 JP2019046987W WO2021111495A1 WO 2021111495 A1 WO2021111495 A1 WO 2021111495A1 JP 2019046987 W JP2019046987 W JP 2019046987W WO 2021111495 A1 WO2021111495 A1 WO 2021111495A1
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Prior art keywords
positive electrode
air battery
negative electrode
continuum
metal
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English (en)
French (fr)
Japanese (ja)
Inventor
三佳誉 岩田
正也 野原
田口　博章
柚子 小林
武志 小松
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NTT Inc
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Nippon Telegraph and Telephone Corp
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Priority to PCT/JP2019/046987 priority Critical patent/WO2021111495A1/ja
Priority to JP2021562208A priority patent/JP7356053B2/ja
Priority to US17/779,917 priority patent/US12080867B2/en
Publication of WO2021111495A1 publication Critical patent/WO2021111495A1/ja
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/10—Primary casings; Jackets or wrappings
    • H01M50/138—Primary casings; Jackets or wrappings adapted for specific cells, e.g. electrochemical cells operating at high temperature
    • H01M50/1385—Hybrid cells
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M12/00—Hybrid cells; Manufacture thereof
    • H01M12/04—Hybrid cells; Manufacture thereof composed of a half-cell of the fuel-cell type and of a half-cell of the primary-cell type
    • H01M12/06—Hybrid cells; Manufacture thereof composed of a half-cell of the fuel-cell type and of a half-cell of the primary-cell type with one metallic and one gaseous electrode
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M12/00—Hybrid cells; Manufacture thereof
    • H01M12/02—Details
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
    • H01M4/381—Alkaline or alkaline earth metals elements
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/90—Selection of catalytic material
    • H01M4/9016—Oxides, hydroxides or oxygenated metallic salts
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/90—Selection of catalytic material
    • H01M4/9041—Metals or alloys
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/90—Selection of catalytic material
    • H01M4/9075—Catalytic material supported on carriers, e.g. powder carriers
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/90—Selection of catalytic material
    • H01M4/9075—Catalytic material supported on carriers, e.g. powder carriers
    • H01M4/9083—Catalytic material supported on carriers, e.g. powder carriers on carbon or graphite
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/96—Carbon-based electrodes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/10—Primary casings; Jackets or wrappings
    • H01M50/102—Primary casings; Jackets or wrappings characterised by their shape or physical structure
    • H01M50/107—Primary casings; Jackets or wrappings characterised by their shape or physical structure having curved cross-section, e.g. round or elliptic
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/10—Primary casings; Jackets or wrappings
    • H01M50/116—Primary casings; Jackets or wrappings characterised by the material
    • H01M50/121—Organic material
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/409—Separators, membranes or diaphragms characterised by the material
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2300/00—Electrolytes
    • H01M2300/0002—Aqueous electrolytes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2300/00—Electrolytes
    • H01M2300/0002—Aqueous electrolytes
    • H01M2300/0005—Acid electrolytes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2300/00—Electrolytes
    • H01M2300/0002—Aqueous electrolytes
    • H01M2300/0005—Acid electrolytes
    • H01M2300/0008—Phosphoric acid-based
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Definitions

  • the present invention relates to an air battery and a method for manufacturing a positive electrode of an air battery.
  • Non-Patent Documents 1 and 2 Air batteries are being researched and developed (Non-Patent Documents 1 and 2). Since a conventional air battery requires oxygen in the air used as a positive electrode active material, a positive electrode is arranged outside the battery cell and a negative electrode is arranged inside the battery cell. Powdered carbon or the like is used for the positive electrode. Metals such as magnesium, iron, aluminum and zinc are used for the negative electrode.
  • the conventional air battery uses fluororesin as a binder such as powdered carbon for the positive electrode, it is not easy to dispose of it at the time of use and disposal, and there is a concern that it may affect the surrounding environment. It is not easy to handle.
  • the positive electrode is arranged on the outside of the battery cell, and the negative electrode that does not need to come into contact with air is arranged on the inside of the battery cell. Therefore, a housing for accommodating the positive electrode such as powder carbon is required. Yes, the structure of the battery cell was complicated.
  • the present invention has been made in view of the above circumstances, and an object of the present invention is to provide a technique capable of easily handling an air battery.
  • the air battery of one aspect of the present invention is an air battery in which oxygen in the air is used as a positive electrode active material, and is three-dimensional by having a plurality of nanostructures integrated with a cylindrical negative electrode which is a metal having branches.
  • a positive electrode composed of a co-continuum having a network structure and a separator arranged between the positive electrode and the negative electrode and absorbing an electrolytic solution are provided, and the positive electrode is formed of the negative electrode via the separator.
  • the negative electrode Arranged inside, the negative electrode has an open hole that reaches the separator and constitutes the housing of the air battery.
  • the method for manufacturing a positive electrode of an air battery is a method for manufacturing a positive electrode of an air battery using oxygen in the air as a positive electrode active material.
  • a positive electrode composed of a co-continuum having a three-dimensional network structure due to the plurality of nanostructures having branches, a separator arranged between the positive electrode and the negative electrode and absorbing an electrolytic solution, and a separator.
  • the positive electrode is arranged inside the negative electrode via the separator, the negative electrode has an opening hole reaching the separator, constitutes a housing of the air battery, and the positive electrode is the nano. It is produced by a step of freezing a sol or gel in which a structure is dispersed and a step of drying the frozen frozen body in a vacuum.
  • the method for manufacturing a positive electrode of an air battery is a method for manufacturing a positive electrode of an air battery using oxygen in the air as a positive electrode active material.
  • a positive electrode composed of a co-continuum having a three-dimensional network structure due to the plurality of nanostructures having branches, a separator arranged between the positive electrode and the negative electrode and absorbing an electrolytic solution, and a separator.
  • the positive electrode is arranged inside the negative electrode via the separator, the negative electrode has an opening hole reaching the separator, constitutes a housing of the air battery, and the positive electrode is a predetermined positive electrode.
  • FIG. 1 is a configuration diagram showing the configuration of an aluminum-air battery.
