WO2018131578A1 - Batterie au nickel-magnésium - Google Patents

Batterie au nickel-magnésium Download PDF

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Publication number
WO2018131578A1
WO2018131578A1 PCT/JP2018/000226 JP2018000226W WO2018131578A1 WO 2018131578 A1 WO2018131578 A1 WO 2018131578A1 JP 2018000226 W JP2018000226 W JP 2018000226W WO 2018131578 A1 WO2018131578 A1 WO 2018131578A1
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Prior art keywords
magnesium
nickel
negative electrode
positive electrode
battery
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PCT/JP2018/000226
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English (en)
Japanese (ja)
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幸信 森
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幸信 森
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Publication of WO2018131578A1 publication Critical patent/WO2018131578A1/fr

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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
    • H01M12/00—Hybrid cells; Manufacture thereof
    • H01M12/08—Hybrid cells; Manufacture thereof composed of a half-cell of a fuel-cell type and a half-cell of the secondary-cell type
    • 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
    • H01M4/46—Alloys based on magnesium or aluminium
    • 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
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • 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
    • 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 a nickel-magnesium battery. More specifically, the present invention includes a positive electrode made of nickel oxide, a negative electrode made of a magnesium alloy, a separator provided between the positive electrode and the negative electrode, and an alkaline electrolyte. Relates to a nickel-magnesium battery characterized in that it comprises a ligand chelating magnesium ions.
  • NiCd batteries lithium-ion secondary batteries with higher electric capacity were developed, so they lost their share in the field of portable devices, but in the field of dry batteries, they have become mainstream instead of NiCd batteries.
  • larger nickel / hydrogen rechargeable batteries have been developed, and a Ni—H 2 type that stores hydrogen in a high-pressure tank and supplies hydrogen to the cathode is being studied.
  • a nickel-hydrogen rechargeable battery for vehicle use has a small volumetric energy density, there is a problem that the shape of the battery becomes large when obtaining a large capacity of electricity.
  • the reason why the nickel-hydrogen rechargeable battery is used as a drive power source for the motor of an automobile is that there is less risk of explosion than the lithium ion rechargeable battery described later.
  • the biggest drawback of nickel-hydrogen rechargeable batteries is that a memory phenomenon occurs in which the voltage temporarily drops during discharging when added to a nickel-hydrogen storage battery. It must be recharged after being discharged.
  • Lithium ion secondary batteries use lithium transition metal composite oxides for the positive electrode, carbon materials for the negative electrode, nonaqueous electrolytes such as organic solvents for the electrolyte, and lithium ions move between the positive electrode and the negative electrode for charging and discharging. Is what you do.
  • the strengths of lithium-ion secondary batteries are twice the weight energy density (100 to 243 Wh / kg) and three times the volume energy density (250 to 676 Wh / L) of nickel / hydrogen batteries. In the field of appliances, nickel-metal hydride batteries were dominant. However, since the energy density is high, abnormal heat is generated during charging, and even an ignition accident has occurred.
  • magnesium hydroxide forms a passive state on the surface of the magnesium electrode and stops power generation.
  • the present invention has been made to solve such problems, and the object of the present invention is to have a larger electric capacity than a conventional lithium ion secondary battery, which can be miniaturized, and a lithium secondary battery. It is to provide a safer nickel-magnesium battery.
