WO2017119494A1 - Composé de magnésium, matériau actif d'électrode positive pour batterie secondaire, batterie secondaire et procédé de production du compose de magnésium - Google Patents

Composé de magnésium, matériau actif d'électrode positive pour batterie secondaire, batterie secondaire et procédé de production du compose de magnésium Download PDF

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WO2017119494A1
WO2017119494A1 PCT/JP2017/000303 JP2017000303W WO2017119494A1 WO 2017119494 A1 WO2017119494 A1 WO 2017119494A1 JP 2017000303 W JP2017000303 W JP 2017000303W WO 2017119494 A1 WO2017119494 A1 WO 2017119494A1
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magnesium
secondary battery
positive electrode
raw material
magnesium compound
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PCT/JP2017/000303
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Japanese (ja)
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タイタス ニャムワロ マセセ
鹿野　昌弘
栄部　比夏里
博 妹尾
光 佐野
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国立研究開発法人産業技術総合研究所
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Priority to JP2017560438A priority Critical patent/JP7060866B2/ja
Publication of WO2017119494A1 publication Critical patent/WO2017119494A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G3/00—Compounds of copper
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G45/00—Compounds of manganese
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G49/00—Compounds of iron
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G51/00—Compounds of cobalt
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G53/00—Compounds of nickel
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/054—Accumulators with insertion or intercalation of metals other than lithium, e.g. with 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
    • H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
    • H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
    • 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
    • H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
    • H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
    • 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 magnesium compound, a positive electrode active material for a secondary battery, a secondary battery, and a method for producing a magnesium compound.
  • Carrier such as calcium secondary battery using Ca 2+ as the carrier, beryllium secondary battery using Be 2+ and carrier, manganese secondary battery using Mn 2+ as the carrier, nickel secondary battery using Ni 2+ and careers, Zn 2+ Zinc secondary battery, Yt + secondary battery using Y 3+ as a carrier, Al secondary battery using Al 3+ as a carrier, Magnesium secondary battery using Mg 2+ as a carrier, and the like. Recently, research on magnesium secondary batteries has attracted attention.
  • Magnesium has a high theoretical weight and volume capacity, and exhibits a relatively base redox potential. Therefore, a secondary battery using magnesium as a negative electrode is expected to have a high energy density.
  • the theoretical capacity per volume is higher than that of lithium, which is advantageous in that a large capacity can be packed in a limited space (volume) such as a secondary battery for an electric vehicle.
  • the amount of magnesium reserves is abundant in the crust layer, and the problems of resource depletion and cost, which are disadvantages of the lithium ion secondary battery, can be cleared.
  • Magnesium has a melting point of about 650 ° C., which is very high compared to Li (180 ° C.), Na (98 ° C.) and the like.
  • the melting point is an indicator of metal stability.
  • secondary batteries using magnesium can be expected to improve safety.
  • the safety of the negative electrode metal will be a very important factor in view of the practical application of the metal negative electrode.
  • lithium, sodium, and the like are difficult to handle because they react vigorously with moisture in the air, but magnesium is stable in the air and easy to handle.
  • magnesium ion secondary batteries are regarded as candidates for post lithium ion secondary batteries, and many studies have been conducted so far.
  • Non-Patent Document 1 the secondary battery using the Mo 6 S 8 having a Chevrel phase as a positive electrode (including expensive Mo) is to show a stable and reversible charge and discharge characteristics as magnesium ion secondary battery Is disclosed.
  • Multivalent ions have a dramatic increase in Coulomb interaction with anions in the solid phase compared to lithium ions, so the diffusion of polyvalent ions in the positive electrode host compound in the solid phase is slow, greatly limiting the reaction. Can be a factor. Even in a compound containing a soft base such as sulfur ion as disclosed in Non-Patent Document 1, the reaction potential tends to decrease (about 1.1 V), and the chevrel phase has a large molecular weight and a low theoretical capacity ( There was also a problem of about 116 mAhg ⁇ 1 ).
  • the present invention has been made in view of the above, and a novel magnesium compound capable of constructing a magnesium secondary battery having high theoretical capacity, high potential, low cost, and high theoretical energy density, and a positive electrode including the magnesium compound It aims at providing the manufacturing method of an active material and a magnesium compound.
  • the present inventor has found that the above object can be achieved by a magnesium compound having a specific composition, and has completed the present invention.
  • the present invention includes, for example, the subject matters described in the following sections.
  • Item 1 The following general formula (1) Mg a X b Mn c O d (1)
  • X is at least one selected from the group consisting of Fe and Cu. Further, a is 0.5 to 1.5, b is 0.5 to 1.5, c Represents 0.5 to 1.5, and d represents 3.8 to 4.1.
  • the following general formula (2) Mg a Y b Mn c O d (2) (In the formula (2), Y is at least one selected from the group consisting of Fe, Cu, Mn, Co and Ni. Further, a is 0.5 to 1.5, and b is 0.5.
  • Item 3. A secondary battery comprising the positive electrode active material according to Item 2 as a constituent element.
  • Item 4. The method for producing a magnesium compound according to Item 1, comprising: A manufacturing method provided with the heating process which heats the raw material mixture containing the raw material containing Mg, the raw material containing said X, and the raw material containing Mn.
  • Item 5. The production method according to Item 4, wherein the heating temperature in the heating step is 500 to 1500 ° C.
  • the magnesium compound according to the present invention is suitable as a positive electrode active material for constituting a magnesium secondary battery having a high energy density, can make the magnesium ion secondary battery have a high capacity, and can be produced at a low cost. It is a material that can provide a secondary battery.
  • the positive electrode active material for magnesium ion secondary batteries according to the present invention contains the magnesium compound, it is suitable for use in magnesium secondary batteries.
  • the XRD pattern of the product obtained in Example 1 is shown.
  • the XRD pattern of the product obtained in Example 1 (upper stage) and each raw material used in Example 1 (lower stage) is shown.
  • the SEM image of MgFeMnO 4 obtained in Example 1 is shown.
  • the result of the open circuit potential measurement of MgFeMnO 4 obtained in Example 1 is shown.
  • the charge / discharge characteristics when MgFeMnO 4 obtained in Example 1 is used as the positive electrode material, and the relationship between each cycle and the discharge capacity are shown.
  • the result of the potential-time characteristic of all the Mg batteries when using MgFeMnO 4 obtained in Example 1 as a positive electrode material is shown. It shows the results of examining the relationship between the discharge capacity and the cycle of Mg total battery when using the MgFeMnO 4 obtained in Example 1 as a positive electrode material.
  • the XRD pattern of the product obtained in Example 2 is shown. It shows an SEM image of MgCuMnO 4 obtained in Example 2.
  • the charge / discharge characteristics when MgCuMnO 4 obtained in Example 2 is used as the positive electrode material, and the relationship between each cycle and the discharge capacity are shown.
