WO2016143675A1 - Magnesium secondary battery and charge/discharge method - Google Patents

Magnesium secondary battery and charge/discharge method Download PDF

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WO2016143675A1
WO2016143675A1 PCT/JP2016/056667 JP2016056667W WO2016143675A1 WO 2016143675 A1 WO2016143675 A1 WO 2016143675A1 JP 2016056667 W JP2016056667 W JP 2016056667W WO 2016143675 A1 WO2016143675 A1 WO 2016143675A1
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magnesium
secondary battery
positive electrode
magnesium secondary
charge
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PCT/JP2016/056667
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French (fr)
Japanese (ja)
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井手本　康
尚斗 北村
直哉 石田
松本　一
啓吾 窪田
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学校法人東京理科大学
国立研究開発法人産業技術総合研究所
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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
    • 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
    • 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
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
    • H01M10/0566—Liquid materials
    • H01M10/0569—Liquid materials characterised by the solvents
    • 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 disclosure relates to a magnesium secondary battery and a charge / discharge method using the same.
  • next-generation secondary batteries with low energy density and high energy density is expected to replace conventional lithium ion secondary batteries.
  • next-generation secondary batteries especially magnesium secondary batteries can be expected to have high capacity because (i) two-electron reaction can be used for charging and discharging, and (ii) magnesium that can be used for the negative electrode has excellent safety.
  • the battery can be operated at a high voltage.
  • Magnesium has many advantages such as low risk of uneven distribution in the production area and is inexpensive, and research and development are progressing.
  • Japanese Patent Laid-Open No. 2002-100344 discloses Mg (M 1-x A x ) 2 O 4 (wherein x is a number in the range of 0 ⁇ x ⁇ 0.2, and M is a transition metal) And A is a typical element, an alkali metal, or an alkaline earth metal.)
  • a magnesium secondary battery including a magnesium compound represented by the following formula is disclosed.
  • Japanese Patent Application Laid-Open No. 2011-165639 discloses a magnesium secondary battery containing a magnesium metal oxide having a spinel crystal structure composed of magnesium ions, metal ions, and oxygen ions as a positive electrode active material.
  • JP-A-2014-007155 discloses, for example, MgMn (2-x) M1 (x) O 4 (wherein M1 is one or more elements selected from Fe, Co, Ni, and x Is a number in the range of 0.4 ⁇ x ⁇ 2.)
  • Tetsu Ichitsubo, et al., J. Mater. Chem., 2011, 21, 11764 is magnesium secondary battery comprising MgCo 2 O 4 or MgNi 2 O 4 as a positive electrode active material is disclosed.
  • the mobility of magnesium ions can be improved as compared with the magnesium composite oxide having another structure.
  • a magnesium composite oxide is used as the positive electrode active material, it is difficult to obtain a magnesium secondary battery having a small discharge capacity and good charge / discharge characteristics because magnesium in the crystal is difficult to be detached. It was.
  • an object of the present disclosure is to provide a magnesium secondary battery exhibiting good charge / discharge characteristics and a charge / discharge method using the same.
  • a positive electrode comprising a positive electrode active material represented by: at least one element selected from the group consisting of 0.7 ⁇ x ⁇ 1.2; A negative electrode, And a non-aqueous electrolyte containing an ionic liquid whose anion portion is bis (trifluoromethanesulfonyl) amide or bis (fluorosulfonyl) amide.
  • M in the formula is at least one element selected from the group consisting of Co, Ni, and Mn.
  • ⁇ 4> The magnesium secondary battery according to any one of ⁇ 1> to ⁇ 3>, wherein the cation portion of the ionic liquid is tetraethylammonium.
  • ⁇ 5> A charge / discharge method using the magnesium secondary battery according to any one of ⁇ 1> to ⁇ 4> and performing charge / discharge at an operating temperature of 85 ° C. or higher.
  • FIG. 3 is a diagram showing an initial charge / discharge curve of a magnesium secondary battery produced in Example 1.
  • 5 is a diagram showing an initial charge / discharge curve of a magnesium secondary battery produced in Comparative Example 1.
  • FIG. 6 is a graph showing an initial charge / discharge curve of a magnesium secondary battery produced in Example 2.
  • FIG. 6 is a diagram showing an initial charge / discharge curve of a magnesium secondary battery produced in Comparative Example 2.
  • the term “layer” includes a configuration formed in a part in addition to a configuration formed in the entire surface when observed as a plan view.
  • a numerical range indicated by using “to” indicates a range including the numerical values described before and after “to” as the minimum value and the maximum value, respectively.
  • the magnesium secondary battery of this embodiment has the following formula: Mg x M 3-x O 4 (where M is Co, Ni, Mn, Ti, V, Cr, Fe, Cu, Ru, Ge, Mo, Si , Al, Zr, and B, at least one element selected from the group consisting of 0.7 ⁇ x ⁇ 1.2)), a negative electrode, and an anion And a non-aqueous electrolyte containing an ionic liquid whose part is bis (trifluoromethanesulfonyl) amide or bis (fluorosulfonyl) amide.
  • a separator is interposed between the positive electrode and the negative electrode.
  • the magnesium secondary battery of the present embodiment has a large discharge capacity and good charge / discharge characteristics by adopting the above configuration. This is because the ionic liquid whose anion portion is bis (trifluoromethanesulfonyl) amide or bis (fluorosulfonyl) amide has high heat resistance, so that the magnesium secondary battery can be operated at a high temperature (for example, 85 ° C. or more). As a result, it is assumed that the conductivity of magnesium ions in the positive electrode active material is increased.
  • the positive electrode in the magnesium secondary battery of the present embodiment has the following formula: Mg x M 3-x O 4 (where M is Co, Ni, Mn, Ti, V, Cr, Fe, Cu, Ru, Ge, Mo) And at least one element selected from the group consisting of Si, Al, Zr, and B, and 0.7 ⁇ x ⁇ 1.2.
  • the magnesium secondary battery of the present embodiment exhibits good charge / discharge characteristics by having a positive electrode active material having a spinel structure represented by the above formula and a specific non-aqueous electrolyte described later.
  • M in the above formula is at least one element selected from the group consisting of Co, Ni, Mn, Ti, V, Cr, Fe, Cu, Ru, Ge, Mo, Si, Al, Zr, and B. .
  • at least one element selected from the group consisting of Co, Ni, Mn, Cr, Fe, and Cu is preferable, and at least selected from the group consisting of Co, Ni, and Mn.
  • M in the above formula is Co.
  • M in the above formula is a combination of Ni and Mn.
  • X in the above formula is in the range of 0.7 to 1.2.
  • the value of x is preferably in the range of 0.8 to 1.2, and more preferably in the range of 0.9 to 1.2.