  • the nickel-magnesium battery of the present invention which has been made to achieve the above object, comprises a positive electrode made of nickel oxide, a negative electrode made of a magnesium alloy, a separator provided between the positive electrode and the negative electrode, and a positive electrode and a negative electrode. It consists of an alkaline electrolyte filled in between, and the electrolyte contains a ligand that forms a chelate complex with magnesium ions.
  • the ligand is ethylenediaminetetraacetic acid. It is preferable to have a catalyst layer to which fine particles of carbon carrying a noble metal catalyst are attached around the negative electrode.
  • the negative electrode can be a flame retardant magnesium alloy containing calcium.
  • the positive electrode is preferably a porous molded body obtained by sintering nickel hydroxide.
  • An activated carbon layer is preferably formed between the positive electrode and the separator.
  • the nickel-magnesium battery of the present invention prevents the formation of a nonconductor, which was the biggest problem of a magnesium-air battery, by blending a ligand that forms a chelate complex with magnesium in an alkaline electrolyte.
  • a secondary battery having a larger electric capacity than a conventional lithium ion secondary battery can be provided.
  • the battery can be reduced in size, and a battery suitable not only for electric vehicles and hybrid cars but also for artificial satellites and space probes can be provided.
  • the nickel-magnesium battery of the present invention by providing a catalyst layer of carbon fine particles carrying a noble metal catalyst around the negative electrode, hydrogen (H 2 ) generated by the reaction between magnesium of the negative electrode and water of the electrolyte is converted into hydrogen ions ( In order to prevent hydrogen gas from being accumulated in the battery cell by being decomposed into H + ) and electrons (e ⁇ ), the cell can be prevented from expanding and accidents such as liquid leakage can be prevented.
  • the nickel-magnesium battery of the present invention can ensure safety by providing an activated carbon layer between the positive electrode and the separator to buffer the intense oxidation / reduction reaction at the positive electrode and the negative electrode during charging.
  • FIG. 1 is a cross-sectional view of a prismatic nickel-magnesium battery according to an embodiment of the present invention. It is a figure which shows the structure of the chelate complex of magnesium ion by ethylenediaminetetraacetic acid (EDTA).
  • EDTA ethylenediaminetetraacetic acid
  • the present invention drives secondary batteries for various electronic / electrical devices such as mobile phones, digital cameras / videos, portable music players, and dedicated batteries for laptop computers, and motors and interior devices for electric vehicles and hybrid cars.
  • the present invention relates to nickel-magnesium batteries that can be used from dry batteries to artificial satellites and space probes, such as secondary batteries.
  • the nickel-magnesium battery of the present invention can be provided in various shapes to meet the many needs listed above. For example, there are single, single, single, single, single, button, square, box, and other industrial special products.
  • the nickel-magnesium battery of the present invention comprises a positive electrode made of nickel oxide, a negative electrode made of a magnesium alloy, a separator provided between the positive electrode and the negative electrode, and an alkaline electrolyte filled between the positive electrode and the negative electrode. And the electrolyte includes a ligand that forms a chelate with magnesium ions.
  • FIG. 1 is a sectional view of a prismatic nickel-magnesium battery according to an embodiment of the present invention.
  • reference numeral 1 is a nickel-magnesium battery
  • 10 is a positive electrode
  • 20 is a negative electrode
  • 30 is a separator
  • 40 is an electrolyte
  • 50 is a catalyst layer
  • 60 is an activated carbon layer.
  • the positive electrode 10 is a porous molded body made of nickel oxide.