  • FIG. 2 is a flowchart showing a positive electrode manufacturing method 1.
  • FIG. 3 is a flowchart showing the positive electrode manufacturing method 2.
  • FIG. 4 is a flowchart showing the positive electrode manufacturing method 3.
  • FIG. 5 is a flowchart showing the positive electrode manufacturing methods 4, 5 and 6.
  • FIG. 6 is a cross-sectional view showing the configuration of a cylindrical aluminum-air battery.
  • FIG. 7 is an external view showing the configuration of the cylindrical aluminum-air battery according to the first embodiment.
  • FIG. 8 is a characteristic diagram showing the initial discharge curve of the cylindrical aluminum-air battery according to the first embodiment.
  • FIG. 9 is an external view showing the configuration of the cylindrical aluminum-air battery according to the second embodiment.
  • FIG. 10 is an external view showing the configuration of the cylindrical aluminum-air battery according to the third embodiment.
  • FIG. 11 is a configuration diagram showing the configuration of the pH measurement cell in Example 8.
  • Air battery configuration In this embodiment, an aluminum-air battery is used as an example of the air battery.
  • FIG. 1 is a configuration diagram showing a configuration of an aluminum-air battery according to an embodiment of the present invention.
  • the aluminum-air battery is an air battery in which oxygen in the air is used as a positive electrode active material.
  • the aluminum air battery of the present embodiment has a positive electrode (air electrode) 1, a negative electrode 2 composed of aluminum, and an electrolyte arranged between the positive electrode 1 and the negative electrode 2. 3 and.
  • the aluminum-air battery of the present embodiment does not need to expose one surface of the positive electrode 1 to the atmosphere.
  • the negative electrode 2 is formed with an opening hole H in which the gas generated in the negative electrode 2 is opened to the atmosphere and oxygen in the air used for the positive electrode reaction in the positive electrode 1 is taken in.
  • the electrolyte 3 may be either an electrolytic solution or a solid electrolyte.
  • the electrolyte solution refers to a case where the electrolyte 3 is in a liquid form.
  • the solid electrolyte means a case where the electrolyte 3 is in a gel form or a solid form.
  • the positive electrode 1 is composed of a co-continuum having a three-dimensional network structure by having a plurality of integrated nanostructures having branches.
  • the co-continuum is a porous body and has an integral structure.
  • Nanostructures are nanosheets or nanofibers. Since a plurality of integrated nanostructures have branches, the co-continuum of the three-dimensional network structure has a stretchable structure in which the branches between the nanostructures can be deformed. There is.
  • the nanosheet may be, for example, one composed of at least one of carbon, iron oxide, manganese oxide, zinc oxide, molybdenum oxide, and molybdenum sulfide.
  • the elements of these materials are 22 kinds of elements (C, O, H, N, P, K, S, Ca, Mg, Fe, Mn, B, Zn, Cu, Mo, Cl, which are indispensable for plant growth. It may be composed of Si, Na, Se, Co, Al, V).
  • the nanofiber may be composed of at least one of carbon, iron oxide, manganese oxide, zinc oxide, magnesium oxide, molybdenum oxide, molybdenum sulfide, and cellulose (carbonized cellulose).
  • the elements of these materials are 16 kinds of essential elements (C, O, H, N, P, K, S, Ca, Mg, Fe, Mn, B, Zn, Cu, Mo, Cl, which are indispensable for plant growth. ) May be used.
  • Nanofibers are fibrous substances having a diameter of 1 nm to 1 ⁇ m and a length of 100 times or more the diameter.
  • the nanofiber may have a hollow shape, a coil shape, or any shape.
  • the nanofiber is composed of cellulose, the cellulose is made conductive by carbonization as described later.
  • a method for manufacturing the positive electrode 1 will be briefly described. For example, first, a sol or gel in which nanostructures are dispersed is frozen to form a frozen body (freezing step), and the frozen body is dried in a vacuum (drying step) to prepare a co-continuum having a positive electrode 1. can do. Any gel in which nanofibers made of iron oxide, manganese oxide, silicon, or cellulose are dispersed can be produced by a predetermined bacterium (gel production step).
  • a co-continuum is obtained by causing a predetermined bacterium to produce a gel in which nanofibers made of cellulose are dispersed (gel production step) and heating this gel in an atmosphere of an inert gas to carbonize it (carbonization step). You may do so.
  • the co-continuum constituting the positive electrode 1 preferably has, for example, an average pore diameter of 0.1 to 50 ⁇ m, and more preferably 0.1 to 2 ⁇ m.
  • the value of this average pore size is a value obtained by the mercury intrusion method.
  • Electrode reaction between positive and negative electrodes The electrode reaction in the positive electrode 1 and the negative electrode 2 will be described.
  • aluminum is used for the negative electrode 2.
  • a reaction that emits n electrons occurs when a negative electrode that becomes an n-valent metal ion is used.
  • the positive electrode reaction, the surface of the positive electrode 1 having conductivity, by oxygen and electrolyte 3 in the air in contact with, the reaction proceeds as indicated by "1 / 2O 2 + H 2 O + 2e - - ⁇ 2OH ⁇ (1) " To do.
  • the reaction represented by the formula (1) proceeds on the surface of the positive electrode 1, so it is considered that it is better to generate a large amount of reaction sites inside the positive electrode 1.
  • the positive electrode 1 can be produced by a known process such as molding carbon powder with a binder. As described above, in the aluminum-air battery, it is important to generate a large amount of reaction sites inside the positive electrode 1, and it is desirable that the positive electrode 1 has a high specific surface area.
  • the specific surface area of the cocontinuum constituting the positive electrode 1 is preferably 200 m 2 / g% or more, and more preferably 300 m 2 / g or more.
  • the conventional positive electrode 1 produced by molding carbon powder with a binder and pelletizing it, when the specific surface area is increased, the bonding strength between the carbon powders decreases and the structure deteriorates. It is difficult to discharge stably, and the discharge capacity decreases.
  • the positive electrode 1 of the present embodiment which is composed of a co-continuum having a three-dimensional network structure by having a plurality of integrated nanostructures having branches, the above-mentioned conventional method.