  • the method for producing the positive electrode active material represented by the above formula is not particularly limited, and a known production method such as a solid phase method or a coprecipitation method can be appropriately employed. Among these production methods, the coprecipitation method is preferable because a homogeneous phase is easily obtained.
  • a method for producing a compound in which M in the above formula is Co by a coprecipitation method is, for example, as follows. First, an aqueous solution containing a magnesium compound and a cobalt compound and a precipitating agent in a predetermined ratio is stirred at 20 ° C. to 100 ° C. to form a precipitate. Next, the precipitate is washed and dried to obtain a precursor. By calcination of this precursor at 250 ° C. to 350 ° C., a magnesium cobalt composite oxide can be obtained.
  • magnesium compound examples include magnesium nitrate, magnesium carbonate, magnesium acetate, magnesium oxalate, magnesium phosphate, magnesium sulfate, magnesium hydroxide, magnesium fluoride, magnesium chloride, magnesium bromide, and magnesium iodide.
  • the magnesium compound may be a hydrate.
  • a magnesium compound may be used individually by 1 type, and may use 2 or more types together.
  • the cobalt compound include cobalt nitrate, cobalt acetate, cobalt phosphate, cobalt sulfate, cobalt fluoride, cobalt chloride, and cobalt bromide.
  • the cobalt compound may be a hydrate.
  • a cobalt compound may be used individually by 1 type, and may use 2 or more types together.
  • sodium carbonate, sodium hydroxide or the like can be used as the precipitating agent.
  • the precipitant it is preferable to use the precipitant excessively with respect to the total amount of the magnesium compound and the cobalt compound.
  • a method for producing a compound in which M in the above formula is a combination of Ni and Mn by a coprecipitation method is, for example, as follows. First, an aqueous solution containing a nickel compound and a manganese compound and a precipitating agent in a predetermined ratio is stirred while blowing air at 20 ° C. to 80 ° C. to generate a precipitate. Next, the precipitate is washed and dried, and then mixed with a magnesium compound to obtain a precursor. By firing this precursor at 600 ° C. to 1000 ° C., a magnesium nickel manganese composite oxide can be obtained.
  • the same compounds as those used in producing the magnesium cobalt composite oxide can be used.
  • the nickel compound include nickel nitrate, nickel carbonate, nickel acetate, nickel oxalate, nickel sulfate, nickel fluoride, nickel chloride, nickel bromide, nickel iodide and the like.
  • the nickel compound may be a hydrate.
  • a nickel compound may be used individually by 1 type, and may use 2 or more types together.
  • manganese compound examples include manganese nitrate, manganese carbonate, manganese acetate, manganese oxalate, manganese sulfate, manganese fluoride, manganese chloride, manganese bromide, and manganese iodide.
  • the manganese compound may be a hydrate.
  • a manganese compound may be used individually by 1 type, and may use 2 or more types together.
  • the positive electrode in the magnesium secondary battery of this embodiment can be produced by applying a positive electrode mixture paste containing the above positive electrode active material on a current collector, drying it, and rolling it as necessary. .
  • Examples of the current collector include foils and meshes made of aluminum, stainless steel, copper, and the like.
  • the positive electrode mixture paste can be prepared by adding a positive electrode active material and, if necessary, a binder, a conductive auxiliary agent and the like to an organic solvent and mixing them.
  • a binder include polyimide, polyvinyl acetate, nitrocellulose, polyvinylidene fluoride, tetrafluoroethylene-hexafluoropropylene copolymer, styrene butadiene rubber, and acrylonitrile rubber.
  • a binder may be used individually by 1 type and may use 2 or more types together.
  • the conductive aid include carbon black, graphite, carbon fiber, and metal fiber. Examples of carbon black include acetylene black, ketjen black, channel black, furnace black, lamp black, and thermal black.
  • a conductive support agent may be used individually by 1 type, and may use 2 or more types together.
  • the organic solvent include N-methyl-2-pyrrolidone, tetrahydrofuran, N, N-dimethylformamide and the like.
  • An organic solvent may be used individually by 1 type, and may use 2 or more types together.
  • the amount of the positive electrode mixture paste applied to the current collector is preferably appropriately determined according to the use of the magnesium secondary battery.
  • the negative electrode in the magnesium secondary battery of this embodiment includes a negative electrode active material capable of occluding and releasing magnesium ions.
  • Examples of the negative electrode active material include magnesium metal and magnesium alloys.
  • Examples of the magnesium alloy include Mg—Al alloy, Mg—Zn alloy, Mg—Mn alloy, Mg—Ni alloy, Mg—Sb alloy, Mg—Sn alloy, Mg—In alloy and the like.
  • materials such as aluminum, zinc, lithium, silicon, and tin that are alloyed with magnesium can be used.
  • a carbon material such as graphite or amorphous carbon capable of electrochemically occluding and releasing magnesium ions can be used.
  • the negative electrode in the magnesium secondary battery of this embodiment can be formed by forming a negative electrode active material such as magnesium metal or a magnesium alloy into a shape (plate shape or the like) suitable for the electrode.
  • the negative electrode can also be produced by applying a negative electrode mixture paste containing the above negative electrode active material on a current collector, drying it, and rolling it as necessary.
  • a current collector include foils and meshes made of aluminum, stainless steel, copper, and the like.
  • the negative electrode mixture paste can be prepared by adding a negative electrode active material and, if necessary, a binder, a conductive auxiliary agent and the like to an organic solvent and mixing them.
  • a binder As the binder, the conductive additive, and the organic solvent, the same materials as those for the positive electrode can be used.
  • the separator in the magnesium secondary battery of this embodiment is provided so as to be interposed between the positive electrode and the negative electrode, and insulates the positive electrode and the negative electrode.
  • the material for the separator include polyethylene, polypropylene, polyamide, polyimide, polytetrafluoroethylene, glass, and ceramics.
  • the shape of the separator include a porous body.
  • the nonaqueous electrolytic solution in the magnesium secondary battery of the present embodiment includes an ionic liquid that is a nonaqueous solvent and a supporting salt that is a solute.
  • the anion portion is bis (trifluoromethanesulfonyl) amide ((CF 3 SO 2 ) 2 N ⁇ ) or bis (fluorosulfonyl) amide ((FSO 2 ) 2 N ⁇ ).
  • the magnesium secondary battery of the present embodiment has good charge / discharge characteristics by having a non-aqueous electrolyte containing an ionic liquid whose anion portion is bis (trifluoromethanesulfonyl) amide or bis (fluorosulfonyl) amide.
  • the cation portion of the ionic liquid is not particularly limited and can be appropriately selected from those known as the cation portion of the ionic liquid.