  • the result of the potential-time characteristic of all the Mg batteries when MgCuMnO 4 obtained in Example 2 is used as the positive electrode material is shown.
  • the XRD pattern of the product obtained in Example 3 is shown.
  • the SEM image of the product obtained in Example 4 is shown.
  • the XRD patterns of the products obtained in Examples 4 to 5 are shown.
  • the result of the potential-time characteristic of all the Mg batteries when MgCoMnO 4 obtained in Example 4 is used as the positive electrode material is shown.
  • the SEM image of the product obtained in Example 5 is shown.
  • the XRD pattern of the product obtained in Examples 6 and 7 is shown.
  • the SEM image of the product obtained in Example 6 is shown.
  • the high resolution SEM image of the product obtained in Example 6 is shown.
  • the SEM image of the product obtained in Example 7 is shown.
  • the XRD pattern of the product obtained in Example 8 is shown.
  • the SEM image of the product obtained in Example 8 is shown.
  • the XRD pattern of each compound is shown.
  • the magnesium compound of the present embodiment has the following general formula (1) Mg a X b Mn c O d (1)
  • X is at least one selected from the group consisting of Fe and Cu.
  • A is 0.5 to 1.5
  • b is 0.5 to 1.5
  • c is 0. .5 to 1.5
  • d is 3.8 to 4.1.
  • Such a magnesium compound is useful as a positive electrode active material for a magnesium ion secondary battery because it can insert and desorb magnesium ions.
  • X is any one selected from the group consisting of Fe and Cu.
  • X is any one selected from the group consisting of Fe and Cu.
  • the value of a is more preferably 0.8 to 1.3, and more preferably 0.9 to 1.1, from the viewpoints of easy insertion and desorption of magnesium ions, capacity, and high potential. It is particularly preferred.
  • the value of b is more preferably 0.5 to 1.1, and more preferably 0.8 to 1.1, from the viewpoints of easy insertion and desorption of magnesium ions, capacity, and high potential. It is particularly preferred.
  • the value of b represents the total amount of each of the two types of elements.
  • the value of c is more preferably 0.5 to 1.1, and more preferably 0.8 to 1.1, from the viewpoints of easy insertion and desorption of magnesium ions, capacity, and high potential. It is particularly preferred.
  • the value of d is more preferably 3.8 to 4.0 from the viewpoint of easy insertion and desorption of magnesium ions, capacity, and high potential, and is 3.9 to 4.0. It is particularly preferred.
  • MgFeMnO 4 and MgCuMnO 4 are preferable from the viewpoint of easy insertion and desorption of magnesium ions, low cost, capacity, and high potential. .
  • the valence of X is preferably divalent, and the valence of Mn is preferably tetravalent. That is, the magnesium compound in the general formula (1) is preferably a MgX 2+ Mn 4+ O 4. In this case, insertion and desorption of magnesium ions are likely to occur, and when used as a positive electrode active material for a magnesium ion secondary battery, the magnesium ion secondary battery is likely to have a high capacity and a high potential.
  • the crystal structure of the magnesium compound is not particularly limited.
  • X in the general formula (1) includes at least one selected from the group consisting of Fe and Co
  • the magnesium compound can have a cubic system (Fd-3m space group), so that a spinel structure is formed. It's easy to do. With such a spinel-type magnesium compound, the magnesium ion secondary battery can have a higher capacity when used as a positive electrode active material for a magnesium ion secondary battery.
  • the abundance of the crystal structure as the main phase is not particularly limited, and is preferably 80 mol% or more, more preferably 90 mol% or more based on the entire magnesium compound represented by the general formula (1). .
  • the magnesium compound represented by the general formula (1) can be formed as a material having a single-phase crystal structure.
  • the magnesium compound represented by the general formula (1) may be formed as a material having a plurality of crystal structures as long as the effects of the present invention are not impaired.
  • the crystal structure of the magnesium compound represented by the general formula (1) can be confirmed by X-ray diffraction measurement.
  • the diffraction angles represented by 2 ⁇ are 17.1 to 19.1 °, 29.2 to 31.0 °, 34.4 to 36. 4 °, 36.7-38.4 °, 42.1-44.5 °, 52.6-54.2 °, 56.2-58.2 °, 61.6-63.7 °, 73. It is preferable to have peaks at 1 to 75.4 ° and 78.3 to 79.6 °.
  • the crystal structure of the magnesium compound represented by the general formula (1) can be a spinel structure, and when used as a positive electrode active material for a magnesium ion secondary battery, the capacity of the magnesium ion secondary battery Easy to improve.
  • the magnesium compound represented by the general formula (1) having the crystal structure and composition as described above can be, for example, in the form of a particulate powder.
  • the average particle size is preferably 0.005 to 50 ⁇ m, preferably 0.01 to 0.5 ⁇ m from the viewpoints of easy insertion and desorption of magnesium ions, capacity, and high potential. 2 ⁇ m is more preferable.
  • the average particle diameter of the magnesium compound represented by the general formula (1) is measured by observation with an electron microscope (SEM).
  • SEM electron microscope
  • the average particle diameter here refers to, for example, an arithmetic average value of equivalent circle diameters measured by direct observation with an electron microscope.
  • the positive electrode active material for a secondary battery of the present embodiment has the following general formula (2) Mg a Y b Mn c O d (2)
  • Y is at least one selected from the group consisting of Fe, Cu, Mn, Co and Ni.
  • A is 0.5 to 1.5
  • b is 0.5 to 1.
  • c is 0.5 to 1.5
  • d is 3.8 to 4.1.
  • the positive electrode active material of the present embodiment includes Y as Mn, Co and / or Ni in addition to the above-described magnesium compound (Y in Formula (2) is at least one selected from the group consisting of Fe and Cu). Including some cases.
  • Y is Mn, one Mn and the other Mn have different valences.
  • the value of a is more preferably 0.8 to 1.3, and more preferably 0.9 to 1.1, from the viewpoints of easy insertion and desorption of magnesium ions, capacity, and high potential. It is particularly preferred.
  • the value of b is more preferably 0.5 to 1.1, and more preferably 0.8 to 1.1, from the viewpoints of easy insertion and desorption of magnesium ions, capacity, and high potential. It is particularly preferred.
  • Y includes two or more selected from the group consisting of Fe, Cu, Mn, Co and Ni at the same time, the value of b represents the total amount of each element.
  • the value of c is more preferably 0.5 to 1.1, and more preferably 0.8 to 1.1, from the viewpoints of easy insertion and desorption of magnesium ions, capacity, and high potential. It is particularly preferred.
  • the value of d is more preferably 3.8 to 4.0 from the viewpoint of easy insertion and desorption of magnesium ions, capacity, and high potential, and is 3.9 to 4.0. It is particularly preferred.
  • the magnesium ion secondary battery can have a high capacity.
  • the redox reaction in two steps of Y 2+ / Y 3+ and Y 3+ / Y 4+ occurs, which increases the capacity of the magnesium ion secondary battery.