  • the problem can be solved and the discharge capacity can be increased.
  • the positive electrode 1 For example, on a co-continuous for the positive electrode 1, those of manganese oxide hydrate (MnO 2 ⁇ nH 2 O) was deposited in a highly dispersed as fine particles of nano size (added) by using as the positive electrode 1, It is possible to show excellent battery performance.
  • the content of the catalyst contained in the positive electrode 1 is 0.1 to 70% by weight, preferably 1 to 30% by weight, based on the total weight of the positive electrode 1. By adding the transition metal oxide as a catalyst to the positive electrode 1, the battery performance is greatly improved.
  • the positive electrode 1 and the electrolyte 3 are in contact with each other, and at the same time, oxygen gas in the atmosphere is supplied, and the three-phase interface of the electrolyte-electrode-gas (oxygen) as described above is formed. If the catalyst has high activity at this three-phase interface site, oxygen reduction (discharge) on the electrode surface proceeds smoothly, and the battery performance is greatly improved. At this time, since the catalyst has a strong interaction with oxygen, which is a positive electrode active material, many oxygen species can be adsorbed on its own surface, or oxygen species can be occluded in oxygen vacancies.
  • the positive electrode 1 to which the catalyst is added can be manufactured by the method for manufacturing the positive electrode 1 described later.
  • the negative electrode 2 is composed of a negative electrode active material.
  • This negative electrode active material is composed of a material that can be used as a negative electrode material for an aluminum-air battery. That is, the metal is not particularly limited as long as it is any metal of magnesium, aluminum, calcium, iron and zinc, or an alloy containing these as a main component.
  • the negative electrode 2 may be made of a metal as the negative electrode 2, a metal sheet, or a powder obtained by crimping powder onto a metal foil such as copper.
  • the negative electrode 2 can be formed by a known method.
  • the negative electrode 2 can be manufactured by stacking a plurality of metal magnesium foils and forming them into a predetermined shape.
  • the housing 4 of the aluminum-air battery may be made of a material that is naturally decomposed.
  • the housing 4 may be made of a natural product-based material, a microbial-based material, or a chemically synthesized material.
  • it can be composed of polylactic acid, polycaprolactone, polyhydroxyalkanoate, polyglycolic acid, modified polyvinyl alcohol, casein, modified starch and the like.
  • a chemically synthesized system such as plant-derived polylactic acid is preferable.
  • the shape of the housing 4 is not limited as long as it is a shape obtained by processing biodegradable plastic, and it is sufficient that the housing 4 is provided with an opening hole communicating with the opening hole H of the negative electrode 2.
  • the negative electrode 2 can be used as the housing 4 of the aluminum-air battery. In order to suppress the residue of the components of the aluminum-air battery in the natural environment, it is preferable to use the negative electrode 2 itself as the housing instead of using the housing 4.
  • the electrolyte 3 may be a substance capable of transferring metal ions and hydroxide ions between the positive electrode 1 and the negative electrode 2.
  • an aqueous solution composed of a metal salt containing potassium and sodium, which are abundant on the earth, can be mentioned.
  • This metal salt contains 22 kinds of elements (C, O, H, N, P, K, S, Ca, Mg, Fe, Mn, B, Zn, Cu, Mo, Cl, which are indispensable for plant growth. It may be composed of elements contained in Si, Na, Se, Co, Al, V), seawater, rainwater, and hot springs.
  • Electrolyte 3 is, for example, acetic acid, carbonic acid, citric acid, malic acid, oxalic acid, phosphoric acid, or salts thereof, HEPES (4- (2-hydroxyethyl) -1-piperazineethhanesulphonic acid), chloride salt, pyrophosphoric acid. It may be composed of one or more of a salt and a metaphosphate.
  • Citric acid, malic acid, and oxalic acid are used as fertilizers, and have the function of promoting phosphorus absorption into plants by forming a complex with phosphorus, which is one of the major elements of fertilizer components. Therefore, not only does it have no effect when the electrolyte leaks into the soil, but it also functions as a fertilizer. Therefore, citric acid, malic acid, oxalic acid, or a salt composed of these is particularly preferable to be used for the electrolyte 3.
  • an aromatic anion exchange polymer solid electrolyte having ionic conductivity through which metal ions and hydroxide ions pass, or an inorganic layered compound-based solid electrolyte may be used.
  • the aluminum air battery can include a separator, a battery case, a structural member such as a metal foil (for example, copper foil), and elements required for a general aluminum air battery.
  • a separator is not particularly limited as long as it is a fiber material, but a cellulosic separator made from plant fibers or bacteria is particularly preferable.
  • the positive electrode 1, the negative electrode 2, and the electrolyte 3 obtained by the air electrode manufacturing method described later are suitable, such as a case, together with other necessary elements based on the desired structure of the aluminum-air battery. It can be produced by appropriately arranging it in a container. A conventionally known method can be applied to the manufacturing procedure of this aluminum-air battery.
  • FIG. 2 is a flowchart for explaining the manufacturing method 1 of the positive electrode 1.
  • step S101 a sol or gel in which nanostructures such as nanosheets and nanofibers are dispersed is frozen to obtain a frozen product (freezing step).
  • step S102 the obtained frozen product is dried in vacuum to obtain a co-continuum (drying step).
  • a three-dimensional network structure is used, which is a raw material of an elastic co-continuum having a three-dimensional network structure composed of a plurality of nanostructures integrated by non-covalent bonds. Is the process of maintaining or building.
  • the gel means a gel in which the dispersion medium loses fluidity due to the three-dimensional network structure of the nanostructures which are dispersoids and becomes a solid state. Specifically, it means a dispersion system having a shear modulus of 102 to 106 Pa.
  • the sol means a colloid composed of a dispersion medium and nanostructures that are dispersoids. Specifically, it means a dispersion system having a shear modulus of 1 Pa or less.
  • the dispersion medium of the sol is an aqueous system such as water, or carboxylic acid, methanol, ethanol, propanol, n-butanol, isobutanol, n-butylamine, dodecane, unsaturated fatty acid, ethylene glycol, heptane, hexadecane, isoamyl alcohol, octanol. , Isopropanol, acetone, glycerin and the like, and two or more of them may be mixed.