  • the cation part of the ionic liquid includes quaternary ammonium cations such as tetramethylammonium, tetraethylammonium, tetrabutylammonium, methyltriethylammonium, ethyltrimethylammonium, 2-hydroxyethyltrimethylammonium; 1-methylpyridinium, 1-ethylpyridinium Pyridinium cations such as 1-propylpyridinium; 1,3-dimethylimidazolium, 1-ethyl-3-methylimidazolium, 1-methyl-3-propylimidazolium, 1-butyl-3-methylimidazolium, 1- Imidazolium cations such as ethyl-3-propylimidazolium and 1-butyl-3-ethylimida
  • quaternary ammonium is preferable from the viewpoint of improving charge / discharge characteristics, tetraalkylammonium having 1 to 10 carbon atoms in each alkyl group is more preferable, and tetraethylammonium is more preferable.
  • a magnesium salt that dissolves in an ionic liquid that is a non-aqueous solvent can be used.
  • the supporting salt include magnesium bis (trifluoromethylsulfonyl) amide, magnesium bis (fluorosulfonyl) amide, magnesium bis (pentafluoroethylsulfonyl) amide, magnesium (fluorosulfonyl) (trifluoromethylsulfonyl) amide, and the like.
  • magnesium bis (trifluoromethylsulfonyl) amide and magnesium bis (fluorosulfonyl) amide are preferable from the viewpoint of improving charge / discharge characteristics.
  • the shape of the magnesium secondary battery is not particularly limited, and can be applied to any of a coin type, a cylindrical type, a stacked type, and the like.
  • the electrical connection form (electrode structure) in the magnesium ion secondary battery may be a non-bipolar type (internal parallel connection type) or a bipolar type (internal series connection type).
  • the charging / discharging method of this embodiment performs charging / discharging at the operating temperature of 85 degreeC or more using the magnesium secondary battery of this embodiment.
  • the operating temperature of the magnesium secondary battery is preferably 85 ° C. to 300 ° C., more preferably 90 ° C. to 200 ° C., and 130 ° C. More preferably, the temperature is -200 ° C.
  • the anion portion of the ionic liquid is bis (fluorosulfonyl) amide
  • the operating temperature of the magnesium secondary battery is preferably 85 ° C. to 100 ° C.
  • the obtained precursor was mixed in an automatic mortar for 24 hours, and then fired in the atmosphere at 300 ° C. for 24 hours to obtain a magnesium cobalt composite oxide.
  • the heating rate during firing was 5 ° C./min.
  • the obtained magnesium-cobalt composite oxide, inductively coupled plasma emission spectrometer (manufactured by Shimadzu Corporation, ICPE-9000) Analysis of the chemical composition, the composition formula Mg 0.852 Co 2.148 O 4 It was confirmed that. Further, when the crystal structure was analyzed by a powder X-ray diffractometer (manufactured by PANalytical, X'Pert Pro), it was found that the spinel structure of the space group Fd-3m had good crystallinity.
  • Example 1 90 parts by mass of the magnesium cobalt composite oxide (positive electrode active material) obtained in Synthesis Example 1, 5 parts by mass of polyimide (binder), 2 parts by mass of vapor grown carbon fiber (conducting aid), and ketjen black (Conductive auxiliary agent) 3 parts by mass were mixed, and N-methyl-2-pyrrolidone was added to make a paste to obtain a positive electrode mixture paste.
  • This positive electrode mixture paste was coated on a carbon-coated aluminum foil (current collector, thickness 21 ⁇ m) so that the coating thickness was 20 ⁇ m, and dried at 300 ° C. After drying, a positive electrode was produced by punching out to 16 mm ⁇ . The amount of the positive electrode active material in the positive electrode was 0.842 mg. Further, a metal magnesium plate (manufactured by Niraco Co., Ltd., purity 99.9%, thickness 0.10 mm) was punched out to 16 mm ⁇ to produce a negative electrode.
  • glass paper manufactured by Nippon Sheet Glass Co., Ltd., TGP-008F
  • a non-aqueous solvent for the non-aqueous electrolyte an ionic liquid was prepared in which the anion portion was bis (trifluoromethanesulfonyl) amide and the cation portion was tetraethylammonium.
  • magnesium bis (trifluoromethanesulfonyl) amide was prepared as a supporting salt for the non-aqueous electrolyte.
  • the ionic liquid and the supporting salt were mixed at a molar ratio of 90:10 to prepare a nonaqueous electrolytic solution, and the positive electrode and the separator were melt impregnated.
  • a positive electrode, a separator, and a negative electrode were sequentially laminated in a heat-resistant stainless steel cell (HS2 cell, manufactured by Hosen Co., Ltd.) to produce a magnesium secondary battery for testing.
  • HS2 cell heat-resistant stainless steel cell
  • Example 1 A positive electrode was produced in the same manner as in Example 1. The amount of the positive electrode active material in the positive electrode was 0.770 mg. Further, a metal magnesium plate (manufactured by Niraco Co., Ltd., purity 99.9%, thickness 0.25 mm) was punched out to 16 mm ⁇ to produce a negative electrode.
  • glass paper manufactured by Nippon Sheet Glass Co., Ltd., TGP-008F
  • sulfolane was prepared instead of the ionic liquid used in Example 1.
  • magnesium bis (trifluoromethanesulfonyl) amide was prepared as a supporting salt for the non-aqueous electrolyte.
  • a non-aqueous electrolyte was prepared by dissolving in sulfolane so that the concentration of the supporting salt was 0.5 mol / L, and the positive electrode and the separator were melt impregnated.
  • a positive electrode, a separator, and a negative electrode were sequentially laminated in a heat-resistant stainless steel cell (HS2 cell, manufactured by Hosen Co., Ltd.) to produce a magnesium secondary battery for testing.
  • HS2 cell heat-resistant stainless steel cell
  • Example 1A and 1B show initial charge / discharge curves of the magnesium secondary batteries of Example 1 and Comparative Example 1, respectively.
  • the magnesium secondary battery of Example 1 could be operated at a high temperature of 150 ° C. and showed a high discharge capacity of 439 mAh / g.
  • the magnesium secondary battery of Comparative Example 1 could not be operated at a high temperature of 150 ° C., and the discharge capacity was 103 mAh / g.
  • Example 2 A positive electrode was produced in the same manner as in Example 1 except that the magnesium nickel manganese composite oxide obtained in Synthesis Example 2 was used instead of the magnesium cobalt composite oxide obtained in Synthesis Example 1. The amount of the positive electrode active material in the positive electrode was 1.404 mg. Using the produced positive electrode, a test magnesium secondary battery was produced in the same manner as in Example 1.
