WO2024150394A1 - マグネシウム空気電池およびその製造方法 - Google Patents

マグネシウム空気電池およびその製造方法 Download PDF

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WO2024150394A1
WO2024150394A1 PCT/JP2023/000730 JP2023000730W WO2024150394A1 WO 2024150394 A1 WO2024150394 A1 WO 2024150394A1 JP 2023000730 W JP2023000730 W JP 2023000730W WO 2024150394 A1 WO2024150394 A1 WO 2024150394A1
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magnesium
positive electrode
air
electrode
electrolyte
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English (en)
French (fr)
Japanese (ja)
Inventor
博章 田口
政彦 林
正也 野原
匠 大久保
周平 阪本
淳 荒武
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NTT Inc
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Nippon Telegraph and Telephone Corp
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Priority to JP2024569964A priority patent/JPWO2024150394A1/ja
Publication of WO2024150394A1 publication Critical patent/WO2024150394A1/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
    • 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
    • H01M4/00—Electrodes
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • 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
    • H01M4/88—Processes of manufacture
    • 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

  • This disclosure relates to a magnesium-air battery and a method for manufacturing the same.
  • the laws governing chemical substance management include the Chemical Substances Control Law, the Chemical Substances Management Law, the Agricultural Chemicals Control Law, the Air Pollution Prevention Law, the Water Pollution Prevention Law, the Soil Contamination Countermeasures Law, the Waste Disposal Law, the Poisonous and Hazardous Substances Control Law, the Ozone Layer Protection Law, and the Fluorocarbons Recovery and Destruction Law.
  • the classification of substances under the Chemical Substances Control Law includes Type 1 and Type 2 Specified Chemicals, Monitoring Chemicals, and Priority Assessment Chemicals, which are substances with high risks such as long-term toxicity and persistence, while there are also general chemicals, which are general chemicals for which the risks are less of a concern.
  • General chemicals present in the city should not be designated as chemicals that pose environmental concerns under these laws (Non-Patent Documents 1 and 2).
  • Zinc is used as a constituent element in the magnesium alloy of the negative electrode of commercially available magnesium-air batteries, or as the negative electrode material of commercially available dry batteries.
  • zinc is designated as a Class 1 designated chemical substance in the Act on Reporting, etc. of Releases of Chemical Substances and Promotion of Their Management (Non-Patent Documents 3 and 4). It is described that zinc metal, zinc oxide, etc. dissolve in acidic and basic aqueous solutions.
  • next-generation batteries In order to solve the above environmental problems, the research and development of next-generation batteries is being promoted, and one of these is the air battery.
  • air batteries oxygen in the air used as the positive electrode active material is supplied from outside the battery, so the inside of the battery cell can be filled with a metal anode.
  • Metals such as magnesium, aluminum, or zinc can be used for the anode.
  • zinc-air batteries that use zinc for the anode have been commercialized as a power source for hearing aids
  • magnesium-air batteries that use magnesium for the anode are being researched and developed as primary batteries with a low environmental impact (Non-Patent Documents 5 and 6).
  • a fluororesin is used as a binder. Carbon particles alone cannot form and hold a positive electrode, so a fluororesin is used to bind the carbon particles together to form an electric bus and a positive electrode that can also diffuse gas.
  • the positive electrode which is composed of a gas diffusion layer through which air (oxygen) diffuses and a catalyst layer where the reduction reaction of oxygen occurs, the fluororesin allows for a smooth supply of air and plays a role in preventing the intrusion of water from the outside air and the leakage of electrolyte into the outside air.
  • Fluorine and fluorine compounds are designated as hazardous substances under the Soil Contamination Countermeasures Act and the Water Pollution Prevention Act.
  • metals containing lead and indium are used for the negative electrode, which is a material composition that raises concerns about its impact on the natural environment, such as soil contamination.
  • the chlorine contained in sodium chloride which is simply and widely used as an electrolyte, can cause corrosion inside the furnace and become a component of toxic substances such as dioxins when mixed into general waste incineration facilities, etc.
  • a primary battery with low environmental impact that uses a positive electrode that is a bicontinuous body with a three-dimensional network structure without using fluororesin as a binder is promising.
  • a positive electrode that does not have a water-repellent effect is used, there is a concern that a large amount of electrolyte will cause the positive electrode to become submerged in the liquid, resulting in a decrease in battery performance.
  • This disclosure has been made in light of the above circumstances, and the purpose of this disclosure is to provide a battery that is made of materials that have a low environmental impact and that can smoothly supply air even when there is an excess of electrolyte.