  • the freezing step of step S101 is performed by, for example, storing a sol or gel in which nanostructures are dispersed in a suitable container such as a test tube and cooling the periphery of the test tube in a cooling material such as liquid nitrogen. It is carried out by freezing the sol or gel contained in the tube.
  • the method of freezing is not particularly limited as long as the dispersion medium of the gel or sol can be cooled below the freezing point, and may be cooled in a freezer or the like.
  • the pores act as cushions during compression or tension, and have excellent elasticity.
  • the strain at the elastic limit of the co-continuum is 5% or more, and further preferably 10% or more.
  • the drying step is a step of taking out a dispersoid (a plurality of fine structures integrated) having a three-dimensional network structure maintained or constructed from the frozen body obtained in the freezing step from the dispersion medium.
  • the degree of vacuum in the drying step varies depending on the dispersion medium used, but is not particularly limited as long as the degree of vacuum is such that the dispersion medium sublimates.
  • the degree of vacuum is preferably 1.0 ⁇ 10 -6 to 1.0 ⁇ 10 -2 Pa. Further, heat may be applied using a heater or the like at the time of drying.
  • the dispersion medium changes from a solid to a liquid, and then from a liquid to a gas, so that the frozen body becomes a liquid state and becomes fluid again in the dispersion medium, and is tertiary of a plurality of nanostructures.
  • the original network structure collapses. Therefore, it is difficult to produce a co-continuum having elasticity by drying in an atmospheric pressure atmosphere.
  • FIG. 3 is a flowchart for explaining the manufacturing method 2 of the positive electrode 1.
  • step S201 a predetermined bacterium is allowed to produce a gel in which nanofibers made of iron oxide, manganese oxide, or cellulose are dispersed (gel production step). A cocontinuum is prepared using the gel thus obtained.
  • the gel produced by bacteria has a basic structure of fibers on the order of nm, and by producing a cocontinuum using this gel, the obtained cocontinuum has a high specific surface area.
  • a gel produced by bacteria since it is desirable that the positive electrode 1 of the aluminum-air battery has a high specific surface area, it is preferable to use a gel produced by bacteria. Specifically, by using a gel produced by bacteria, it is possible to synthesize a positive electrode (cocontinuum) 1 having a specific surface area of 300 m 2 / g or more.
  • Bacterial gel has a structure in which fibers are entwined in a coil or mesh shape, and has a structure in which nanofibers are branched based on the growth of bacteria. Therefore, the co-continuum that can be produced has an elastic limit. Achieves excellent elasticity with a distortion of 50% or more. Therefore, a co-continuum made using a bacterial production gel is suitable for the air electrode of an aluminum-air battery.
  • Bacteria include known ones. For example, Acetbacter xylinum subspecies scrofermenta, Acetactor xylinum ATCC23768, Acetactor xylinum ATCC23769, Acetbacter pasturianus ATCC10245, Acetbacter xylinum ATCC14851, Acetbacter xylinum ATCC11142, Acetbacter xylinum ATCC108 Acetic acid bacteria such as Acetate, Agrobacterium, Resovium, Sarcinia, Pseudomonas, Achromobactor, Alkalinegenes, Aerobacter, Azotobacter, Switzerlandrea, Enterobactor, Clubera, Leptoslix, Galionella , Siderocapsa, thiobacillus, and various mutant strains created by mutating them by a known method using NTG (nitrosoguanidine) or the like may be produced.
  • NTG nitrogen tride
  • the frozen product is frozen in step S202 to obtain a frozen product (freezing step), and the frozen product is dried in vacuum in step S203. It may be allowed to form a co-continuum (drying step).
  • bacterial cellulose which is a component contained in the bacterial production gel, does not have conductivity, when it is used as the positive electrode 1, it is imparted by heat treatment in an inert gas atmosphere and carbonized to impart conductivity.
  • the carbonization step (step S204) is important.
  • the co-continuum carbonized in this manner has high conductivity, corrosion resistance, high elasticity, high specific surface area, and high catalytic activity, and is suitable as the positive electrode 1 of an aluminum-air battery.
  • Carbonization of bacterial cellulose is carried out at 500 ° C. to 2000 ° C., more preferably 900 ° C. in an inert gas atmosphere after synthesizing a co-continuum having a three-dimensional network structure composed of bacterial cellulose by the above-mentioned freezing step and drying step. It may be carbonized by firing at ° C. to 1800 ° C.
  • the gas that does not burn cellulose may be, for example, an inert gas such as nitrogen gas or argon gas. Further, it may be a reducing gas such as hydrogen gas or carbon monoxide gas, or may be carbon dioxide gas. In the present embodiment, a carbon dioxide gas or an inert gas containing carbon dioxide gas, which has an activating effect on the carbon material and can be expected to highly activate the cocontinuum, is more preferable.
  • step S301 the cocontinuum obtained in the above-mentioned production method 1 or production method 2 is impregnated with an aqueous solution of a metal salt serving as a precursor of the catalyst (impregnation step).
  • a metal salt serving as a precursor of the catalyst
  • the stretchable co-continuum containing the metal salt may be heat-treated in step S302 (heating step).
  • the preferred metal of the metal salt to be used is at least one metal selected from the group consisting of iron, manganese, zinc, copper and molybdenum. In particular, manganese is preferred.
  • a conventionally known method can be used to support the transition metal oxide on the cocontinuum.
  • co-continuous body was evaporated to dryness by impregnating an aqueous solution of a transition metal chloride or a transition metal nitrate, a method of hydrothermal synthesis in water (H 2 O) hot high pressure.
  • a precipitation method in which a co-continuum is impregnated with an aqueous solution of a transition metal chloride or a transition metal nitrate, and an alkaline aqueous solution is dropped thereto.
  • sol-gel method in which a cocontinuum is impregnated with a transition metal alkoxide solution and hydrolyzed.
  • the conditions of each method by these liquid phase methods are known, and these known conditions can be applied. In this embodiment, the liquid phase method is desirable.