  • electrons (e ⁇ ) generated in the negative electrode 20 move through the cell and react with the electrons (e ⁇ ) and oxygen (O 2 ) in the air at the positive electrode 10.
  • the positive electrode is preferably porous so as to easily absorb oxygen.
  • the nickel oxide used for the positive electrode 10 include nickel hydroxide (Ni (OH) 2 ), nickel oxide hydroxide (NiOOOH), and nickel oxide (NiO).
  • a nickel oxide powder may be put into a mold, pressure-molded, and baked in a sintering furnace. Also, a method of removing the resin by heating and sintering a molded product obtained by injection molding a mixture obtained by melting a synthetic resin and mixing nickel oxide powder can be used.
  • the negative electrode 20 is made of metallic magnesium (Mg), and reacts with the alkaline electrolyte 40 on the surface during discharge to become magnesium ions (Mg 2+ ) and electrons (e ⁇ ). Electrons (e ⁇ ) move toward the positive electrode 10 in the cell.
  • the negative electrode 20 can be made of metallic magnesium (Mg) having a purity of 99% or more, but it is weak and may have insufficient hardness. Therefore, it is usually 2 to 10% aluminum (Al) and about 1%. An alloy mixed with zinc (Zn) is used.
  • the negative electrode 20 is preferably a flame retardant magnesium alloy containing calcium.
  • the amount of calcium mixed is usually about 1 to 5% with respect to the weight of the negative electrode 20. If the calcium content is less than 1% by weight, the effect of disturbing the formation of the passive state may not be sufficiently obtained, and if it exceeds 5%, the electrode may become brittle and may crack.
  • a separator 30 is provided between the negative electrode 20 and the positive electrode 10.
  • the separator 30 is provided to distinguish the negative electrode side from the positive electrode side, and electrons (e ⁇ ) move from the negative electrode side to the positive electrode side during discharging, and electrons (e ⁇ ) move from the positive electrode side to the negative electrode side during charging. To do. For this reason, it is preferable that the separator 30 is a nonpolar porous film.
  • the material used for the separator 30 is a nonwoven fabric made of inorganic fibers such as glass wool, rock wool, sludge wool, polyvinyl alcohol, polyamide, polyacrylonitrile, polyethylene, polypropylene, polystyrene, polyvinyl chloride, polyethylene terephthalate, Woven or non-woven fabrics made from synthetic fibers such as polyurethane, membrane filters made from fluorinated resins such as polytetrafluoroethylene, polyvinylidene fluoride and polyvinyl fluoride, and cellulose acetate, and natural materials such as cellulose.
  • Cotton or Japanese paper can be mentioned. Of these, Japanese paper made of pure cellulose can be preferably used as the separator 30 of the nickel-magnesium battery 1.
  • An electrolyte 40 is filled between the positive electrode 10 and the negative electrode 20.
  • An alkaline aqueous solution is used for the electrolyte 40.
  • An acidic electrolyte reacts with the magnesium (Mg) of the electrode to generate hydrogen (H 2 ) and self-discharge.
  • the alkaline electrolyte 40 may be obtained by dissolving a basic compound in water.
  • the basic substance to be used is not particularly limited as long as the aqueous solution shows alkalinity. However, potassium hydroxide (KOH) or sodium hydroxide (NaOH) is usually used because of its price and availability. The concentration is 0.3-32%.
  • magnesium (Mg) reacts with hydroxide ions (OH ⁇ ) to generate magnesium hydroxide (Mg (OH) 2 ) and electrons (e ⁇ ). Electrons (e ⁇ ) move toward the positive electrode 10, but magnesium hydroxide (Mg (OH) 2 ) has a low water solubility and dissolves only 1.2 mg in 100 mL of water. Mg (OH) 2 ) precipitates out. This becomes passive and the reaction stops. In order to solve this problem, research on an auxiliary agent for dissolving magnesium hydroxide (Mg (OH) 2 ) in water has been conducted, but no practical one has been developed yet. In the present invention, magnesium hydroxide (Mg (OH) 2 ) is not dissolved, but magnesium ions (Mg 2+ ) are isolated as chelate complexes from the electrolyte system to prevent non-conductor formation.
  • the electrolyte 40 of the nickel-magnesium battery 1 of the present invention is characterized by including a ligand that forms a chelate with magnesium ions (Mg 2+ ).