  • the magnesium-air battery of one embodiment of the present disclosure comprises a positive electrode composed of an air electrode, a negative electrode composed of magnesium or a magnesium alloy containing one or more of the group consisting of magnesium and iron, calcium, and aluminum, and a separator disposed between the positive electrode and the negative electrode, providing insulation between the positive electrode and the negative electrode and absorbing an electrolyte composed of salt, and at least one of the positive electrode and the separator is coated with a silica-containing material.
  • the manufacturing method of a magnesium-air battery includes the steps of obtaining a positive electrode made of an air electrode, coating the positive electrode with a silica-containing material, obtaining a negative electrode made of magnesium or a magnesium alloy containing at least one of the group consisting of magnesium and iron, calcium, and aluminum, and disposing an electrolyte made of a salt between the positive electrode and the negative electrode, and the air electrode is composed of a co-continuum having a three-dimensional network structure made of a plurality of nanostructures integrated together by non-covalent bonds, and the step of obtaining the positive electrode includes the steps of causing a specific bacterium to produce a sol or gel in which nanofibers of any one of iron oxide, manganese oxide, and cellulose are dispersed, freezing the dispersed sol or gel to obtain a frozen body, and drying the frozen body in a vacuum to obtain the co-continuum.
  • FIG. 1 is a diagram illustrating a magnesium-air battery according to an embodiment of the present disclosure.
  • FIG. 2 is a diagram for explaining the appearance of the magnesium-air battery according to the embodiment.
  • FIG. 3 is a schematic diagram illustrating a cross section of a magnesium-air battery according to an embodiment of the present invention.
  • FIG. 4 is a diagram illustrating the battery voltage and discharge capacity during discharge in the magnesium-air battery according to the embodiment.
  • the magnesium-air battery 100 includes a positive electrode 101, a negative electrode 102, an electrolyte 103, a positive electrode current collector 104, a negative electrode current collector 105, a separator 106, and a housing 110.
  • the positive electrode 101 is composed of a gas diffusion type air electrode for oxygen, etc.
  • the positive electrode 101 is composed of a bicontinuum with a three-dimensional network structure made up of multiple nanostructures that are integrated by non-covalent bonds. No binder, especially no fluororesin, is used in the air electrode.
  • the negative electrode 102 contains magnesium (Mg).
  • the negative electrode 102 may be made of magnesium or a magnesium alloy containing one or more of the group consisting of magnesium and iron (Fe), calcium (Ca), aluminum (Al), etc. However, magnesium alloys containing zinc components such as AZ31 are excluded.
  • the electrolyte 103 is disposed between the positive electrode 101 and the negative electrode 102 and is composed of a salt.
  • the electrolyte 103 is an aqueous solution or gel containing magnesium acetate.
  • the electrolyte 103 is preferably composed only of an aqueous solution or gel containing a salt such as magnesium acetate.
  • the electrolyte 103 may be composed of, for example, an aqueous solution of any of magnesium acetate, potassium chloride, and sodium chloride, or a mixture of these salts. Since the electrolyte 103 is composed of salt, it is easy to dispose of, has no concerns about the impact on the surrounding environment, and is easy to handle.
  • the electrolyte 103 may be either an electrolytic solution or a solid electrolyte.
  • the electrolytic solution refers to the electrolyte 103 in a liquid form.
  • the solid electrolyte refers to the electrolyte 103 in a gel form or a solid form.
  • the solid electrolyte may be enclosed with agar, cellulose, water-absorbing polymer, etc. to have a role of retaining water.
  • the electrolyte 103 does not have to be initially disposed when the magnesium-air battery 100 is not operating as a battery. When operating as a battery, the electrolyte 103 may be supplied, for example, from the outside through the separator 106.
  • a known material can be used for the positive electrode collector 104.
  • a carbon sheet, carbon cloth, Fe, or Al plate can be used for the positive electrode collector 104.
  • a known negative electrode current collector 105 can be used. If a metal is used for the negative electrode 102, a terminal may be taken out directly from the negative electrode 102 without using the negative electrode current collector 105.
  • the separator 106 is disposed between the positive electrode 101 and the negative electrode 102, provides insulation between the positive electrode 101 and the negative electrode 102, and absorbs the electrolyte 103 composed of salt.
  • the separator 106 may be any insulator that has water absorption properties. For example, coffee filters, kitchen paper, or paper can be used for the separator 106. Using a sheet of a material that decomposes naturally while maintaining its strength, such as a cellulose-based separator made from plant fibers, for the separator 106 reduces the environmental impact. Note that the separator 106 does not need to be installed if insulation between the positive and negative electrodes can be guaranteed.