  • the precursor powder obtained when the above-mentioned amorphous precursor is dried at a relatively low temperature of about 100 to 200 ° C. is in a hydrated state while maintaining an amorphous state.
  • the hydrate of the metal oxide formally means Me x O y ⁇ nH 2 O (where Me means the above metal.
  • the subscripts x and y are the metal and the metal contained in the metal oxide molecule, respectively. It represents the number of oxygen .n can be expressed as representing) the number of moles of H 2 O for 1 mole of metal oxide.
  • the hydrate of the metal oxide obtained by such low temperature drying can be used as a catalyst.
  • Amorphous metal oxide (hydrate) has a large surface area because sintering has hardly progressed, and the particle size is also very small, about 30 nm. This is suitable as a catalyst, and by using this, excellent battery performance can be obtained.
  • the crystalline metal oxide exhibits high activity, but the metal oxide crystallized by the heat treatment at a high temperature as described above may have a significantly reduced surface area, and the particle size may be significantly reduced due to the aggregation of the particles. May be about 100 nm.
  • the particle size (average particle size) is a value obtained by magnifying and observing with a scanning electron microscope (SEM) or the like and measuring the diameter of the particles per 10 ⁇ m square (10 ⁇ m ⁇ 10 ⁇ m) to obtain an average value. ..
  • manufacturing method 4 manufacturing method 5, and manufacturing method 6 may be used.
  • FIG. 5 is a flowchart for explaining the manufacturing methods 4, 5 and 6 of the positive electrode 1.
  • the catalyst is supported on the co-continuum produced as described in the production method 1 and the production method 2.
  • the following catalyst-supporting step of supporting the catalyst is added.
  • the co-continuum is immersed in an aqueous solution of the surfactant, and the surfactant is attached to the surface of the co-continuum.
  • the co-continuum to which the surfactant is attached may be impregnated with an aqueous solution in which a metal salt is dissolved. If necessary, an alkaline aqueous solution may be added dropwise to the co-continuum containing (adhering) the obtained metal salt. These treatments allow the metal or metal oxide precursor to adhere to the co-continuum.
  • the catalyst made of the metal constituting the metal salt is supported on the co-continuum by heat treatment on the co-continuum to which the metal salt is attached.
  • the catalyst is made into a hydrate of a metal oxide by allowing the catalyst-supported co-continuum to act on high-temperature and high-pressure water.
  • the metal is a metal oxide composed of at least one metal among iron, manganese, zinc, copper and molybdenum, or at least one metal among calcium, iron, manganese, zinc, copper and molybdenum.
  • manganese or manganese oxide (MnO 2 ) is preferable.
  • an aqueous solution of a metal or a metal salt as a precursor of a metal oxide to be finally used as a catalyst is attached (supported) to the surface of the co-continuum.
  • an aqueous solution in which the above metal salt is dissolved may be prepared separately and the cocontinuum may be impregnated with this aqueous solution.
  • the impregnation conditions and the like are the same as those in the prior art as described above.
  • the hydrate of the metal oxide is brought into a state of being attached to the cocontinuum.
  • the metal-adhered co-continuum obtained in the second catalyst-supporting step of the production method 5 is immersed in high-temperature and high-pressure water, and the adhered metal is hydrated with a metal oxide. Converts to a catalyst consisting of.
  • a co-continuum to which a metal is attached is immersed in water at 100 ° C. to 250 ° C., more preferably 150 ° C. to 200 ° C., and the attached metal is oxidized to form a hydrate of a metal oxide. Just do it.
  • the boiling point of water under atmospheric pressure (0.1 MPa) is 100 ° C.
  • the pressure By increasing the pressure to, for example, about 10 to 50 MPa, preferably about 25 MPa, the boiling point of water rises in the closed container, and liquid water of 100 ° C. to 250 ° C. can be realized.
  • the metal By immersing the cocontinuum to which the metal is attached in the high-temperature water thus obtained, the metal can be made into a hydrate of a metal oxide.
  • the manufacturing method 6 of the positive electrode 1 will be described.
  • the catalyst is supported on the co-continuum produced as described in the production methods 1 and 2 by a method different from that of the production methods 4 and 5 described above.
  • the following catalyst-supporting step of supporting the catalyst is added.
  • the process up to the second catalyst supporting step is performed, and the third catalyst supporting step is not performed.
  • the co-continuum is immersed in an aqueous solution of the metal salt to attach the metal salt to the surface of the co-continuum.
  • the co-continuum to which the metal salt is attached is allowed to act on high-temperature and high-pressure water to obtain a catalyst composed of a hydrate of a metal oxide made of a metal constituting the metal salt. It is carried on a co-continuum.
  • the metal may be at least one metal of iron, manganese, zinc, copper and molybdenum.
  • the first catalyst supporting step in the manufacturing method 6 is the same as the first catalyst supporting step in the manufacturing method 5, and the description thereof is omitted here.
  • the co-continuum to which the precursor is attached is allowed to act on high-temperature and high-pressure water, and then dried at a relatively low temperature of about 100 to 200 ° C.
  • the precursor becomes a hydrate in which water molecules are present in the particles while maintaining the amorphous state of the precursor.
  • the hydrate of the metal oxide obtained by such low temperature drying is used as a catalyst.
  • the co-continuum obtained by each of the above-mentioned production methods 1 to 6 can be formed into a predetermined shape by a known procedure to form a positive electrode 1.
  • the catalyst-unsupported and catalyst-supported co-continuum may be processed into a plate-like body, a sheet, or a powder, and packed in a cylindrical negative electrode 2 described later to form a positive electrode 1.
  • the positive electrode 1 is arranged inside the negative electrode 2 via an electrolyte (separator described later) 3.
  • the positive electrode 1 is composed of, for example, commercially available powder carbon and a co-continuum having a three-dimensional network structure by having a plurality of integrated nanostructures having branches.
  • a positive electrode current collector 11 is provided on the positive electrode 1, and a current collector is taken out from the outside of the housing 4.
  • the positive electrode current collector 11 is composed of a current collector 11a for ensuring continuity with the positive electrode 1 and a current collector 11b for ensuring continuity and as a part of a housing.