  • a chelate is a bond to a metal ion by a ligand having a plurality of coordination sites (ligand).
  • a compound made of a chelate bond is called a chelate complex.
  • chelate complexes of magnesium ions (Mg 2+) located magnesium ions (Mg 2+) in the center of complex molecules (Mg 2+), to form a complex compound surrounds ligand (ligand) is with shared electrons it .
  • the ligand has a plurality of coordination sites and wraps the metal, it is difficult to separate the metal from the coordinated substance. This is called a chelate effect, and is the principle of isolating magnesium ions (Mg 2+ ) from the electrolyte solution system.
  • Mg 2+ magnesium ions
  • the number of ligands is determined to be 2, 4 or 6 depending on the nature of the metal, and magnesium (Mg) is 6.
  • the structure of the chelate complex of magnesium ions (Mg 2+ ) takes an octahedron.
  • Ethylenediaminetetraacetic acid (EDTA: (HOCOCH 2 ) 2 NCH 2 CH 2 N (CH 2 COOH) 2
  • EDTA Ethylenediaminetetraacetic acid
  • EDTA ethylenediaminetetraacetic magnesium with acetic acid (EDTA) ion (Mg 2+) in FIG. 2
  • a magnesium ion (Mg 2+) is ethylenediaminetetraacetic two nitrogen (N) and four oxygen acid (EDTA) ( Coordinated by O).
  • Ethylenediaminetetraacetic acid (EDTA) is freely soluble in an aqueous alkaline solution.
  • concentration of ethylenediaminetetraacetic acid (EDTA) in the electrolyte of the present invention is 0.5 to 50% by weight, preferably 3 to 30% by weight, more preferably 6 to 24% by weight.
  • EDTA ethylenediaminetetraacetic acid
  • Mg 2+ magnesium ions
  • the concentration of ethylenediaminetetraacetic acid (EDTA) reaches 50% by weight or more, sodium hydroxide (NaOH) or potassium hydroxide (KOH) dissolved in the electrolyte 40 starts to be deposited, so that the function of the electrolyte is lowered. There is a fear.
  • Magnesium (Mg) powder reacts with water to generate hydrogen (H 2 ) violently.
  • Magnesium (Mg) forming the negative electrode 20 does not react violently with the alkaline electrolyte 40 because it is a metal lump, but reacts gently to generate hydrogen (H 2 ). Since the generated hydrogen (H 2 ) stays in the cell, the performance of the battery may be deteriorated. Further, when hydrogen gas accumulates in the cell, the cell may expand and cause liquid leakage.
  • a catalyst layer 50 made of carbon fine particles carrying a catalyst around the negative electrode 20 is preferably formed.
  • the catalyst layer 50 formed around the negative electrode 20 converts hydrogen (H 2 ) generated by the reaction of magnesium (Mg) of the negative electrode 20 and water of the electrolyte 40 into hydrogen ions (H + ) and electrons (e ⁇ ).
  • the hydrogen ions (H + ) react with the hydroxide ions (OH ⁇ ) of the electrolyte 40 to form water (H 2 O), and the electrons (e ⁇ ) move to the positive electrode 10.
  • the catalyst supported on the catalyst layer 50 formed around the negative electrode 20 is one or more selected from catalysts containing noble metals such as platinum (Pt), palladium (Pd), rhodium (Rh), and ruthenium (Ru).
  • the noble metal catalyst may be fine metal particles, or may be a chelate catalyst in which a noble metal catalyst is coordinated.
  • a platinum black catalyst obtained by reducing fine particles (Adams catalyst) of platinum oxide (PtO 2 ) can be preferably used.
  • the catalyst is supported on carbon by, for example, nano-sized in a state where chloroplatinic acid (H 2 PtCl 6 ) or ammonium chloroplatinate ((NH 4 ) 2 PtCl 6 ) is melted in sodium nitrate (NaNO 3 ).
  • the carbon carrying the catalyst is applied to the surface of the negative electrode 20 through water or a liquid having a boiling point of 500 ° C. or less, and near the melting point of the magnesium alloy (500 to 1000 ° C.) in an argon (Ar) or nitrogen (N 2 ) atmosphere. ),
  • the catalyst layer can be fixed on the surface of the negative electrode 20.
  • the amount of catalyst contained in the catalyst layer 50 is about 0.001% of the weight of the negative electrode 20.
  • An activated carbon layer 60 is formed between the positive electrode 10 and the separator 30.