  • the positive electrode 101 is in contact with the positive electrode collector 104.
  • the positive electrode 101 is also exposed to the atmosphere.
  • the positive electrode 101 is in contact with the electrolyte 103 on a surface other than the surface in contact with the positive electrode collector 104.
  • the negative electrode 102 is in contact with the negative electrode current collector 105.
  • the negative electrode 102 is in contact with the electrolyte 103 on a surface other than the surface in contact with the negative electrode current collector 105.
  • a positive electrode current collector 104 and a negative electrode current collector 105 are provided in the embodiment of the present disclosure, but this is not limited to the above. If the strength of the positive electrode 101 and the negative electrode 102 is guaranteed when connected to an external load, the positive electrode current collector 104 and the negative electrode current collector 105 can be omitted.
  • the housing 110 contains the positive electrode 101, the negative electrode 102, and the electrolyte 103.
  • the electrolyte 103 may be contained inside the housing 110 when the magnesium-air battery 100 is in operation.
  • the housing 110 has an air hole that exposes the positive electrode 101 (air electrode) to the atmosphere.
  • a portion of the positive electrode current collector 104 and a portion of the negative electrode current collector 105 are exposed from the housing 110 in order to supply power.
  • the housing 110 can be, for example, a known laminate film type.
  • the housing 110 may be made of any of natural, microbial, and chemically synthesized materials, such as polylactic acid, polycaprolactone, polyhydroxyalkanoate, polyglycolic acid, and modified starch.
  • chemically synthesized materials such as plant-derived polylactic acid are preferable.
  • a 3D printer is used as a processing means for the housing 110.
  • the housing 110 can be molded or cut using a 3D printer or the like, and the shape is not limited.
  • the housing 110 can also be made of paper coated with a resin such as polyethylene used in milk cartons, or agar film.
  • the positive electrode 101 can be made of a conductive material that is used in the positive electrodes of common, well-known metal-air batteries.
  • a typical example is a carbon material, but it is not limited to this.
  • the positive electrode 101 can be made by a known process, such as forming carbon powder with a binder. In a primary battery, it is important to generate a large number of reaction sites inside the positive electrode, and it is desirable for the positive electrode 101 to have a high specific surface area.
  • a bicontinuum having a three-dimensional network structure may be used as the positive electrode 101.
  • a bicontinuum having a three-dimensional network structure for the positive electrode 101, it is not necessary to use a binder, and the discharge capacity can be increased.
  • a cocontinuum for example, multiple nanostructures are integrated together through non-covalent bonds to form a three-dimensional network structure.
  • the cocontinuum is a porous body that has an integrated structure.
  • the nanostructure is a nanosheet or nanofiber.
  • the bonds between the nanostructures are deformable, giving the structure flexibility.
  • a nanosheet is a compound that contains carbon or iron oxide, and is mainly composed of carbon or iron oxide.
  • a nanosheet is composed of at least one of carbon and iron oxide. It is important that the nanosheet is conductive.
  • a nanosheet is defined as a sheet-like material with a thickness of 1 nm to 1 um, and with a planar length and width of 100 times or more the thickness.
  • graphene is an example of a carbon nanosheet.
  • a nanosheet may be rolled or wavy, curved or bent, or of any other shape.
  • Nanofibers are compounds that contain carbon, iron oxide, or cellulose, and are primarily composed of carbon, iron oxide, or cellulose. Nanofibers are composed of at least one of carbon, iron oxide, and cellulose. It is important that nanofibers also have electrical conductivity. Nanofibers are defined as fibrous materials with a diameter of 1 nm to 1 ⁇ m and a length of 100 times or more the diameter. Nanofibers may be hollow or coiled, and may have any shape. As for cellulose, it is made electrically conductive by carbonization, as described later.
  • At least one of the positive electrode 101 and the separator 106 is coated with a silica-containing material.
  • the silica-containing material may be coated with a silane coupling agent.
  • the surface of the positive electrode 101 or the cellulose forming the separator 106 is coated with the silica-containing material by a gas layer method using a silane coupling agent. This allows for a smooth supply of air even when the electrolyte 103 is in an excess state.
  • the interface between the positive electrode 101 and the electrolyte 103 can play a role in preventing the intrusion of water from the outside air and the leakage of the electrolyte into the outside air.