  • it is composed of a conductive material such as carbon rod, carbon cloth, and graphite sheet.
  • the negative electrode 2 is a metal, has a cylindrical shape, and has an opening hole H that reaches the electrolyte (separator described later) 3.
  • the opening hole H makes it possible to open the gas generated in the negative electrode 2 to the atmosphere and to take in oxygen used for the positive electrode reaction in the positive electrode 1.
  • the cylindrical negative electrode 2 itself constitutes the housing of the aluminum-air battery.
  • the negative electrode 2 is preferably made of a material that is naturally biodegradable.
  • the positive electrode 1 is cut into a size that fits inside the separator as a roll, and the positive electrode 1 is rolled and packed inside the separator. Further, a carbon rod was inserted as the current collector electrode 11a at the center, and the upper surface of the cylinder was sealed using the carbon cloth of the current collector 11b.
  • thermocompression-bonding biodegradable resin to the carbon cloth in advance in addition to the terminal part the contact resistance of the fibers in the carbon cloth is reduced, and after sealing, it is overlapped with the separator folded on the outside of the cylinder.
  • the biodegradable resin could be infiltrated into the electrolyte 3 and the housing 4, and the seal on the upper surface was fixed in this way.
  • the electrolytic solution was impregnated from one of the open holes H1 of the negative electrode 2 and a discharge test was carried out.
  • a discharge test for the discharge test of the aluminum air battery, a commercially available charge / discharge measurement system (SD8 charge / discharge system manufactured by Hokuto Denko Co., Ltd.) is used, and 0.1 mA / cm 2 is energized at the current density per effective area of the positive electrode 1 to open the circuit. The measurement was performed until the battery voltage dropped from the voltage to 0V.
  • the battery discharge test was carried out in a constant temperature bath at 25 ° C. (atmosphere is a normal living environment). The discharge capacity was expressed as a value per weight of the positive electrode (mAh / g).
  • the discharge curve in Example 1 is shown in FIG.
  • Table 1 shows the discharge capacity of an aluminum-air battery in which a commercially available carbon powder is used for the positive electrode 1 and an aluminum pipe having a perforated open hole H1 is used for the negative electrode 2. Table 1 also shows the results of Examples 2 and 3.
  • Example 1 the average discharge voltage was 0.4 V or more.
  • the discharge capacity was 400 mAh / g or more.
  • the value was larger than that of Comparative Example 1 evaluated for an aluminum-air battery in which powdered carbon (Ketjen Black EC600JD), which will be described later, was used as the positive electrode 1 and an aluminum pipe having no opening hole H1 was used as the negative electrode 2. It is considered that the discharge voltage was improved because the reaction overvoltage of the positive electrode 1, which is the reaction rate-determining factor of the aluminum-air battery, was lowered because oxygen was easily supplied to the positive electrode 1 from the opening hole H1 of the negative electrode 2.
  • a method for manufacturing the notch type negative electrode 2 shown in FIG. 9a will be described.
  • a commercially available metal aluminum pipe was cut out to a length of 50 mm with a pipe cutter, and one part of the aluminum pipe was cut from the lower surface to the upper surface with a snips or the like to prepare an opening hole H2 having a width of about 3 mm.
  • the holes to be drilled by this method can be drilled at any length and at any location as shown in FIG. 9b, but when making two or more cuts, the shape of the housing 4 is maintained. From the second place onward, it is preferable not to cut out from one end of the cylinder to the other, but to leave a part.
  • the housing 4 wound around the negative electrode 2 was wound around the negative electrode 2 and thermocompression bonded in the same manner as in Example 1, and then cuts were made with scissors in accordance with the positions of the cut portions created in Example 2.
  • a method for manufacturing the spiral negative electrode shown in FIG. 10 will be described.
  • a commercially available metal aluminum pipe is cut out to a length of 50 mm with a pipe cutter, and one part of the aluminum pipe is diagonally cut with a width of about 3 mm from the bottom surface to the top surface using a snips, etc., and a spiral type An opening hole H3 was prepared.
  • the housing 4 wound around the negative electrode 2 was wound around the negative electrode 2 and thermocompression bonded in the same manner as in Example 1, and then cuts were made with scissors in accordance with the positions of the cut portions created in Example 3.
  • Example 3 The discharge voltage of the manufactured aluminum-air battery in Example 3 is shown in Table 1 above. In Example 3, the average discharge voltage was 0.7V. The value was higher than when the perforated negative electrode 2 of Example 1 was used or when the notched negative electrode 2 of Example 2 was used. It is considered that such improvement in characteristics is due to an increase in oxygen supply to the positive electrode 1 due to the use of the negative electrode 2 having a larger opening hole.
  • Example 4 Next, Example 4 will be described.
  • the negative electrode 2 can be treated as a housing without providing the housing 4.
  • the aluminum-air battery used in the third embodiment is not provided with a housing.
  • An aluminum-air battery was produced in the same manner as in Example 3, and a discharge test was conducted in the same manner as in Example 1 without providing the housing 4.
  • the aluminum plate 2a cut out according to the inner diameter of the cylinder embedded in the lower surface of the cylinder may come off without the housing 4, and thus may not be provided in the fourth embodiment.
  • Table 2 shows the discharge voltage and the discharge capacity of the manufactured aluminum-air battery in Example 4.
  • Example 4 the actual average discharge voltage was 0.7 V or more.
  • the discharge capacity was 550 mAh / g or more.
  • the discharge voltage did not change and the discharge capacity was improved. This means that the contact area between the negative electrode 2 and the positive electrode 1 does not change depending on the presence or absence of the housing 4, indicating that it is not necessary to press the negative electrode 2 with the housing 4.
  • the reason why the discharge capacity is increased is that the elimination of the housing 4 prevents the electrolytic solution from entering the narrow gap generated between the housing 4 and the negative electrode 2 due to the capillary phenomenon, and is used for the battery reaction. It is considered that this is because the elution (corrosion) of the negative electrode 2 could be suppressed. By eliminating the housing 4 in this way, Al can be used more effectively for the battery reaction without changing the voltage.