  • the activated carbon layer 60 is a support for maintaining the structure of the cell, and at the same time, a pool of electrons (e ⁇ ) moving from the negative electrode 20.
  • the rate-limiting step of the nickel-magnesium battery 1 of the present invention is to incorporate oxygen (O 2 ) into the positive electrode 10. For this reason, the electrons (e ⁇ ) generated at the negative electrode 20 and moved to the positive electrode 10 wait for the order of oxidation.
  • Activated carbon is a mixture of conductive SP 2 -bonded carbon and non-conductive SP 3 -bonded carbon, and is generally non-conductive. At the end of SP 3 bond type carbon, there are many covalent bond branches that have no bond partner.
  • This unbonded branch is considered to retain the waiting electron (e ⁇ ).
  • the activated carbon layer 60 between the positive electrode 10 and the separator 30 adjusts the amount of electrons (e ⁇ ) supplied to the positive electrode 10 and the negative electrode 20, thereby buffering the intense oxidation / reduction reaction that occurs at the positive electrode 10 and the negative electrode 20 during charging. By doing so, safety can be ensured.
  • Magnesium hydroxide (Mg (OH) 2 ) is converted to a magnesium ion (Mg 2+ ) chelate complex (EDTA-Mg 2+ ) by ethylenediaminetetraacetic acid (EDTA), and the interaction with the ions present in the electrolyte 40 is Extremely small.
  • oxygen (O 2 ) in the atmosphere, water (H 2 O) in the electrolyte, and electrons (e ⁇ ) transferred from the negative electrode 20 are combined to form hydroxide ions (OH ⁇ ). ) Occurs.
  • the positive electrode 10 uses the supplied electron (e ⁇ ), and nickel oxide hydroxide (NiOOH) becomes nickel hydroxide (Ni (OH) 2 ).
  • a chelate complex (EDTA-Mg 2+ ) electrons present are magnesium ions (Mg 2+) is supplied as the (e -) magnesium metal combined with (Mg), and the ethylenediamine had formed a chelate complex (EDTA-Mg 2+) tetraacetic acid (EDTA) is Magnesium ions (Mg) are released to enter a free state.
  • the negative electrode 20 is converted into metallic magnesium (Mg) and hydroxide ions (OH ⁇ ) using electrons supplied with magnesium hydroxide (Mg (OH) 2 ).
  • Positive electrode Nickel hydroxide (made by Sumitomo Metal Mining Co., Ltd .: Nickel powder) was pulverized and dried to form a fine nickel oxide hydroxide powder to create a porous nickel plate.
  • Negative electrode 4% of calcium, 7% of aluminum, 1% of flame retardant magnesium alloy (made by Kurimoto Steel Co., Ltd.) plate (thickness 2.5mm) cut into a rectangle of 950mm length and 1450mm width It was.
  • the catalyst layer chloroplatinic acid (H 2 PtCl 6 ⁇ 6H 2 O: Yoneyama Yakuhin Kogyo Co., Ltd.) Sodium nitrate: melted (NaNO 3 manufactured by Wako Pure Chemical Industries, Ltd.), carbon black (Mitsubishi Chemical Corporation, brand : No. 44), platinum was supported thereon, washed with water to remove nitrate to form platinum oxide (PtO), and immersed in formaldehyde (HCHO: manufactured by Wako Pure Chemical Industries, Ltd.). Platinum black (Pt) was prepared by expanding sales at 60 ° C. for 1 hour and reducing. After applying this suspension to both sides of the negative electrode, the catalyst layer was fixed by heating at 500 ° C. in a nitrogen atmosphere.
  • the negative electrode with the catalyst layer fixed on the separator surface was packaged with handmade Japanese paper (Mino paper) and placed in the center of the positive electrode nickel oxide cell.
  • Electrolyte Dissolve potassium hydroxide manufactured by Wako Pure Chemical Industries, Ltd.
  • EDTA ethylenediaminetetraacetic acid
  • An alkaline electrolyte containing was prepared.
  • Activated carbon manufactured by Kuraray Chemical Co., Ltd., product name: Kuraray Coal (registered trademark), brand: PW, standard particle size: 150 ⁇ m or less
  • Kuraray Coal registered trademark
  • PW standard particle size: 150 ⁇ m or less
  • the nickel-magnesium battery of the present invention has a weight energy density of 515 Wh / kg and a volume energy density of 550 Wh / L, and has a power capacity approximately twice that of a conventional lithium ion secondary battery. .
  • Nickel-magnesium battery 10 Positive electrode 20: Negative electrode 30: Separator 40: Electrolyte 50: Catalyst layer 60: Activated carbon layer