  • Example 2 A positive electrode was produced in the same manner as in Example 1 except that the magnesium nickel manganese composite oxide obtained in Synthesis Example 2 was used instead of the magnesium cobalt composite oxide obtained in Synthesis Example 1. The amount of the positive electrode active material in the positive electrode was 1.38 mg. Using the produced positive electrode, a magnesium secondary battery for test was produced in the same manner as in Comparative Example 1.
  • Example 2A and 2B show initial charge / discharge curves of the magnesium secondary batteries of Example 2 and Comparative Example 2, respectively.
  • the magnesium secondary battery of Example 2 could be operated at a high temperature of 150 ° C. and showed a high discharge capacity of 246 mAh / g.
  • the magnesium secondary battery of Comparative Example 2 could not be operated at a high temperature of 150 ° C., and the discharge capacity was 103 mAh / g.

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Abstract

Provided are: a magnesium secondary battery which comprises a positive electrode containing a positive electrode active material that is represented by formula MgxM3-xO4 (wherein M represents at least one element selected from the group consisting of Co, Ni, Mn, Ti, V, Cr, Fe, Cu, Ru, Ge, Mo, Si, Al, Zr and B, and 0.7 ≤ x ≤ 1.2), a negative electrode, and a nonaqueous electrolyte solution containing an ionic liquid wherein the anionic component is bis(trifluoromethanesulfonyl)amide or bis(fluorosulfonyl)amide; and a charge/discharge method which uses this magnesium secondary battery.

Description

マグネシウム二次電池及び充放電方法Magnesium secondary battery and charge / discharge method
　本開示は、マグネシウム二次電池及びそれを用いた充放電方法に関する。 The present disclosure relates to a magnesium secondary battery and a charge / discharge method using the same.
　近年、蓄電池の用途がモバイル機器から自動車、定置用電源等へと多様化しており、従来のリチウムイオン二次電池に代わる安価で高エネルギー密度を有する次世代二次電池の開発が期待されている。次世代二次電池の中でも特にマグネシウム二次電池は、（ｉ）充放電で二電子反応を利用できるため高容量が期待できる、（ii）負極に使用可能なマグネシウムは安全性に優れていることに加えて電位が比較的低いため、電池の高電圧作動が可能になる、（iii）マグネシウムは産地偏在のリスクが少なく安価である、等の多くの利点があり、研究開発が進みつつある。 In recent years, the use of storage batteries has been diversified from mobile devices to automobiles, stationary power supplies, etc., and development of next-generation secondary batteries with low energy density and high energy density is expected to replace conventional lithium ion secondary batteries. . Among the next-generation secondary batteries, especially magnesium secondary batteries can be expected to have high capacity because (i) two-electron reaction can be used for charging and discharging, and (ii) magnesium that can be used for the negative electrode has excellent safety. In addition, since the potential is relatively low, the battery can be operated at a high voltage. (Iii) Magnesium has many advantages such as low risk of uneven distribution in the production area and is inexpensive, and research and development are progressing.
　開発当初、マグネシウム二次電池の正極活物質としてはＴｉＳ２、ＺｒＳ２、ＲｕＯ２、Ｃｏ３Ｏ４、Ｖ２Ｏ５等が用いられていたが、近年では、スピネル型構造を有するマグネシウム複合酸化物が種々提案されている。 Initially, TiS 2 , ZrS 2 , RuO 2 , Co 3 O 4 , V 2 O 5, etc. were used as positive electrode active materials for magnesium secondary batteries, but in recent years, magnesium composite oxide having a spinel structure has been used. Various things have been proposed.
　例えば、特開２００２－１００３４４号公報には、Ｍｇ（Ｍ１－ｘＡｘ）２Ｏ４（式中、ｘは０≦ｘ≦０．２の範囲の数である。また、Ｍは遷移金属であり、Ａは典型元素、アルカリ金属、又はアルカリ土類金属である。）で表されるマグネシウム化合物を正極活物質として含むマグネシウム二次電池が開示されている。
　また、特開２０１１－１６５６３９号公報には、マグネシウムイオン、金属イオン、及び酸素イオンからなるスピネル結晶構造を有するマグネシウム金属酸化物を正極活物質として含むマグネシウム二次電池が開示されている。
　また、特開２０１４－００７１５５号公報には、例えば、ＭｇＭｎ（２－ｘ）Ｍ１（ｘ）Ｏ４（式中、Ｍ１は、Ｆｅ、Ｃｏ、Ｎｉから選ばれる１種以上の元素であり、ｘは０．４≦ｘ＜２の範囲の数である。）で表される正極活物質を含むマグネシウム二次電池が開示されている。 For example, Japanese Patent Laid-Open No. 2002-100344 discloses Mg (M 1-x A x ) 2 O 4 (wherein x is a number in the range of 0 ≦ x ≦ 0.2, and M is a transition metal) And A is a typical element, an alkali metal, or an alkaline earth metal.) A magnesium secondary battery including a magnesium compound represented by the following formula is disclosed.
Japanese Patent Application Laid-Open No. 2011-165639 discloses a magnesium secondary battery containing a magnesium metal oxide having a spinel crystal structure composed of magnesium ions, metal ions, and oxygen ions as a positive electrode active material.
JP-A-2014-007155 discloses, for example, MgMn (2-x) M1 (x) O 4 (wherein M1 is one or more elements selected from Fe, Co, Ni, and x Is a number in the range of 0.4 ≦ x <2.) A magnesium secondary battery including a positive electrode active material represented by:
　また、Tetsu Ichitsubo, et al., J. Mater. Chem., 2011, 21, 11764には、ＭｇＣｏ２Ｏ４又はＭｇＮｉ２Ｏ４を正極活物質として含むマグネシウム二次電池が開示されている。 Further, Tetsu Ichitsubo, et al., J. Mater. Chem., 2011, 21, 11764 is magnesium secondary battery comprising MgCo 2 O 4 or MgNi 2 O 4 as a positive electrode active material is disclosed.
　上記のスピネル型構造を有するマグネシウム複合酸化物によれば、他の構造を有するマグネシウム複合酸化物と比較して、マグネシウムイオンの移動性を向上させることができると考えられる。
　しかし、マグネシウム複合酸化物を正極活物質とした場合、結晶中のマグネシウムが脱離し難い等の理由から、放電容量が小さく、良好な充放電特性を示すマグネシウム二次電池を得ることは困難であった。 According to the magnesium composite oxide having the above spinel structure, it is considered that the mobility of magnesium ions can be improved as compared with the magnesium composite oxide having another structure.