  • Example 5 Based on the results of Example 4, from Example 5 onward, the constituent materials of the aluminum-air battery will be examined without using the housing 4.
  • Example 5 a co-continuum having a three-dimensional network structure composed of a plurality of nanosheets and nanofibers integrated by non-covalent bonds is used as the positive electrode 1.
  • the positive electrode 1 was synthesized as follows. In the following description, as a representative, a manufacturing method using graphene as a nanosheet and a manufacturing method using carbon nanofibers as nanofibers will be shown. By changing graphene and carbon nanofibers to nanosheets and nanofibers made of other materials, it is possible to prepare a co-continuum having a three-dimensional network structure. The porosity shown below was calculated by modeling the pores as a cylinder from the pore size distribution obtained by the mercury intrusion method for the co-continuum.
  • the obtained cocontinuum was evaluated by performing X-ray diffraction (XRD) measurement, scanning electron microscope (SEM) observation, porosity measurement, tensile test, and BET specific surface area measurement. It was confirmed by XRD measurement that the co-continuum produced in Example 5 was a carbon (C, PDF card No. 01-075-0444) single phase.
  • the PDF card No. is a card number of PDF (Power Diffraction File), which is a database collected by the International Center for Diffraction Data (ICDD), and the same applies hereinafter.
  • the obtained co-continuum was a co-continuum in which nanosheets (graphene pieces) were continuously connected and had an average pore size of 1 ⁇ m.
  • the BET specific surface area measurement of the co-continuum was measured by the mercury intrusion method, it was 510 m 2 / g.
  • the porosity of the co-continuum was measured by the mercury intrusion method, it was 90% or more.
  • the obtained co-continuum does not exceed the elastic region even when a strain of 20% is applied due to the tensile stress, and is restored to the shape before the stress is applied.
  • Such a graphene co-continuum was cut out with a laser cutter to a size capable of being packed inside the negative electrode 2 described below to obtain a positive electrode 1.
  • Co continuum is produced in the same manner as the positive electrode 1 consisting of nanosheet mentioned above, the raw material in the carbon nanofibers sol [dispersion medium: water (H 2 O), 0.4 wt%, manufactured by Sigma-Aldrich] It was used.
  • the obtained co-continuum was evaluated by XRD measurement, SEM observation, porosity measurement, tensile test, and BET specific surface area measurement. It was confirmed by XRD measurement that the co-continuum produced in Example 5 was a carbon (C, PDF card No. 00-058-1638) single phase. In addition, it was confirmed by SEM observation and mercury intrusion method that the nanofibers were continuously connected to form a co-continuum having an average pore diameter of 1 ⁇ m. Moreover, when the BET specific surface area measurement of the co-continuum was measured by the mercury intrusion method, it was 620 m2 / g. Moreover, when the porosity of the co-continuum was measured by the mercury intrusion method, it was 93% or more. Furthermore, from the results of the tensile test, it was confirmed that the nanofiber co-continuum does not exceed the elastic region even when strain is applied by 40% due to tensile stress, and is restored to the shape before the stress is applied.
  • Table 3 shows nanosheets made of carbon (C), iron oxide (Fe 2 O 3 ), manganese oxide (MnO 2 ), zinc oxide (ZnO), molybdenum oxide (MoO 3 ), molybdenum sulfide (MoS 2 ), and carbon (MoS 2).
  • the discharge capacity of the aluminum air cell set to 1 is shown.
  • the discharge capacity was 600 mAh / g or more, which was a larger value than that of Example 4 evaluated for the positive electrode 1 using powdered carbon.
  • the surface area is high, so it is considered that the discharge capacity was improved by the efficient precipitation of the discharge product [Al (OH) 3]. Be done.
  • the iron bacterium Leptothrix ochracea was put into a JOP liquid medium in a test tube together with iron small pieces (purity 99.9% or more, manufactured by the Institute of High Purity Chemistry), and 20 with a shaker. The cells were cultured at ° C for 14 days.
  • the JOP liquid medium contained 0.076 g of disodium hydrogen phosphate dodecahydrate, 0.02 g of potassium dihydrogen phosphate dihydrate, and HEPES [4- (2-hydroxyethyl) -1-piperazine essulphonic acid in 1 L of sterile ground water.
  • Example 5 After culturing, small iron pieces were removed, and the obtained gel was washed in pure water for 24 hours using a shaker. In this wash, the pure water was replaced three times. Using the washed gel as a raw material, a co-continuum was prepared in the same manner as in the process shown in Example 5. Then, an aluminum-air battery was prepared in the same manner as the battery manufacturing method shown in Example 1 and the catalyst supporting method shown in Example 6.
  • the obtained co-continuum was evaluated by XRD measurement, SEM observation, porosity measurement, tensile test, and BET specific surface area measurement.
  • the co-continues produced in Example 7 were amorphous Fe 3 O 4 and ⁇ -Fe 2 O 3 (Fe 3 O 4 , PDF card No. 01-075-1372, ⁇ -Fe 2 O 3 , as measured by XRD). It was confirmed that it was a PDF card No. 00-039-1346).
  • nata de coco manufactured by Fujicco
  • Acetobacter xylinum which is an acetic acid bacterium
  • this nata de coco was subsequently shown in the battery manufacturing method shown in Example 4 and Example 6.
  • An aluminum battery was produced in the same manner as in the catalyst carrying method.
  • the bacterial cellulose gel was used, it was dried in a vacuum and then calcined at 1200 ° C. for 2 hours in a nitrogen atmosphere to carbonize the co-continuum, whereby a positive electrode 1 was prepared.
  • Discharge voltage of the aluminum air battery using the iron oxide nanofiber co-continuum produced by iron bacteria in Example 7 as the positive electrode and the aluminum air battery using the co-continuum made of bacterial cellulose nanofibers as the positive electrode 1 It is shown in Table 5 below. Table 5 below also shows the results when other co-continuums were used.