  • the manufacturing method includes a step of obtaining a positive electrode 101 composed of an air electrode, a step of coating the positive electrode 101 with a silica-containing material, a step of obtaining a negative electrode 102 composed of magnesium or a magnesium alloy containing at least one of a group consisting of magnesium and iron, calcium, and aluminum, and a step of disposing an electrolyte 103 composed of a salt between the positive electrode 101 and the negative electrode 102.
  • the positive electrode 101 is composed of a bicontinuum having a three-dimensional network structure composed of a plurality of nanostructures integrated by non-covalent bonds.
  • the process for obtaining the positive electrode 101 includes a production step of causing a specific bacterium with nanostructures to produce a sol or gel in which nanofibers of either iron oxide, manganese oxide, or cellulose are dispersed, a freezing step of freezing the dispersed sol or gel to obtain a frozen body, and a drying step of drying the frozen body in a vacuum to obtain the co-continuum.
  • the co-continuum that serves as the positive electrode 101 may be created by the freezing step of freezing the sol or gel in which the nanostructures are dispersed to obtain a frozen body and the drying step of drying the frozen body in a vacuum to obtain a co-continuum.
  • the positive electrode 101 is composed of the co-continuum obtained in the drying step.
  • the sol or gel has dispersed nanofibers made of any of iron oxide, manganese oxide, silicon, and cellulose, it may be produced by a specific bacterium (sol or gel production process).
  • the process of obtaining the positive electrode 101 includes a production process of producing a sol or gel with dispersed cellulose nanofibers by a specific bacterium, and a carbonization process of heating and carbonizing the sol or gel in an inert gas atmosphere to obtain a co-continuum.
  • the positive electrode 101 is composed of the co-continuum obtained in the carbonization process.
  • the co-continuum constituting the positive electrode 101 preferably has an average pore size of, for example, 0.1 to 50 ⁇ m, and more preferably 0.1 to 2 ⁇ m.
  • the average pore size is a value determined by mercury intrusion porosimetry. In this case, there is no need to use additional materials such as binders as in the case of using carbon powder, which is advantageous in terms of cost and also in terms of the environment.
  • Electrochemical reaction the electrochemical reactions at the positive electrode 101 and the negative electrode 102 will be described taking as an example a primary battery using magnesium metal for the negative electrode.
  • the positive electrode reaction proceeds as shown in "1/2O2 + H2O + 2e- ⁇ 2OH- ... (1)” when oxygen in the air and the electrolyte come into contact with the surface of the conductive positive electrode 101.
  • the negative electrode reaction proceeds as shown in "Mg ⁇ Mg2+ + 2e- ... (2)" at the negative electrode 102 in contact with the electrolyte 103, and the magnesium constituting the negative electrode 102 releases electrons and dissolves into the electrolyte as magnesium ions.
  • the overall reaction is "Mg + 1/2O2 + H2O + 2e- ⁇ Mg(OH)2 ... (3)", which is the reaction that produces (precipitates) magnesium hydroxide.
  • the theoretical electromotive force is approximately 2.7 V.
  • the reaction shown in formula (1) proceeds on the surface of the positive electrode 101, so it is considered better to produce a large number of reaction sites inside the positive electrode 101.
  • the magnesium-air battery 100 is made of materials with low environmental impact and does not pollute waste treatment facilities or the natural environment. Furthermore, the magnesium-air battery 100 is made only of materials that do not contain regulated substances specified by various laws and regulations. Such a magnesium-air battery 100 places an extremely low burden on the living environment and the natural environment, even when used in a disposable device such as a soil moisture sensor, and when it is not collected or is discarded as general waste.
  • At least one of the positive electrode 101 and the separator 106 is coated with a silica-containing material. This allows for a smooth supply of air even when the electrolyte 103 is in excess. Furthermore, the interface between the positive electrode 101 and the electrolyte 103 can serve to prevent the intrusion of water from the outside air and the leakage of the electrolyte into the outside air.
  • Examples 1-1 to 1-4 are examples in which a bicontinuum having a three-dimensional network structure made up of multiple nanosheets bound together by non-covalent bonds is used as an air electrode (positive electrode 101).
  • the magnesium air battery 100a includes a positive electrode 101, a negative electrode 102, an electrolyte 103, a positive electrode current collector 104, a negative electrode current collector 105, a separator 106, a housing 110, a housing cover 111, and a fastener 112.
  • the cathode (air electrode) 101 was synthesized as follows. In the following explanation, a manufacturing method using graphene as a nanosheet is shown as a representative example, but by changing the graphene to a nanosheet of another material, it is possible to prepare a bicontinuum having a three-dimensional network structure.