  • the positive electrode active material of this embodiment is suitable as a positive electrode material constituting a magnesium secondary battery (for example, a magnesium ion secondary battery) having a high energy density.
  • Y is any one selected from the group consisting of Fe and Cu, a magnesium compound can be produced at low cost.
  • Y is at least one selected from the group consisting of Co and Ni, the potential of the secondary battery can be easily improved.
  • the positive electrode active material may contain other materials.
  • the positive electrode active material can also contain inevitable impurities in addition to the magnesium compound. Examples of such inevitable impurities include a raw material mixture described later.
  • the positive electrode active material for a magnesium ion secondary battery about 10 mol% or less, preferably about 5 mol% or less, more preferably 2 mol%. It can be contained to the following extent.
  • the magnesium compound and a carbon material may form a composite.
  • a carbon material suppresses the grain growth of a magnesium compound at the time of baking, it can become a particulate positive electrode active material excellent in electrode characteristics.
  • the content of the carbon material is preferably adjusted so as to be 3 to 40% by mass, particularly 5 to 15% by mass in the positive electrode active material.
  • Method for producing a positive electrode active material represented by magnesium compound represented by the production method above general formula of the magnesium compound (1) and the general formula (2) is not particularly limited.
  • the magnesium compound represented by the general formula (1) by a manufacturing method including a heating step of heating a raw material mixture containing a raw material containing Mg, a raw material containing X, and a raw material containing Mn Can be manufactured.
  • a substance can be produced.
  • the manufacturing method of a magnesium compound is demonstrated concretely.
  • the magnesium compound represented by the general formula (1) is a raw material mixture including a raw material containing Mg, a raw material containing Y, and a raw material containing Mn. It can also be manufactured by a manufacturing method including a heating step of heating
  • the raw material mixture in the said manufacturing method contains the raw material containing Mg, the raw material containing said Y, and the raw material containing Mn.
  • the raw material mixture may be three kinds of mixtures including one raw material containing Mg, one raw material containing Y, and one raw material containing Mn.
  • the raw material containing Mg, the raw material containing Y, and the raw material containing Mn can be one kind or two or more kinds.
  • the raw material mixture can use, as part of the raw material, a compound containing Mg, Y and Mn, or two or more elements at the same time. In this case, the raw material mixture is a mixture of less than three types.
  • the raw material containing Mg may be, for example, metallic Mg or a compound containing Mg element.
  • the compound containing Mg element include magnesium oxide (MgO), magnesium hydroxide (Mg (OH) 2 ), magnesium chloride (MgCl 2 ), magnesium carbonate (MgCO 3 ), and magnesium nitrate (Mg (NO 3 ) 2. ), Magnesium oxalate (MgC 2 O 4 ), magnesium acetate (Mg (CH 3 COO) 2 ) and the like. Hydrate may be sufficient as the compound containing Mg element.
  • the raw material containing Y may be a single metal or a compound containing metal Y.
  • the compound containing metal Y include metal Y oxides, hydroxides, chlorides, carbonates, nitrates, and oxalates.
  • the compound containing metal Y may be a hydrate.
  • Y is Fe, FeC 2 O 4 , if Y is Mn, MnC 2 O 4 , if Y is Ni, Ni (OH) 2 , Y is Co. If there is CoC 2 O 4 and Y is Cu, CuO is exemplified.
  • the raw material containing Mn may be, for example, metal Mn or a compound containing Mn element.
  • the compound containing Mn element include manganese oxide (MnO 2 ), manganese hydroxide (Mn (OH) 2 ), manganese chloride (MnCl 2 ), manganese carbonate (MgCO 3 ), and manganese acetate (Mn (CH 3 COO). 2 ) etc. are exemplified.
  • the compound containing Mn element may be a hydrate.
  • the raw material containing Mn when Y is also Mn, the valence of one Mn is different from the valence of Mn.
  • the raw material containing Mn is manganese oxide (MnO 2 ) containing tetravalent Mn. it can.
  • the raw material mixture does not contain Mg, other metal elements other than the above metals Y and Mn (particularly rare metal elements).
  • other metal elements those that are detached and volatilized by heat treatment in a non-oxidizing atmosphere are desirable.
  • any of the above-described raw materials containing Mg, raw materials containing Y, and raw materials containing Mn may be commercially available products, or may be synthesized separately and used.
  • the shape of the raw material mixture there is no particular limitation on the shape of the raw material mixture, and powder is preferable from the viewpoint of handleability. Further, from the viewpoint of reactivity, the particles are preferably fine, and a powder having an average particle size of 1 ⁇ m or less (particularly about 60 to 80 nm) is preferable. The average particle diameter of each raw material is measured by electron microscope observation (SEM).
  • the raw material mixture can be prepared by mixing the raw material containing Mg, the raw material containing Y, and the raw material containing Mn at a predetermined blending ratio.
  • the mixing method is not particularly limited, and for example, a method that can uniformly mix the raw materials can be employed. Specifically, mortar mixing, mechanical milling treatment, coprecipitation method, a method of mixing after each raw material is dispersed in a solvent, a method of mixing each raw material at once in a solvent, etc. may be adopted. it can. Among these, a magnesium compound can be obtained by a simpler method when mortar mixing is employed. A coprecipitation method can be employed to obtain a more uniformly mixed raw material mixture.
  • the mixing ratio of each raw material in each raw material mixture is not particularly limited. For example, it is preferable to blend each raw material so that a magnesium compound having a desired composition as a final product is obtained. Specifically, it is preferable to adjust the blending ratio of each raw material so that the ratio of each element contained in each raw material is the same as the ratio of each element in the target magnesium compound.
  • the heating step can be performed, for example, in an inert gas atmosphere such as argon or nitrogen. Alternatively, the heating step may be performed under reduced pressure such as vacuum.
  • the heating temperature (that is, the firing temperature) in the heating step is preferably 500 to 1500 ° C.
  • the operation of the heating step can be performed more easily, and the obtained magnesium compound can easily form a spinel structure.
  • the crystallinity and electrode characteristics (particularly capacity and potential) of the obtained magnesium compound are likely to be improved.
  • the lower limit of the heating temperature in the heating step is preferably 700 ° C., particularly preferably 800 ° C., if Y is Fe.
  • the upper limit of heating temperature can be suitably determined in the range which can operate easily in manufacture of a magnesium compound (for example, 1500 degreeC).
  • the lower limit of the heating temperature in the heating step is preferably 500 ° C., more preferably 800 ° C., and 1150 ° C. if Y is Cu, Mn (Mn 2+ ), Co or Ni. Particularly preferred.
  • the upper limit of a calcination temperature can be suitably determined in the range which can perform operation in manufacture of a magnesium compound easily (for example, 1500 degreeC).
  • the heating time in the heating step is not particularly limited, and for example, 10 minutes to 48 hours is preferable, and 30 minutes to 24 hours is more preferable.