  • Example 7 an aluminum air battery in which a co-continuity having high porosity and elasticity is obtained, and the co-continuity having catalytic activity is used for the positive electrode 1 is discharged. Efficient discharge product [Al (OH) 3 ] precipitation is realized. It is considered that the improvement of the above-mentioned characteristics is due to various improvements according to the present invention.
  • Example 8 In Example 8, the manganese oxide-supported bacterial carbonized cellulose used in Example 7 was used, and the test method for the co-continuum, the preparation of the aluminum-air battery, and the discharge test method were carried out in the same manner as in Examples 4 and 5. To adjust the electrolytic solution, a solution purely dissolved at a concentration of 1 mol / L is used, but magnesium citrate, calcium citrate, calcium carbonate, and calcium oxalate have low solubility in water, so 0.1 mol / L. A solution dissolved in L citric acid was used.
  • a pH meter (manufactured by HORIBA, D-52) was used to measure the pH. As shown in FIG. 11, the battery reaction was allowed to proceed in the beaker cell 22 filled with the electrolytic solution 21, and the pH before and after the reaction was measured.
  • the positive electrode 1 and the negative electrode 2 were adjusted by cutting out into a circle having a diameter of 14 mm with a punching blade, a laser cutter, or the like. First, the peripheral edge of the copper mesh foil 23 (manufactured by MIT Japan) was stopped by spot welding, and the positive electrode 1 was installed inside the copper mesh foil 23. Similarly, the negative electrode 2 made of an aluminum plate was also fixed in the copper mesh foil 24 (manufactured by MIT Japan) by spot welding.
  • Copper ribbons 25 and 26 are fixed to these in advance by spot welding.
  • a charge / discharge measurement system (SD8 charge / discharge system manufactured by Hokuto Denko Co., Ltd.) is connected to the copper ribbons 25 and 26, and 0.1 mA / cm 2 is energized at a current density per effective area of the positive electrode 1 from the open circuit voltage. Current was applied until the battery voltage dropped to 0V.
  • Example 8 when a salt was used as the electrolyte, the discharge capacity was 1100 mAh / g or more. Some salts, as in Examples 1-7, showed higher values than when potassium chloride was used as the electrolyte. In particular, the discharge capacity of the salt containing no magnesium ion was large.
  • Example 8 the discharge capacity can be improved by using a salt that does not contain chloride ion, magnesium ion, or calcium ion. Further, since the electrolytic solution used in Example 8 is a component used for fertilizer and the like, it is a preferable electrolytic solution from the viewpoint of environmental load. It is considered that the improvement of the above-mentioned characteristics is due to various improvements according to the present invention.
  • Example 9 Next, Example 9 will be described.
  • Example 9 As shown in Table 7, in Example 9, the average discharge voltage was 1.16V. Although it was lower than that of Example 6, it was shown that it works without problems even in a soil environment. When the aluminum-air battery of Example 9 was left in the soil after being discharged, it completely disappeared about one month after the start of the discharge test.
  • Comparative Example 1 a cylindrical aluminum-air battery was produced by using a negative electrode having no open holes in the positive electrode similar to that in Example 1. The conditions for the battery discharge test are the same as in Example 1. The average discharge voltage of the aluminum-air battery according to Comparative Example 1 is as shown in Table 1.
  • the average discharge voltage of Comparative Example 1 was 0.20 V, which was smaller than that of Example 1. Further, when the positive electrode 1 of Comparative Example 1 was observed after the measurement, the positive electrode in the separator was completely submerged. Further, the hydrogen generated from the negative electrode 2 due to the contact with the electrolytic solution creates a gap between the separator and the negative electrode 2, and the negative electrode portion not in contact with the separator is not used for the battery reaction, so that the reaction area is reduced. It was found that it not only became the resistance of the battery, but also caused the capacity to decrease.
  • a plurality of nanostructures in which the positive electrode 1 is integrated are configured as a co-continuum having a three-dimensional network structure by having branches, and the negative electrode 2 is configured as a housing of an air battery. Since the negative electrode 2 is formed with an opening hole, it is possible to realize an air battery that can be easily handled while making it possible to increase the discharge capacity and the discharge voltage.
  • the positive electrode 1 since the positive electrode 1 has a catalyst, it is possible to realize an air battery that can be easily handled while making it possible to further increase the discharge capacity and the discharge voltage.
  • Positive electrode (air electrode) 11a Collector electrode 11b: Current collector 2: Negative electrode 2a: Aluminum plate 3: Electrolyte 4: Housing 11: Positive electrode Current collector 21: Electrolyte 22: Beaker cell 23, 24: Copper mesh foil 25, 26: Copper ribbon

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPWO2023233522A1 (https=) * 2022-05-31 2023-12-07
EP4343930A4 (en) * 2021-07-02 2024-10-30 Mitsubishi Heavy Industries, Ltd. Metal-air battery system

Families Citing this family (1)

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CN116314855B (zh) * 2023-05-15 2023-09-15 安徽大学 一种锌空气电池、锌空气电池制备方法及装置

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5692365U (https=) * 1979-12-18 1981-07-23
JP2011253789A (ja) * 2010-06-04 2011-12-15 Hitachi Zosen Corp 金属空気電池
JP2017117524A (ja) * 2015-12-21 2017-06-29 日本電信電話株式会社 リチウム空気二次電池用空気極およびその製造方法並びにリチウム空気二次電池

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7157171B2 (en) * 2003-05-09 2007-01-02 Nanotek Instruments, Inc. Metal-air battery with programmed-timing activation
WO2018003724A1 (ja) * 2016-07-01 2018-01-04 日本電信電話株式会社 電池およびその正極の製造方法

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5692365U (https=) * 1979-12-18 1981-07-23
JP2011253789A (ja) * 2010-06-04 2011-12-15 Hitachi Zosen Corp 金属空気電池
JP2017117524A (ja) * 2015-12-21 2017-06-29 日本電信電話株式会社 リチウム空気二次電池用空気極およびその製造方法並びにリチウム空気二次電池

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP4343930A4 (en) * 2021-07-02 2024-10-30 Mitsubishi Heavy Industries, Ltd. Metal-air battery system
JPWO2023233522A1 (https=) * 2022-05-31 2023-12-07

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