  • a commercially available carbon nanofiber sol [dispersion medium: water (H 2 O), 0.4 wt %, manufactured by Sigma-Aldrich] was placed in a test tube, and the test tube was immersed in liquid nitrogen for 30 minutes to completely freeze the carbon nanofiber sol. After completely freezing the carbon nanofiber sol, the frozen carbon nanofiber sol was taken out into an eggplant flask, and this was dried in a vacuum of 10 Pa or less using a freeze dryer (manufactured by Tokyo Rikakikai Co., Ltd.), to obtain an elastic bicontinuum having a three-dimensional network structure containing carbon nanosheets.
  • a freeze dryer manufactured by Tokyo Rikakikai Co., Ltd.
  • the obtained co-continuum was evaluated by X-ray diffraction (XRD) measurement, scanning electron microscope (SEM) observation, porosity measurement, tensile test, and BET (Brunauer Emmett Teller) specific surface area measurement.
  • the prepared co-continuum was confirmed to be a single phase of carbon (C, PDF card No. 01-075-0444) by XRD measurement.
  • the PDF card No. is the card number of the PDF (Powder Diffraction File), a database collected by the International Centre for Diffraction Data (ICDD), and the same applies below.
  • the obtained co-continuum was a co-continuum with an average pore size of 1 ⁇ m in which nanosheets (graphene pieces) were continuously connected.
  • the BET specific surface area of the co-continuum was measured by mercury intrusion porosimetry, and it was found to be 510 m 2 /g.
  • the porosity of the co-continuum was measured by mercury intrusion porosimetry and found to be over 90%.
  • the results of a tensile test confirmed that the co-continuum did not exceed its elastic region and restored its shape before the application of stress even when a 20% strain was applied due to tensile stress.
  • the above-mentioned co-continuum was cut into a square shape with a side length of 9 mm using a punching blade or a laser cutter, etc., to obtain a gas diffusion type air electrode (positive electrode 101).
  • the air electrodes of Examples 2-1 to 2-5 and 3-1 to 3-6 are explained below.
  • the molded air electrodes were sealed in the same container and subjected to the gas phase method, in which they were maintained at a specified temperature for a specified time.
  • the reagent used was methyltrimethoxysilane (Tokyo Chemical Industry Co., Ltd.), and the coating process was carried out with silica-containing silica at 100°C for 1 to 24 hours.
  • the positive electrode current collector 104 was made by compressing commercially available carbon paper and a PLA film of about 100 ⁇ m, which was made by melting and laminating PLA (Poly-Lactic Acid) filaments using the FFF (Fused Filament Fabrication) method with a 3D printer, at 180°C for 10 seconds at 5 kPa to integrate them.
  • the positive electrode current collector 104 was processed into a convex shape for connection to an external load. Specifically, the part that contacts the positive electrode 101 was processed into a square shape with one side measuring 10 mm, and the part that connects to the external load was processed into a rectangle measuring 2 mm x 10 mm.
  • the negative electrode 102 was obtained by cutting commercially available magnesium metal (thickness 100 ⁇ m) into a square shape with each side measuring 10 mm using a punching blade or laser cutter.
  • the negative electrode current collector 105 is made of the same material as the negative electrode 102, but is processed into the same shape as the positive electrode current collector.
  • the electrolyte 103 was a solution of magnesium acetate tetrahydrate dissolved in pure water at a concentration of 1 mol/L.
  • Separator 106 is a cellulose-based separator for batteries.
  • the cellulose-based separator for batteries used in Examples 2-1 to 2-8 will be described.
  • the molded air electrode was sealed in the same container and subjected to the gas layer method, which involved maintaining the electrode at a specified temperature for a specified period of time.
  • the reagent used was methyltrimethoxysilane, and the coating process was carried out with a silica-containing solvent at 100°C for 1 to 24 hours, just like the positive electrode.
  • the housing 110 is designed to accommodate each component, with inner dimensions of 10.1 mm square and outer dimensions of 20 mm, with two gaps for the positive and negative electrode collectors for connection to an external load, and one gap at the bottom for the separator to be exposed.
  • the housing lid 111 is a lid for the housing 110.
  • the housing lid 111 fixes the positive electrode collector 104 from above.
  • the housing lid 111 has an air hole 111a for supplying air to the positive electrode collector 104.
  • the fixture 112 is used to fix the positive electrode 101.