  • Y is Cu, Mn (Mn 2+ ), Co or Ni
  • the heating time is preferably 1 hour or longer, more preferably 12 hours or longer, and even more preferably within 24 hours.
  • the desired magnesium compound After heating for a predetermined time, the desired magnesium compound is obtained by cooling. In addition, after cooling once, baking may be performed again at the heating temperature.
  • a magnesium compound can be manufactured by methods other than the said manufacturing method, for example, methods, such as a coprecipitation method, a sol gel method, a hydrothermal synthesis method, and a Pecchini method.
  • Secondary battery includes the above-described positive electrode active material for a secondary battery as a constituent element.
  • the positive electrode active material for a secondary battery is suitable as a component of a magnesium ion secondary battery.
  • the basic structure of the magnesium ion secondary battery can be configured with reference to a known non-aqueous electrolyte magnesium ion secondary battery except that the positive electrode active material for secondary battery is used as the positive electrode active material.
  • the positive electrode, the negative electrode, and the separator can be disposed in the battery container so that the positive electrode and the negative electrode are separated from each other by the separator. Then, after filling the non-aqueous electrolyte into the battery container, the magnesium ion secondary battery can be manufactured by sealing the battery container.
  • the magnesium ion secondary battery may be a magnesium secondary battery.
  • “magnesium ion secondary battery” means a secondary battery using magnesium ions as carrier ions
  • “magnesium secondary battery” means a secondary that uses magnesium metal or a magnesium alloy as a negative electrode active material. Means battery.
  • the positive electrode can adopt a structure in which a positive electrode material containing a positive electrode active material for a secondary battery is supported on a positive electrode current collector.
  • a positive electrode material containing a positive electrode active material for a secondary battery is supported on a positive electrode current collector.
  • it can be produced by applying the positive electrode active material for a secondary battery, a conductive additive, and, if necessary, a positive electrode mixture containing a binder to a positive electrode current collector.
  • conductive aid for example, carbon materials such as acetylene black, ketjen black, carbon nanotube, vapor grown carbon fiber, carbon nanofiber, graphite, and coke can be used.
  • carbon materials such as acetylene black, ketjen black, carbon nanotube, vapor grown carbon fiber, carbon nanofiber, graphite, and coke
  • a powder form etc. are employable.
  • binder examples include fluorine resins such as polyvinylidene fluoride resin and polytetrafluoroethylene.
  • the content of various components in the positive electrode material is not particularly limited and can be appropriately determined.
  • the positive electrode active material for a secondary battery is 50 to 95% by volume (particularly 70 to 90% by volume), the conductive auxiliary agent. Is preferably contained in an amount of 2.5 to 25% by volume (particularly 5 to 15% by volume), and the binder is preferably contained in an amount of 2.5 to 25% by volume (particularly 5 to 15% by volume).
  • Examples of the material constituting the positive electrode current collector include aluminum, titanium, platinum, molybdenum, stainless steel, and copper.
  • Examples of the shape of the positive electrode current collector include a porous body, a foil, a plate, and a mesh made of fibers.
  • the amount of the positive electrode material applied to the positive electrode current collector is preferably determined as appropriate according to the use of the magnesium ion secondary battery.
  • Examples of the negative electrode active material constituting the negative electrode of the magnesium ion secondary battery include magnesium metal; silicon; silicon-containing acrylate compound; magnesium alloy; M 1 M 2 2 O 4 (M 1 : Co, Ni, Mn, Sn, etc. , M 2 : Mn, Fe, Zn, etc.) or a ternary or quaternary oxide; M 3 3 O 4 (M 3 : Fe, Co, Ni, Mn, etc.), M 4 2 O 3 (M 4 : Fe, Co, Ni, Mn, etc.), MnV 2 O 6 , M 5 O 2 (M 5 : Sn, Ti etc.), M 6 O (M 6 : Fe, Co, Ni, Mn, Sn, Cu etc.) Metal oxides represented by, etc .; graphite, hard carbon, soft carbon, graphene; the above-mentioned carbon materials; organic compounds such as MgC 8 H 4 O 4 , MgC 8 H 4 O 4 .2H 2 O, etc.
  • magnesium alloys include alloys containing magnesium and aluminum as constituent elements, alloys containing magnesium and zinc as constituent elements, alloys containing magnesium and manganese as constituent elements, alloys containing magnesium and bismuth as constituent elements, magnesium and nickel Alloy containing magnesium, alloy containing magnesium and antimony as constituent elements, alloy containing magnesium and tin as constituent elements, alloy containing magnesium and indium as constituent elements; metal (scandium, titanium, vanadium, chromium, zirconium, niobium) , molybdenum, hafnium, MXene based alloy containing as constituent elements carbon and tantalum), M 7 x BC 3 alloy (M 7: Sc, Ti, V, Cr, Zr, Nb, Mo, Hf, T Quaternary layered carbide or nitride compound etc.) and the like; alloys containing magnesium and lead as a constituent element thereof.
  • the negative electrode can be composed of a negative electrode active material, and adopts a configuration in which a negative electrode material containing a negative electrode active material, a conductive additive, and a binder as necessary is supported on the negative electrode current collector. You can also. When adopting a configuration in which the negative electrode material is supported on the negative electrode current collector, a negative electrode mixture containing a negative electrode active material, a conductive additive, and a binder as necessary is applied to the negative electrode current collector. Can be manufactured.
  • the negative electrode When the negative electrode is composed of a negative electrode active material, it can be obtained by molding the negative electrode active material into a shape (such as a plate shape) suitable for the electrode.
  • the types of the conductive auxiliary agent and the binder, and the negative electrode active material, the conductive auxiliary agent, and the binder content are those of the positive electrode described above. Can be applied.
  • the material constituting the negative electrode current collector include aluminum, copper, nickel, and stainless steel.
  • Examples of the shape of the negative electrode current collector include a porous body, a foil, a plate, and a mesh made of fibers. In addition, it is preferable to determine suitably the application quantity of the negative electrode material with respect to a negative electrode collector according to the use etc. of a magnesium ion secondary battery.
  • the separator is not limited as long as it is made of a material that can separate the positive electrode and the negative electrode in the battery and can hold the electrolytic solution to ensure the ionic conductivity between the positive electrode and the negative electrode.
  • polyolefin resin such as polyethylene, polypropylene, polyimide, polyvinyl alcohol, terminal aminated polyethylene oxide
  • fluorine resin such as polytetrafluoroethylene
  • acrylic resin nylon
  • aromatic aramid inorganic glass
  • Materials in the form of a membrane, nonwoven fabric, woven fabric, etc. can be used.
  • the non-aqueous electrolyte is preferably an electrolyte containing magnesium ions.
  • an electrolytic solution include a magnesium salt solution, an ionic liquid composed of an inorganic material containing magnesium, and the like.
  • the electrolytic solution may contain a magnesium cation.