However, when a magnesium composite oxide is used as the positive electrode active material, it is difficult to obtain a magnesium secondary battery having a small discharge capacity and good charge / discharge characteristics because magnesium in the crystal is difficult to be detached. It was.
　そこで、本開示は、良好な充放電特性を示すマグネシウム二次電池及びそれを用いた充放電方法を提供することを課題とする。 Therefore, an object of the present disclosure is to provide a magnesium secondary battery exhibiting good charge / discharge characteristics and a charge / discharge method using the same.
　上記課題を解決するための具体的な手段には、以下の実施態様が含まれる。
＜１＞　次式：ＭｇｘＭ３－ｘＯ４（式中、ＭはＣｏ、Ｎｉ、Ｍｎ、Ｔｉ、Ｖ、Ｃｒ、Ｆｅ、Ｃｕ、Ｒｕ、Ｇｅ、Ｍｏ、Ｓｉ、Ａｌ、Ｚｒ、及びＢからなる群より選ばれる少なくとも１種の元素であり、０．７≦ｘ≦１．２である。）で表される正極活物質を含む正極と、
　負極と、
　アニオン部がビス（トリフルオロメタンスルホニル）アミド又はビス（フルオロスルホニル）アミドであるイオン液体を含む非水電解液と、を有するマグネシウム二次電池。 Specific means for solving the above problems include the following embodiments.
<1> following formula: Mg x M 3-x O 4 ( where, M is Co, Ni, Mn, Ti, V, Cr, Fe, Cu, Ru, Ge, Mo, Si, Al, Zr, and B A positive electrode comprising a positive electrode active material represented by: at least one element selected from the group consisting of 0.7 ≦ x ≦ 1.2;
A negative electrode,
And a non-aqueous electrolyte containing an ionic liquid whose anion portion is bis (trifluoromethanesulfonyl) amide or bis (fluorosulfonyl) amide.
＜２＞　前記式中のＭがＣｏ、Ｎｉ、及びＭｎからなる群より選ばれる少なくとも１種の元素である、＜１＞に記載のマグネシウム二次電池。 <2> The magnesium secondary battery according to <1>, wherein M in the formula is at least one element selected from the group consisting of Co, Ni, and Mn.
＜３＞　前記イオン液体のカチオン部が第４級アンモニウムである、＜１＞又は＜２＞に記載のマグネシウム二次電池。 <3> The magnesium secondary battery according to <1> or <2>, wherein the cation portion of the ionic liquid is quaternary ammonium.
＜４＞　前記イオン液体のカチオン部がテトラエチルアンモニウムである、＜１＞～＜３＞のいずれか１つに記載のマグネシウム二次電池。 <4> The magnesium secondary battery according to any one of <1> to <3>, wherein the cation portion of the ionic liquid is tetraethylammonium.
＜５＞　＜１＞～＜４＞のいずれか１つに記載のマグネシウム二次電池を用い、８５℃以上の作動温度で充放電を行う充放電方法。 <5> A charge / discharge method using the magnesium secondary battery according to any one of <1> to <4> and performing charge / discharge at an operating temperature of 85 ° C. or higher.
　本開示によれば、良好な充放電特性を示すマグネシウム二次電池及びそれを用いた充放電方法を提供することができる。 According to the present disclosure, it is possible to provide a magnesium secondary battery exhibiting good charge / discharge characteristics and a charge / discharge method using the same.
実施例１で作製したマグネシウム二次電池の初回充放電曲線を示す図である。FIG. 3 is a diagram showing an initial charge / discharge curve of a magnesium secondary battery produced in Example 1. 比較例１で作製したマグネシウム二次電池の初回充放電曲線を示す図である。5 is a diagram showing an initial charge / discharge curve of a magnesium secondary battery produced in Comparative Example 1. FIG. 実施例２で作製したマグネシウム二次電池の初回充放電曲線を示す図である。6 is a graph showing an initial charge / discharge curve of a magnesium secondary battery produced in Example 2. FIG. 比較例２で作製したマグネシウム二次電池の初回充放電曲線を示す図である。6 is a diagram showing an initial charge / discharge curve of a magnesium secondary battery produced in Comparative Example 2. FIG.
　以下、本発明を適用した具体的な実施形態について詳細に説明する。ただし、本発明は以下の実施形態に限定されるものではない。
　本明細書において「層」との語は、平面図として観察したときに、全面に形成されている形状の構成に加え、一部に形成されている形状の構成も包含される。また、本明細書において「～」を用いて示された数値範囲は、「～」の前後に記載される数値をそれぞれ最小値及び最大値として含む範囲を示す。 Hereinafter, specific embodiments to which the present invention is applied will be described in detail. However, the present invention is not limited to the following embodiments.
In this specification, the term “layer” includes a configuration formed in a part in addition to a configuration formed in the entire surface when observed as a plan view. In the present specification, a numerical range indicated by using “to” indicates a range including the numerical values described before and after “to” as the minimum value and the maximum value, respectively.
＜マグネシウム二次電池＞
　本実施形態のマグネシウム二次電池は、次式：ＭｇｘＭ３－ｘＯ４（式中、ＭはＣｏ、Ｎｉ、Ｍｎ、Ｔｉ、Ｖ、Ｃｒ、Ｆｅ、Ｃｕ、Ｒｕ、Ｇｅ、Ｍｏ、Ｓｉ、Ａｌ、Ｚｒ、及びＢからなる群より選ばれる少なくとも１種の元素であり、０．７≦ｘ≦１．２である。）で表される正極活物質を含む正極と、負極と、アニオン部がビス（トリフルオロメタンスルホニル）アミド又はビス（フルオロスルホニル）アミドであるイオン液体を含む非水電解液と、を有する。正極と負極との間にはセパレータが介在している。
　本実施形態のマグネシウム二次電池は、上記構成とすることにより、放電容量が大きく、良好な充放電特性を示す。これは、アニオン部がビス（トリフルオロメタンスルホニル）アミド又はビス（フルオロスルホニル）アミドであるイオン液体は耐熱性が高いため、マグネシウム二次電池を高温（例えば、８５℃以上）で作動させることが可能であり、その結果、正極活物質内におけるマグネシウムイオンの伝導性が高まるためと推察される。 <Magnesium secondary battery>
The magnesium secondary battery of this embodiment has the following formula: Mg x M 3-x O 4 (where M is Co, Ni, Mn, Ti, V, Cr, Fe, Cu, Ru, Ge, Mo, Si , Al, Zr, and B, at least one element selected from the group consisting of 0.7 ≦ x ≦ 1.2)), a negative electrode, and an anion And a non-aqueous electrolyte containing an ionic liquid whose part is bis (trifluoromethanesulfonyl) amide or bis (fluorosulfonyl) amide. A separator is interposed between the positive electrode and the negative electrode.