  • the fixture 112 has a rectangular shape with inner dimensions of 9 mm and outer dimensions of 10 mm, and is formed so that the positive electrode 101 can be accommodated inside.
  • the housing 110, housing lid 111, and fixture 112 were produced by melting and stacking PLA filament using the FFF (Fused Filament Fabrication) method with a 3D printer.
  • the negative electrode collector 105, the negative electrode 102, and the separator 106 are placed in the housing 110.
  • a part of the negative electrode collector 105 is exposed to the outside of the housing 110 from the gap for the negative electrode collector in the housing 110, and a part of the separator 106 is exposed to the outside of the housing 110 from the gap for the separator provided at the bottom of the housing 110.
  • a fixing device 112 for improving insulation and fixing the positive electrode is placed on the separator 106.
  • the positive electrode 101 is stored inside the fixing device 112, and the positive electrode collector 104 is placed on top of it. At this time, a part of the positive electrode collector 104 is exposed from the gap for the positive electrode collector.
  • the battery material is fixed from above with the housing lid 111, and the housing 110 and the housing lid 111 are fixed using heat generated by vibrations from an ultrasonic cutter or the like.
  • the magnesium-air battery 100a was produced by injecting the electrolyte 103 into the separator 106 exposed to the outside.
  • the battery performance of the prepared magnesium-air battery 100a was measured. First, a discharge test was performed. The discharge test of the air battery was performed using a commercially available charge/discharge measurement system (SD8 charge/discharge system, manufactured by Hokuto Denko Corporation). In the discharge test, a current density of 0.5 mA/ cm2 was applied per effective area of the air electrode, and measurements were performed in a thermostatic chamber at 25°C (atmosphere: normal living environment) until the battery voltage decreased from the open circuit voltage to 0V. The discharge capacity was expressed as a value (mAh/g) per weight of the air electrode made of a bicontinuum.
  • SD8 charge/discharge system manufactured by Hokuto Denko Corporation
  • Example 1-1 The initial discharge curve when the negative electrode is made of magnesium in Example 1-1 is shown in Figure 4.
  • the average discharge voltage is 1.15 V and the discharge capacity is 1200 mAh/g.
  • the average discharge voltage is the battery voltage when the discharge capacity is 1/2 of the battery's discharge capacity.
  • the battery discharge capacity is 1200 mAh/g and the discharge capacity in the experiment is 600 mAh/g.
  • Table 1 shows the results of Examples 1-1 to 1-4, in which only the amount of electrolyte was changed. As the amount of electrolyte increased, the discharge capacity and average discharge voltage decreased. This is presumably because the electrolyte seeped into the positive electrode, reducing the length of the three-phase interface, which is the reaction site at the positive electrode.
  • Table 2 shows the results of Examples 2-1 to 2-8, which used a positive electrode made of an elastic bicontinuum that had been coated with silica-containing electrolyte. It can be seen that all of the batteries 2-1 to 2-4 exhibit average voltages and discharge capacities equal to or greater than those of Example 1-1, which had the same amount of electrolyte. It can also be seen that batteries 2-5 to 2-8, which had an increased amount of electrolyte, had higher battery performance than Examples 1-2 and 1-3.
  • Table 3 shows the results of examples using an elastic bicontinuous positive electrode coated with a silica-containing electrolyte for 6 hours and a separator coated with a silica-containing electrolyte. It can be seen that all of the batteries 3-1 to 3-4 show average voltage and discharge capacity values equal to or greater than those of Examples 1-1 and 2-1, which have the same amount of electrolyte. Also, batteries 3-5 to 3-6, which have an increased amount of electrolyte, show values equal to or greater than those of Examples 1-2, 1-3, 2-5, and 2-7.
  • the magnesium-air battery 100 has an air electrode made of a co-continuum with a three-dimensional network structure consisting of multiple nanostructures that are integrated by non-covalent bonds.
  • a silane coupling agent is applied to the separator 106 and the positive electrode 101 by a gas layer method, and the cellulose and positive electrode surface are coated with silica-containing material.
  • a magnesium-air battery 100 that does not pollute waste treatment facilities or the natural environment and is made only of materials with low environmental impact, without using regulated substances that are of concern for their impact on human health and the environment via the environment.
  • Such a magnesium-air battery 100 can be effectively used as a variety of power sources, including disposable batteries in everyday environments and sensors used in soil.

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PCT/JP2023/000730 2023-01-13 2023-01-13 マグネシウム空気電池およびその製造方法 Ceased WO2024150394A1 (ja)

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