  • an electrolytic solution include a solution in which a magnesium salt is dissolved in a solvent, an ionic liquid composed of an inorganic material containing magnesium, and the like, but is not limited to such an example.
  • the magnesium salt include magnesium halides such as magnesium chloride, magnesium bromide and magnesium iodide, magnesium inorganic salts such as magnesium perchlorate, magnesium tetrafluoroborate, magnesium hexafluorophosphate and magnesium hexafluoroarsenate.
  • Magnesium organic salt compounds such as bis (trifluoromethylsulfonyl) imidomagnesium, tris (pentafluoroethane) trifluorophosphate magnesium, magnesium benzoate, magnesium salicylate, magnesium phthalate, magnesium acetate, magnesium propionate, Grignard reagent, etc.
  • the present invention is not limited to such examples.
  • the solvent examples include carbonate compounds such as propylene carbonate, ethylene carbonate, dimethol carbonate, ethylmethyl carbonate, and diethyl carbonate; lactone compounds such as ⁇ -butyrolactone and ⁇ -valerolactone; tetrahydrofuran, 2-methyltetrahydrofuran, diethyl ether, Such as diisopropyl ether, dibutyl ether, methoxymethane, N, N-dimethylformamide, glyme, N-propyl-N-methylpyrrolidinium bis (trifluoromethanesulfonyl) imide, dimethoxyethane, dimethoxymethane, diethoxymethane, dietochiethane, propylene glycol dimethyl ether Ether compounds; acetonitrile and the like.
  • carbonate compounds such as propylene carbonate, ethylene carbonate, dimethol carbonate, ethylmethyl carbonate, and diethyl
  • a solid electrolyte can be used instead of the non-aqueous electrolyte.
  • Example 1 MgO (Wako Chemical, 0.05 ⁇ m, 99.9% (3N)), FeC 2 O 4 .2H 2 O (Pure Chemical, 99.9% (3N)), MnO 2 (rare metallic, 99) .99% (4N)). MgO, FeC 2 O 4 .2H 2 O and MnO 2 were weighed so that the molar ratio of magnesium, iron and manganese was 1: 1: 1 and mixed in an agate mortar for about 30 minutes to obtain a raw material mixture.
  • the raw material mixture was placed in a chrome steel container together with zirconia balls (15 mm ⁇ ⁇ 10), added with acetone, and pulverized and mixed at 400 rpm for 6 hours in a planetary ball mill (Fritsch; P-6). Then, after distilling acetone off under reduced pressure, the recovered powder was formed into pellets at 40 MPa and fired at a firing temperature of 800 ° C. for 1 hour, 2 hours, 4 hours, or 6 hours under an Ar stream. At this time, the temperature raising rate was set to 400 ° C./h. The cooling rate was set to 100 ° C./h up to 300 ° C., and thereafter it was allowed to cool to room temperature by natural cooling. The product obtained after firing was brought into a glove box kept in an Ar atmosphere and stored in an environment without contact with air.
  • Example 2 MgO (Wako Chemical, 0.05 ⁇ m, 99.9% (3N)), CuO (high purity chemistry, 99.99% (4N)), MnO 2 (rare metallic, 99.99% (4N)) ) was used.
  • MgO, CuO and MnO 2 were weighed so that the molar ratio of magnesium, copper and manganese was 1: 1: 1 and mixed in an agate mortar for about 30 minutes to obtain a raw material mixture. Thereafter, the raw material mixture was placed in a chrome steel container together with zirconia balls (15 mm ⁇ ⁇ 10), added with acetone, and pulverized and mixed at 400 rpm for 6 hours in a planetary ball mill (Fritsch; P-6).
  • the recovered powder was formed into pellets at 40 MPa and fired at a firing temperature of 800 ° C. for 1 hour, 2 hours, 4 hours, or 6 hours under an Ar stream.
  • the temperature raising rate was set to 400 ° C./h.
  • the cooling rate was set to 100 ° C./h up to 300 ° C., and thereafter it was allowed to cool to room temperature by natural cooling.
  • the product obtained after firing was brought into a glove box kept in an Ar atmosphere and stored in an environment without contact with air.
  • Example 3 MgO (Wako Chemical, 0.05 ⁇ m, 99.9% (3N)), MnC 2 O 4 (high purity chemistry, 99.9% (3N)) and MnO 2 (rare metallic, 99.99%) as raw material powders (4N)) was used. MgO, MnC 2 O 4 and MnO 2 were weighed so that the molar ratio of magnesium, Mn 2+ and Mn 4+ was 1: 1: 1, and mixed in an agate mortar for about 30 minutes to obtain a raw material mixture.
  • the raw material mixture was placed in a chrome steel container together with zirconia balls (15 mm ⁇ ⁇ 10), added with acetone, and pulverized and mixed at 400 rpm for 6 hours in a planetary ball mill (Fritsch; P-6). Thereafter, acetone was distilled off under reduced pressure, and the recovered powder was pelleted at 40 MPa, and calcined at a calcining temperature of 800 to 1150 ° C. for 3 or 8 hours under Ar flow. At this time, the temperature raising rate was set to 400 ° C./h. The cooling rate was set to 100 ° C./h up to 300 ° C., and thereafter it was allowed to cool to room temperature by natural cooling. The product obtained after firing was brought into a glove box kept in an Ar atmosphere and stored in an environment without contact with air.
  • Example 4 MgO (Wako Chemical, 0.05 ⁇ m, 99.9% (3N)), CoC 2 O 4 (high purity chemistry, 99% (2N)) and MnO 2 (rare metallic, 99.99% (4N) as raw material powders )) was used. MgO, CoC 2 O 4 and MnO 2 were weighed so that the molar ratio of magnesium, cobalt and manganese was 1: 1: 1 and mixed in an agate mortar for about 30 minutes to obtain a raw material mixture.
  • the raw material mixture was placed in a chrome steel container together with zirconia balls (15 mm ⁇ ⁇ 10), added with acetone, and pulverized and mixed at 400 rpm for 6 hours in a planetary ball mill (Fritsch; P-6). Thereafter, acetone was distilled off under reduced pressure, and the recovered powder was pelleted at 40 MPa, and calcined at a calcining temperature of 800 to 1150 ° C. for 3 or 8 hours under Ar flow. At this time, the temperature raising rate was set to 400 ° C./h. The cooling rate was set to 100 ° C./h up to 300 ° C., and thereafter it was allowed to cool to room temperature by natural cooling. The product obtained after firing was brought into a glove box kept in an Ar atmosphere and stored in an environment without contact with air.
  • Example 5 MgO (Wako Chemical, 0.05 ⁇ m, 99.9% (3N)), Ni (OH) 2 (high purity chemistry, 99.9% (3N)) and MnO 2 (rare metallic, 99.99) were used as raw material powders. % (4N)). MgO, Ni (OH) 2 and MnO 2 were weighed so that the molar ratio of magnesium, nickel and manganese was 1: 1: 1 and mixed in an agate mortar for about 30 minutes to obtain a raw material mixture.