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Inorganic Chemistry (AREA)
  • Battery Electrode And Active Subsutance (AREA)
  • Secondary Cells (AREA)
  • Inert Electrodes (AREA)
  • Hybrid Cells (AREA)

Abstract

L'invention concerne une batterie au nickel-magnésium pouvant être réduite en taille, tout en disposant d'une capacité électrique supérieure à celle des batteries rechargeables au lithium-ion classiques et qui est plus sûre que des batteries rechargeables au lithium. Cette batterie au nickel-magnésium est caractérisée en ce qu'elle est composée d'une électrode positive formée à partir d'un oxyde de nickel, d'une électrode négative formée à partir d'un alliage de magnésium, d'un séparateur disposé entre les électrodes positive et négative, et d'un électrolyte alcalin qui remplit l'espace entre les électrodes positive et négative. Cette batterie au nickel-magnésium est également caractérisée en ce que l'électrolyte contient un ligand qui forme un complexe chélaté avec un ion magnésium. De préférence, le ligand est de l'acide éthylènediaminetétraacétique.
PCT/JP2018/000226 2017-01-11 2018-01-09 Batterie au nickel-magnésium WO2018131578A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2017002789A JP2021073635A (ja) 2017-01-11 2017-01-11 ニッケル−マグネシウム電池
JP2017-002789 2017-01-11

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WO2018131578A1 true WO2018131578A1 (fr) 2018-07-19

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPWO2021166655A1 (fr) * 2020-02-21 2021-08-26
CN114497535A (zh) * 2021-12-30 2022-05-13 贵州梅岭电源有限公司 一种层状结构α-Ni(OH)2正极的镁离子电池及其制备方法

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH08124568A (ja) * 1994-10-19 1996-05-17 Canon Inc 二次電池並びに、その負極材料形成方法及び負極材料の取扱方法
JP2012038666A (ja) * 2010-08-10 2012-02-23 Aqumo Co Ltd マグネシウム電池
JP2015022871A (ja) * 2013-07-18 2015-02-02 トヨタ自動車株式会社 金属空気電池
JP2016110728A (ja) * 2014-12-03 2016-06-20 充 吉川 複数セルを有するマグネシウム空気電池
JP2016131063A (ja) * 2015-01-13 2016-07-21 三鷹光器株式会社 マグネシウム空気電池

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH08124568A (ja) * 1994-10-19 1996-05-17 Canon Inc 二次電池並びに、その負極材料形成方法及び負極材料の取扱方法
JP2012038666A (ja) * 2010-08-10 2012-02-23 Aqumo Co Ltd マグネシウム電池
JP2015022871A (ja) * 2013-07-18 2015-02-02 トヨタ自動車株式会社 金属空気電池
JP2016110728A (ja) * 2014-12-03 2016-06-20 充 吉川 複数セルを有するマグネシウム空気電池
JP2016131063A (ja) * 2015-01-13 2016-07-21 三鷹光器株式会社 マグネシウム空気電池

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPWO2021166655A1 (fr) * 2020-02-21 2021-08-26
JP7362164B2 (ja) 2020-02-21 2023-10-17 国立研究開発法人物質・材料研究機構 Ｍｇ基合金負極材及びその製造方法、並びにこれを用いたＭｇ二次電池
CN114497535A (zh) * 2021-12-30 2022-05-13 贵州梅岭电源有限公司 一种层状结构α-Ni(OH)2正极的镁离子电池及其制备方法

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