The magnesium secondary battery of the present embodiment has a large discharge capacity and good charge / discharge characteristics by adopting the above configuration. This is because the ionic liquid whose anion portion is bis (trifluoromethanesulfonyl) amide or bis (fluorosulfonyl) amide has high heat resistance, so that the magnesium secondary battery can be operated at a high temperature (for example, 85 ° C. or more). As a result, it is assumed that the conductivity of magnesium ions in the positive electrode active material is increased.
　以下、本実施形態のマグネシウム二次電池について詳細に説明する。 Hereinafter, the magnesium secondary battery of this embodiment will be described in detail.
（正極）
　本実施形態のマグネシウム二次電池における正極は、次式：ＭｇｘＭ３－ｘＯ４（式中、ＭはＣｏ、Ｎｉ、Ｍｎ、Ｔｉ、Ｖ、Ｃｒ、Ｆｅ、Ｃｕ、Ｒｕ、Ｇｅ、Ｍｏ、Ｓｉ、Ａｌ、Ｚｒ、及びＢからなる群より選ばれる少なくとも１種の元素であり、０．７≦ｘ≦１．２である。）で表される正極活物質を含む。本実施形態のマグネシウム二次電池は、上記式で表されるスピネル型構造を有する正極活物質と、後述する特定の非水電解液とを有することにより、良好な充放電特性を示す。 (Positive electrode)
The positive electrode in the magnesium secondary battery of the present embodiment has the following formula: Mg x M 3-x O 4 (where M is Co, Ni, Mn, Ti, V, Cr, Fe, Cu, Ru, Ge, Mo) And at least one element selected from the group consisting of Si, Al, Zr, and B, and 0.7 ≦ x ≦ 1.2. The magnesium secondary battery of the present embodiment exhibits good charge / discharge characteristics by having a positive electrode active material having a spinel structure represented by the above formula and a specific non-aqueous electrolyte described later.
　上記式中のＭは、Ｃｏ、Ｎｉ、Ｍｎ、Ｔｉ、Ｖ、Ｃｒ、Ｆｅ、Ｃｕ、Ｒｕ、Ｇｅ、Ｍｏ、Ｓｉ、Ａｌ、Ｚｒ、及びＢからなる群より選ばれる少なくとも１種の元素である。この中でも、エネルギー密度を向上させる観点から、Ｃｏ、Ｎｉ、Ｍｎ、Ｃｒ、Ｆｅ、及びＣｕからなる群より選ばれる少なくとも１種の元素が好ましく、Ｃｏ、Ｎｉ、及びＭｎからなる群より選ばれる少なくとも１種の元素がより好ましい。ある実施態様では、上記式中のＭはＣｏである。他の実施態様では、上記式中のＭはＮｉ及びＭｎの組み合わせである。 M in the above formula is at least one element selected from the group consisting of Co, Ni, Mn, Ti, V, Cr, Fe, Cu, Ru, Ge, Mo, Si, Al, Zr, and B. . Among these, from the viewpoint of improving energy density, at least one element selected from the group consisting of Co, Ni, Mn, Cr, Fe, and Cu is preferable, and at least selected from the group consisting of Co, Ni, and Mn. One element is more preferred. In certain embodiments, M in the above formula is Co. In another embodiment, M in the above formula is a combination of Ni and Mn.
　上記式中のｘは０．７～１．２の範囲である。電池容量を向上させる観点から、ｘの値は０．８～１．２の範囲であることが好ましく、０．９～１．２の範囲であることがより好ましい。 X in the above formula is in the range of 0.7 to 1.2. From the viewpoint of improving battery capacity, the value of x is preferably in the range of 0.8 to 1.2, and more preferably in the range of 0.9 to 1.2.
　上記式で表される正極活物質を製造する方法としては、特に制限されず、固相法、共沈法等の公知の製造方法を適宜採用することができる。これらの製造方法の中でも、均一相を得やすいことから、共沈法が好ましい。 The method for producing the positive electrode active material represented by the above formula is not particularly limited, and a known production method such as a solid phase method or a coprecipitation method can be appropriately employed. Among these production methods, the coprecipitation method is preferable because a homogeneous phase is easily obtained.
　上記式中のＭがＣｏである化合物を共沈法により製造する方法は、例えば以下のとおりである。まず、マグネシウム化合物及びコバルト化合物と沈殿剤とを所定の割合で含む水溶液を２０℃～１００℃で撹拌し、沈殿物を生成させる。次に、沈殿物を洗浄して乾燥することにより、前駆体を得る。この前駆体を２５０℃～３５０℃で焼成することにより、マグネシウムコバルト複合酸化物を得ることができる。 A method for producing a compound in which M in the above formula is Co by a coprecipitation method is, for example, as follows. First, an aqueous solution containing a magnesium compound and a cobalt compound and a precipitating agent in a predetermined ratio is stirred at 20 ° C. to 100 ° C. to form a precipitate. Next, the precipitate is washed and dried to obtain a precursor. By calcination of this precursor at 250 ° C. to 350 ° C., a magnesium cobalt composite oxide can be obtained.
　マグネシウム化合物としては、硝酸マグネシウム、炭酸マグネシウム、酢酸マグネシウム、シュウ酸マグネシウム、リン酸マグネシウム、硫酸マグネシウム、水酸化マグネシウム、フッ化マグネシウム、塩化マグネシウム、臭化マグネシウム、ヨウ化マグネシウム等が挙げられる。マグネシウム化合物は水和物であってもよい。マグネシウム化合物は、１種を単独で使用してもよく、２種以上を併用してもよい。
　コバルト化合物としては、硝酸コバルト、酢酸コバルト、リン酸コバルト、硫酸コバルト、フッ化コバルト、塩化コバルト、臭化コバルト等が挙げられる。コバルト化合物は水和物であってもよい。コバルト化合物は、１種を単独で使用してもよく、２種以上を併用してもよい。 Examples of the magnesium compound include magnesium nitrate, magnesium carbonate, magnesium acetate, magnesium oxalate, magnesium phosphate, magnesium sulfate, magnesium hydroxide, magnesium fluoride, magnesium chloride, magnesium bromide, and magnesium iodide. The magnesium compound may be a hydrate. A magnesium compound may be used individually by 1 type, and may use 2 or more types together.
Examples of the cobalt compound include cobalt nitrate, cobalt acetate, cobalt phosphate, cobalt sulfate, cobalt fluoride, cobalt chloride, and cobalt bromide. The cobalt compound may be a hydrate. A cobalt compound may be used individually by 1 type, and may use 2 or more types together.