  • the raw material mixture was placed in a chrome steel container together with zirconia balls (15 mm ⁇ ⁇ 10), added with acetone, and pulverized and mixed at 400 rpm for 6 hours in a planetary ball mill (Fritsch; P-6). Thereafter, acetone was distilled off under reduced pressure, and the recovered powder was pelleted at 40 MPa, and calcined at a calcining temperature of 800 to 1150 ° C. for 3 or 8 hours under Ar flow. At this time, the temperature raising rate was set to 400 ° C./h. The cooling rate was set to 100 ° C./h up to 300 ° C., and thereafter it was allowed to cool to room temperature by natural cooling. The product obtained after firing was brought into a glove box kept in an Ar atmosphere and stored in an environment without contact with air.
  • Example 6 MgO (Wako Chemical, 0.05 ⁇ m, 99.9% (3N)), CuO (high purity chemistry, 99.99% (4N)), FeC 2 O 4 ⁇ 2H 2 O (pure chemical, 99) .9% (3N)), MnO 2 (rare metallic, 99.99% (4N)).
  • MgO, CuO, FeC 2 O 4 ⁇ 2H 2 O and MnO 2 are weighed so that the molar ratio of magnesium, copper, iron and manganese is 2: 1: 1: 2, and mixed in an agate mortar for about 30 minutes. Thus, a raw material mixture was obtained.
  • the raw material mixture was placed in a chrome steel container together with zirconia balls (15 mm ⁇ ⁇ 10), added with acetone, and pulverized and mixed at 400 rpm for 6 hours in a planetary ball mill (Fritsch; P-6). Then, after distilling acetone off under reduced pressure, the recovered powder was pellet-molded at 40 MPa and fired at a firing temperature of 800 ° C. for 1 hour in an Ar stream. At this time, the temperature raising rate was set to 400 ° C./h. The cooling rate was set to 100 ° C./h up to 300 ° C., and thereafter it was allowed to cool to room temperature by natural cooling. The product obtained after firing was brought into a glove box kept in an Ar atmosphere and stored in an environment without contact with air.
  • Example 7 MgO (Wako Chemical, 0.05 ⁇ m, 99.9% (3N)), Ni (OH) 2 (high purity chemistry, 99.9% (3N)), FeC 2 O 4 .2H 2 O (raw material powder) Pure Chemical, 99.9% (3N)), MnO 2 (rare metallic, 99.99% (4N)) were used.
  • MgO, Ni (OH) 2 , FeC 2 O 4 .2H 2 O and MnO 2 are weighed so that the molar ratio of magnesium, nickel, iron and manganese is 2: 1: 1: 2, and is measured in an agate mortar. The raw material mixture was obtained by mixing for 30 minutes.
  • the raw material mixture was placed in a chrome steel container together with zirconia balls (15 mm ⁇ ⁇ 10), added with acetone, and pulverized and mixed at 400 rpm for 6 hours in a planetary ball mill (Fritsch; P-6). Then, after distilling acetone off under reduced pressure, the recovered powder was pellet-molded at 40 MPa and fired at a firing temperature of 800 ° C. for 1 hour under an Ar stream. At this time, the temperature raising rate was set to 400 ° C./h. The cooling rate was set to 100 ° C./h up to 300 ° C., and thereafter it was allowed to cool to room temperature by natural cooling. The product obtained after firing was brought into a glove box kept in an Ar atmosphere and stored in an environment without contact with air.
  • Example 8 MgO (Wako Chemical, 0.05 ⁇ m, 99.9% (3N)), CuO (high purity chemistry, 99.99% (4N)), Ni (OH) 2 (high purity chemistry, 99.9) % (3N)), MnO 2 (rare metallic, 99.99% (4N)).
  • MgO, CuO, the Ni (OH) 2 and MnO 2, magnesium, copper, the molar ratio of nickel and manganese 2: 1: 1: 2 were weighed so, the raw material mixture is mixed for about 30 minutes in an agate mortar Got.
  • the raw material mixture was placed in a chrome steel container together with zirconia balls (15 mm ⁇ ⁇ 10), added with acetone, and pulverized and mixed at 400 rpm for 6 hours in a planetary ball mill (Fritsch; P-6). Then, after distilling acetone off under reduced pressure, the recovered powder was pellet-molded at 40 MPa and fired at a firing temperature of 800 ° C. for 1 hour under an Ar stream. At this time, the temperature raising rate was set to 400 ° C./h. The cooling rate was set to 100 ° C./h up to 300 ° C., and thereafter it was allowed to cool to room temperature by natural cooling. The product obtained after firing was brought into a glove box kept in an Ar atmosphere and stored in an environment without contact with air.
  • ⁇ Evaluation method> [Powder X-ray diffraction (XRD) measurement]
  • the synthesized sample was measured using an X-ray diffractometer (RINT-UltimaIII / G manufactured by Rigaku Corporation).
  • a CuK ⁇ ray was used as the X-ray source, and the applied voltage was 40 kV and the current value was 40 mA.
  • the measurement was performed at an angle range of 10 ° to 80 ° at a scanning speed of 0.02 ° / sec.
  • ICP-AES measurement ICP-AES measurement was performed using an inductively coupled plasma emission spectrometer (“iCAP6500” manufactured by Thermo Fisher Scientific).
  • the Li box was used as the negative electrode, and the electrolyte used was an electrolyte obtained by dissolving LiPF 6 at a concentration of 1M as a supporting electrolyte in a solvent in which ethylene carbonate (EC) and diethyl carbonate (DEC) were mixed at a volume ratio of 1: 2. .
  • the constant current charge / discharge measurement was started by charging using a voltage switch, setting the current to 10 mAg ⁇ 1 , the upper limit voltage 4.8 V, and the lower limit voltage 1.5 V. Charge / discharge measurement was performed in a state where the cell was placed in a 55 ° C. constant temperature bath.
  • the cell used was a CR2032-type coin cell.
  • the electrolyte solution was prepared by dissolving Mg (TFSI) 2 in ethylene glycol dimethyl ether dimethoxyethylene glycol (trade name: monoglyme) so as to have a concentration of 0.5 M, using the Mg disk as the negative electrode.
  • the constant current charge / discharge measurement was performed by using a voltage switch, setting the current to 5 mAg ⁇ 1 , the upper limit voltage 3.6 V, and the lower limit voltage 0 V, and starting from charge. The measurement was performed at room temperature.
  • FIG. 1 shows the XRD patterns of the products fired at various firing times in Example 1.
  • the firing temperature is 800 ° C.
  • the X-ray wavelength used is 1.5418 mm.
  • FIG. 2 shows a comparison of the XRD pattern of the product (upper stage) obtained by performing the heating process at 800 ° C. for 1 hour in Example 1 and each raw material (lower stage). From the X-ray diffraction pattern of the obtained MgFeMnO 4 , it was found that a single phase of MgFeMnO 4 could be synthesized because no peak derived from the starting material or its related impurity phase was observed.
  • FIG. 3 shows an XRD pattern of MgFeMnO 4 (sintering time is 1 hour) obtained in Example 1 and iron-based manganate compounds (Li 2 FeMnO 4 , LiFeMnO 4 , K 2 FeMnO) containing different cations. 4 ) shows the XRD pattern.
  • the MgFeMnO 4 crystal obtained in Example 1 has a diffraction angle represented by 2 ⁇ of 17.1 to 19.1 °, 29.2 to 31 in an X-ray diffraction pattern by powder X-ray diffraction. 0.0 °, 34.4-36.4 °, 36.7-38.4 °, 42.1-44.5 °, 52.6-54.2 °, 56.2-58.2 °, 61 It can be seen that there are peaks at .6 to 63.7 °, 73.1 to 75.4 °, and 78.3 to 79.6 °.
  • the peak position of MgFeMnO 4 is similar to LiFeMnO 4.
  • the lattice constant of MgFeMnO 4 it can be seen that substantially close to the lattice constant of LiFeMnO 4.
  • MgFeMnO 4 The peak position and intensity of MgFeMnO 4 is because it is similar to Hausmannite type MnFe 2 O 4, MgFeMnO 4 was found to have a spinel structure.
  • FIG. 4 shows an SEM image of MgFeMnO 4 (sintering time is 1 hour) obtained in Example 1.
  • the scale bar indicates 100 nm. It can be seen that the MgFeMnO 4 obtained in Example 1 has an average particle diameter of around 100 nm although the particles tend to aggregate.
  • FIG. 5 shows the result (result of open circuit potential measurement) of Test Example 1 of MgFeMnO 4 (sintering time is 1 hour) obtained in Example 1.
  • the open circuit potential of the MgFeMnO 4 sample was found to be about 3.2V. This is 2.5 Vvs. Since it becomes Mg 2+ , the material obtained in Example 1 can be used as a high potential positive electrode material.
  • FIG. 6 shows the results of Test Example 1 when MgFeMnO 4 (sintering time is 1 hour) obtained in Example 1 was used as the positive electrode material (charge / discharge characteristics and the relationship between each cycle and the discharge capacity). Is shown.
  • the intersection of the discharge curve when the first discharge is performed and the charge curve when the second charge is performed, and the charge curve and the second discharge are performed when the second charge is performed.
  • the point of intersection with the discharge curve at the same time overlaps.
  • the operating potential is 3.2V.
  • the drawable capacity (discharge capacity) is 105 mAhg ⁇ 1 , and it can be seen that even when the charge / discharge cycle is repeated, there is almost no deterioration.
  • FIG. 7 shows the results of Test Example 2 (results of potential-time characteristics of all Mg batteries) when MgFeMnO 4 (sintering time is 1 hour) obtained in Example 1 was used as the positive electrode material. . Initially, it does not work very well, but a potential response is observed suggesting magnesium insertion and removal over time.
  • FIG. 8 shows the results of Test Example 2 when the MgFeMnO 4 (sintering time is 1 hour) obtained in Example 1 was used as a positive electrode material (relationship between each cycle of all Mg batteries and discharge capacity). Result). It can be seen that the capacity that can be extracted increases with the higher cycle, and the discharge capacity is 100 mAhg ⁇ 1 at the 50th cycle.
  • FIG. 9 shows XRD patterns of the products obtained at various firing temperatures in Example 2 (sintering time is 3 hours). The firing time is 1 hour. The X-ray wavelength used is 1.5418 mm.
  • Example 2 the SEM image of MgCuMnO 4 (sintering time is 3 hours) obtained in Example 2 is shown. It can be seen that the MgCuMnO 4 obtained in Example 2 is in the form of particles. In addition, MgCuMnO 4 obtained in Example 2 also has a tendency that the particles are aggregated, but it is understood that the average particle diameter is around 1 to 10 ⁇ m.
  • FIG. 11 shows the results of Test Example 1 (results of open circuit potential measurement) of MgCuMnO 4 (sintering time is 3 hours) obtained in Example 2.
  • the open circuit potential of the MgCuMnO 4 sample was found to be about 3.25V. This is 2.55 Vvs. Since it becomes Mg 2+ , the material obtained in Example 2 can be used as a high potential positive electrode material.
  • FIG. 12 shows the results of Test Example 1 when MgCuMnO 4 (sintering time is 3 hours) obtained in Example 2 was used as the positive electrode material (charge / discharge characteristics, and relationship between each cycle and discharge capacity). Is shown.
  • the intersection of the discharge curve when the first discharge is performed and the charge curve when the second charge is performed, and the charge curve and the second discharge are performed when the second charge is performed.
  • the point of intersection with the discharge curve at the same time overlaps.
  • This result shows that by using the obtained positive electrode material, the charge / discharge reaction can be performed reversibly in charge / discharge after the second cycle.
  • the average operating potential is about 3.0V.
  • the capacity (discharge capacity) that can be extracted in the high-order cycle is 110 mAhg ⁇ 1 , and it can be seen that even when the charge / discharge cycle is repeated, there is almost no deterioration.
  • FIG. 14 shows XRD patterns of the products obtained in Example 3 at various firing temperatures and firing times.
  • the X-ray wavelength used is 1.5418 mm.
  • the 2 ⁇ value is 17.21 to 19.14 °, 28.52 to 28.92 °, 30.57 to 31.84 °, 32.22 to 34.10 °, 35.12 to 37.63 °, 38.01 to 39.99 °, 42.67 to 46.75 °, 49.53 to 52.69 °, 53.88 to 55.27 °, 56.13 to 57 Multiple at .68 °, 58.49 to 59.72 °, 60.08 to 63.73 °, 64.23 to 66.69 °, 67.65 to 71.45 ° or 74.03 to 80.68 ° It can be seen that the main peak of is seen. These peaks, since it corresponds to MgMn 2+ Mn 4+ O 4 single phase, it is understood that MgMn 2+ Mn 4+ O 4 single phase is obtained as the product in Example 3.
  • FIG. 15 shows an SEM image of MgCoMnO 4 (sintering time is 3 hours) obtained in Example 4. It can be seen that MgCoMnO 4 obtained in Example 4 is in the form of particles. Further, as shown in FIG. 15, the average particle diameter is found to be about 1 to 6 ⁇ m.
  • FIG. 16 shows XRD patterns of various products (sintering time is 3 hours) obtained in Examples 4 to 5.
  • the X-ray wavelength used is 1.5418 mm.
  • Example 4 of the single-phase MgCoMnO 4 as product in (MgCo 2+ Mn 4+ O 4) it can be seen that a single phase MgNiMnO 4 (MgNi 2+ Mn 4+ O 4) is obtained as the product in Example 5.