　沈殿剤としては、炭酸ナトリウム、水酸化ナトリウム等を用いることができる。各成分の沈殿速度を近づけるため、沈殿剤は、マグネシウム化合物及びコバルト化合物の合計量に対して過剰に用いることが好ましい。 As the precipitating agent, sodium carbonate, sodium hydroxide or the like can be used. In order to approximate the precipitation rate of each component, it is preferable to use the precipitant excessively with respect to the total amount of the magnesium compound and the cobalt compound.
　また、上記式中のＭがＮｉ及びＭｎの組み合わせである化合物を共沈法により製造する方法は、例えば以下のとおりである。まず、ニッケル化合物及びマンガン化合物と沈殿剤とを所定の割合で含む水溶液を２０℃～８０℃で空気を吹き込みながら撹拌し、沈殿物を生成させる。次に、沈殿物を洗浄して乾燥した後、マグネシウム化合物と混合し、前駆体を得る。この前駆体を６００℃～１０００℃で焼成することにより、マグネシウムニッケルマンガン複合酸化物を得ることができる。 Further, a method for producing a compound in which M in the above formula is a combination of Ni and Mn by a coprecipitation method is, for example, as follows. First, an aqueous solution containing a nickel compound and a manganese compound and a precipitating agent in a predetermined ratio is stirred while blowing air at 20 ° C. to 80 ° C. to generate a precipitate. Next, the precipitate is washed and dried, and then mixed with a magnesium compound to obtain a precursor. By firing this precursor at 600 ° C. to 1000 ° C., a magnesium nickel manganese composite oxide can be obtained.
　マグネシウム化合物及び沈殿剤としては、マグネシウムコバルト複合酸化物を製造する際と同様の化合物を用いることができる。
　ニッケル化合物としては、硝酸ニッケル、炭酸ニッケル、酢酸ニッケル、シュウ酸ニッケル、硫酸ニッケル、フッ化ニッケル、塩化ニッケル、臭化ニッケル、ヨウ化ニッケル等が挙げられる。ニッケル化合物は水和物であってもよい。ニッケル化合物は、１種を単独で使用してもよく、２種以上を併用してもよい。
　マンガン化合物としては、硝酸マンガン、炭酸マンガン、酢酸マンガン、シュウ酸マンガン、硫酸マンガン、フッ化マンガン、塩化マンガン、臭化マンガン、ヨウ化マンガン等が挙げられる。マンガン化合物は水和物であってもよい。マンガン化合物は、１種を単独で使用してもよく、２種以上を併用してもよい。 As the magnesium compound and the precipitating agent, the same compounds as those used in producing the magnesium cobalt composite oxide can be used.
Examples of the nickel compound include nickel nitrate, nickel carbonate, nickel acetate, nickel oxalate, nickel sulfate, nickel fluoride, nickel chloride, nickel bromide, nickel iodide and the like. The nickel compound may be a hydrate. A nickel compound may be used individually by 1 type, and may use 2 or more types together.
Examples of the manganese compound include manganese nitrate, manganese carbonate, manganese acetate, manganese oxalate, manganese sulfate, manganese fluoride, manganese chloride, manganese bromide, and manganese iodide. The manganese compound may be a hydrate. A manganese compound may be used individually by 1 type, and may use 2 or more types together.
　本実施形態のマグネシウム二次電池における正極は、上記の正極活物質を含有する正極合剤ペーストを集電体上に塗布し、乾燥し、更に必要に応じて圧延することにより作製することができる。 The positive electrode in the magnesium secondary battery of this embodiment can be produced by applying a positive electrode mixture paste containing the above positive electrode active material on a current collector, drying it, and rolling it as necessary. .
　集電体としては、アルミニウム、ステンレス、銅等からなる箔、メッシュ等が挙げられる。 Examples of the current collector include foils and meshes made of aluminum, stainless steel, copper, and the like.
　正極合剤ペーストは、正極活物質と、必要に応じて結着剤、導電助剤等とを有機溶媒に添加して混合することにより調製することができる。
　結着剤としては、ポリイミド、ポリ酢酸ビニル、ニトロセルロース、ポリフッ化ビニリデン、テトラフルオロエチレン－ヘキサフルオロプロピレン共重合体、スチレンブタジエンゴム、アクリロニトリルゴム等が挙げられる。結着剤は、１種を単独で使用してもよく、２種以上を併用してもよい。
　導電助剤としては、カーボンブラック、黒鉛、炭素繊維、金属繊維等が挙げられる。カーボンブラックとしては、アセチレンブラック、ケッチェンブラック、チャンネルブラック、ファーネスブラック、ランプブラック、サーマルブラック等が挙げられる。導電助剤は、１種を単独で使用してもよく、２種以上を併用してもよい。
　有機溶媒としては、Ｎ－メチル－２－ピロリドン、テトラヒドロフラン、Ｎ，Ｎ－ジメチルホルムアミド等が挙げられる。有機溶媒は、１種を単独で使用してもよく、２種以上を併用してもよい。 The positive electrode mixture paste can be prepared by adding a positive electrode active material and, if necessary, a binder, a conductive auxiliary agent and the like to an organic solvent and mixing them.
Examples of the binder include polyimide, polyvinyl acetate, nitrocellulose, polyvinylidene fluoride, tetrafluoroethylene-hexafluoropropylene copolymer, styrene butadiene rubber, and acrylonitrile rubber. A binder may be used individually by 1 type and may use 2 or more types together.
Examples of the conductive aid include carbon black, graphite, carbon fiber, and metal fiber. Examples of carbon black include acetylene black, ketjen black, channel black, furnace black, lamp black, and thermal black. A conductive support agent may be used individually by 1 type, and may use 2 or more types together.
Examples of the organic solvent include N-methyl-2-pyrrolidone, tetrahydrofuran, N, N-dimethylformamide and the like. An organic solvent may be used individually by 1 type, and may use 2 or more types together.
　集電体に対する正極合剤ペーストの塗布量は、マグネシウム二次電池の用途等に応じて適宜決定することが好ましい。 The amount of the positive electrode mixture paste applied to the current collector is preferably appropriately determined according to the use of the magnesium secondary battery.
（負極）
　本実施形態のマグネシウム二次電池における負極は、マグネシウムイオンを吸蔵及び放出可能な負極活物質を含む。 (Negative electrode)
The negative electrode in the magnesium secondary battery of this embodiment includes a negative electrode active material capable of occluding and releasing magnesium ions.