  • FIG. 17 shows the result of Test Example 2 when the MgCoMnO 4 (sintering time is 3 hours) obtained in Example 4 was used as a positive electrode material (relationship between each cycle of all Mg batteries and discharge capacity). Result). It was found that by using MgCoMnO 4 (MgCo 2+ Mn 4+ O 4) as a positive electrode material, a potential response suggesting insertion and desorption of magnesium was observed.
  • MgCoMnO 4 MgCo 2+ Mn 4+ O 4
  • FIG. 18 shows an SEM image of MgNiMnO 4 (sintering time is 3 hours) obtained in Example 5. It can be seen that the MgNiMnO 4 obtained in Example 5 is in the form of particles. Further, as shown in FIG. 18, it can be seen that the average particle diameter is about 1 to 3 ⁇ m.
  • MgFeMnO 4 and MgCoMnO 4 have a cubic crystal system (Fd-3m space group) and the crystal structure forms a spinel structure.
  • FIG. 19 is an XRD pattern of the products obtained in Example 6 (MgCu 0.5 Fe 0.5 MnO 4 ) and Example 7 (MgNi 0.5 Fe 0.5 MnO 4 ). It can be seen that synthesis of a solid solution of MgCu 0.5 Fe 0.5 MnO 4 and MgNi 0.5 Fe 0.5 MnO 4 is made.
  • FIG. 20 shows an SEM image of the product obtained in Example 6.
  • FIG. 21 shows a high-resolution SEM image of the product obtained in Example 6.
  • Example 6 the product (MgCu 0.5 Fe 0.5 MnO 4 ) obtained in Example 6 is in the form of particles.
  • FIG. 22 shows the SEM image of the product obtained in Example 7.
  • FIG. 22 shows that the product (MgNi 0.5 Fe 0.5 MnO 4 ) obtained in Example 7 is in the form of particles.
  • the product (MgCu 0.5 Fe 0.5 MnO 4 ) obtained in Example 6 shows that a solid solution can be formed.
  • FIG. 24 is a SEM-EDX result of the product (MgCu 0.5 Fe 0.5 MnO 4 ) obtained in Example 6. This result shows that in the MgCu 0.5 Fe 0.5 MnO 4 obtained in Example 6, Cu and Fe are equivalent.
  • FIG. 25 shows the SEM image of the product obtained in Example 7.
  • FIG. 25 shows that the product (MgNi 0.5 Fe 0.5 MnO 4 ) obtained in Example 7 is in the form of particles.
  • FIG. 26 is an XRD pattern of the product (MgCu 0.5 Ni 0.5 MnO 4 ) obtained in Example 8. It can be seen that a solid solution of MgCu 0.5 Ni 0.5 MnO 4 has been synthesized.
  • FIG. 27 shows the SEM image of the product obtained in Example 8. From FIG. 27, it can be seen that the product obtained in Example 8 is in the form of particles.
  • FIG. 28 is an XRD pattern of MgNi 2 + MnO 4 , MgCu 2 + MnO 4 , MgCo 2 + MnO 4 , MgFe 2 + MnO 4 , and MgMn 2 + MnO 4 .
  • the XRD peaks are shifted to the high angle side in the order of Fe 2+ , Co 2+ , Cu 2+ , Ni 2+ , Cu 2+ , Co 2+ , and Fe 2+ , and lattice contraction occurs. Recognize.

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Abstract

L'invention concerne un nouveau composé de magnésium et un matériau actif d'électrode positive comprenant le composé de magnésium, pouvant servir à construire une batterie secondaire au magnésium possédant une capacité théorique élevée, un potentiel électrique élevé et une densité d'énergie théorique élevée à un faible coût. L'invention concerne également un procédé de production du composé de magnéisum. Le composé de magnésium selon la présente invention est représenté par Mga Xb Mnc Od (1) (dans la formule (1), X est au moins un élément choisi dans le groupe constitué par Fe et Cu. En outre, a représente 0,5 à 1,5, b représente 0,5 à 1,5, c représente 0,5 à 1,5 et d représente 3,8 à 4,1).
PCT/JP2017/000303 2016-01-06 2017-01-06 Composé de magnésium, matériau actif d'électrode positive pour batterie secondaire, batterie secondaire et procédé de production du compose de magnésium WO2017119494A1 (fr)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2020158322A (ja) * 2019-03-25 2020-10-01 株式会社高純度化学研究所 マグネシウム複合酸化物の製造方法

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS4837372A (fr) * 1971-09-14 1973-06-01
JP2002100344A (ja) * 2000-09-22 2002-04-05 Sony Corp 正極及び電池
JP2013533577A (ja) * 2010-05-25 2013-08-22 ペリオン テクノロジーズ インク． マグネシウム電池用の電極材料
JP2014007155A (ja) * 2012-05-30 2014-01-16 Showa Denko Kk マグネシウムイオン二次電池用正極活物質及びその製造方法並びにマグネシウムイオン二次電池
WO2016143675A1 (fr) * 2015-03-06 2016-09-15 学校法人東京理科大学 Batterie secondaire au magnésium et procédé de charge/décharge

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP5387318B2 (ja) * 2009-10-14 2014-01-15 東ソー株式会社 パティキュレート燃焼触媒及びそれを用いたパティキュレートの燃焼除去方法
KR101067115B1 (ko) * 2010-02-04 2011-09-22 삼성전기주식회사 마그네슘을 갖는 양극 활물질 및 이를 구비하는 마그네슘 이차전지
JP6934665B2 (ja) * 2016-01-06 2021-09-15 国立研究開発法人産業技術総合研究所 二次電池用正極活物質及びその製造方法、並びに二次電池

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS4837372A (fr) * 1971-09-14 1973-06-01
JP2002100344A (ja) * 2000-09-22 2002-04-05 Sony Corp 正極及び電池
JP2013533577A (ja) * 2010-05-25 2013-08-22 ペリオン テクノロジーズ インク． マグネシウム電池用の電極材料
JP2014007155A (ja) * 2012-05-30 2014-01-16 Showa Denko Kk マグネシウムイオン二次電池用正極活物質及びその製造方法並びにマグネシウムイオン二次電池
WO2016143675A1 (fr) * 2015-03-06 2016-09-15 学校法人東京理科大学 Batterie secondaire au magnésium et procédé de charge/décharge

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
BRAESTRUP, F. ET AL.: "Characterization of MgMnxFe2-xO4 as a possible cathode material for electrochemical reduction of NO x", JOURNAL OF APPLIEC ELECTROCHEMISTRY, vol. 39, no. 12, December 2009 (2009-12-01), pages 2369 - 2374, XP019749476, DOI: doi:10.1007/s10800-009-9923-1 *

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2020158322A (ja) * 2019-03-25 2020-10-01 株式会社高純度化学研究所 マグネシウム複合酸化物の製造方法

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