　負極活物質としては、金属マグネシウム及びマグネシウム合金が挙げられる。マグネシウム合金としては、Ｍｇ－Ａｌ合金、Ｍｇ－Ｚｎ合金、Ｍｇ－Ｍｎ合金、Ｍｇ－Ｎｉ合金、Ｍｇ－Ｓｂ合金、Ｍｇ－Ｓｎ合金、Ｍｇ－Ｉｎ合金等が挙げられる。
　また、負極活物質としては、マグネシウムと合金化するアルミニウム、亜鉛、リチウム、シリコン、スズ等の材料を用いることもできる。また、負極活物質としては、マグネシウムイオンを電気化学的に吸蔵及び放出可能な黒鉛、非晶質炭素等の炭素材料を用いることもできる。 Examples of the negative electrode active material include magnesium metal and magnesium alloys. Examples of the magnesium alloy include Mg—Al alloy, Mg—Zn alloy, Mg—Mn alloy, Mg—Ni alloy, Mg—Sb alloy, Mg—Sn alloy, Mg—In alloy and the like.
In addition, as the negative electrode active material, materials such as aluminum, zinc, lithium, silicon, and tin that are alloyed with magnesium can be used. Further, as the negative electrode active material, a carbon material such as graphite or amorphous carbon capable of electrochemically occluding and releasing magnesium ions can be used.
　本実施形態のマグネシウム二次電池における負極は、金属マグネシウム、マグネシウム合金等の負極活物質を電極に適した形状（板状等）に成形して作成することができる。 The negative electrode in the magnesium secondary battery of this embodiment can be formed by forming a negative electrode active material such as magnesium metal or a magnesium alloy into a shape (plate shape or the like) suitable for the electrode.
　また、負極は、上記の負極活物質を含有する負極合剤ペーストを集電体上に塗布し、乾燥し、更に必要に応じて圧延することにより作製することもできる。集電体としては、アルミニウム、ステンレス、銅等からなる箔、メッシュ等が挙げられる。 The negative electrode can also be produced by applying a negative electrode mixture paste containing the above negative electrode active material on a current collector, drying it, and rolling it as necessary. Examples of the current collector include foils and meshes made of aluminum, stainless steel, copper, and the like.
　負極合剤ペーストは、負極活物質と、必要に応じて結着剤、導電助剤等とを有機溶媒に添加して混合することにより調製することができる。結着剤、導電助剤、及び有機溶媒としては、正極と同様の材料を用いることができる。 The negative electrode mixture paste can be prepared by adding a negative electrode active material and, if necessary, a binder, a conductive auxiliary agent and the like to an organic solvent and mixing them. As the binder, the conductive additive, and the organic solvent, the same materials as those for the positive electrode can be used.
（セパレータ）
　本実施形態のマグネシウム二次電池におけるセパレータは、正極と負極との間に介在するように設けられ、正極と負極とを絶縁する。セパレータの材料としては、ポリエチレン、ポリプロピレン、ポリアミド、ポリイミド、ポリテトラフルオロエチレン、ガラス、セラミックス等が挙げられる。セパレータの形状としては多孔質体等が挙げられる。 (Separator)
The separator in the magnesium secondary battery of this embodiment is provided so as to be interposed between the positive electrode and the negative electrode, and insulates the positive electrode and the negative electrode. Examples of the material for the separator include polyethylene, polypropylene, polyamide, polyimide, polytetrafluoroethylene, glass, and ceramics. Examples of the shape of the separator include a porous body.
（非水電解液）
　本実施形態のマグネシウム二次電池における非水電解液は、非水溶媒であるイオン液体と、溶質である支持塩とを含む。 (Nonaqueous electrolyte)
The nonaqueous electrolytic solution in the magnesium secondary battery of the present embodiment includes an ionic liquid that is a nonaqueous solvent and a supporting salt that is a solute.
　イオン液体は、アニオン部がビス（トリフルオロメタンスルホニル）アミド（（ＣＦ３ＳＯ２）２Ｎ－）又はビス（フルオロスルホニル）アミド（（ＦＳＯ２）２Ｎ－）である。本実施形態のマグネシウム二次電池は、アニオン部がビス（トリフルオロメタンスルホニル）アミド又はビス（フルオロスルホニル）アミドであるイオン液体を含む非水電解液を有することにより、良好な充放電特性を示す。 In the ionic liquid, the anion portion is bis (trifluoromethanesulfonyl) amide ((CF 3 SO 2 ) 2 N − ) or bis (fluorosulfonyl) amide ((FSO 2 ) 2 N − ). The magnesium secondary battery of the present embodiment has good charge / discharge characteristics by having a non-aqueous electrolyte containing an ionic liquid whose anion portion is bis (trifluoromethanesulfonyl) amide or bis (fluorosulfonyl) amide.
　イオン液体のカチオン部は特に制限されず、イオン液体のカチオン部として公知のものから適宜選択することができる。
　イオン液体のカチオン部としては、テトラメチルアンモニウム、テトラエチルアンモニウム、テトラブチルアンモニウム、メチルトリエチルアンモニウム、エチルトリメチルアンモニウム、２－ヒドロキシエチルトリメチルアンモニウム等の第４級アンモニウムカチオン；１－メチルピリジニウム、１－エチルピリジニウム、１－プロピルピリジニウム等のピリジニウムカチオン；１，３－ジメチルイミダゾリウム、１－エチル－３－メチルイミダゾリウム、１－メチル－３－プロピルイミダゾリウム、１－ブチル－３－メチルイミダゾリウム、１－エチル－３－プロピルイミダゾリウム、１－ブチル－３－エチルイミダゾリウム等のイミダゾリウムカチオン；テトラメチルホスホニウム、テトラエチルホスホニウム、テトラオクチルホスホニウム、トリエチル（メトキシメチル）ホスホニウム、ジエチルメチル（メトキシメチル）ホスホニウム、トリヘキシル（メトキシエチル）ホスホニウム等の第４級ホスホニウムカチオン；などが挙げられる。
　これらのカチオン部の中でも、充放電特性を向上させる観点から、第４級アンモニウムが好ましく、各アルキル基の炭素数が１～１０であるテトラアルキルアンモニウムがより好ましく、テトラエチルアンモニウムが更に好ましい。 The cation portion of the ionic liquid is not particularly limited and can be appropriately selected from those known as the cation portion of the ionic liquid.
The cation part of the ionic liquid includes quaternary ammonium cations such as tetramethylammonium, tetraethylammonium, tetrabutylammonium, methyltriethylammonium, ethyltrimethylammonium, 2-hydroxyethyltrimethylammonium; 1-methylpyridinium, 1-ethylpyridinium Pyridinium cations such as 1-propylpyridinium; 1,3-dimethylimidazolium, 1-ethyl-3-methylimidazolium, 1-methyl-3-propylimidazolium, 1-butyl-3-methylimidazolium, 1- Imidazolium cations such as ethyl-3-propylimidazolium and 1-butyl-3-ethylimidazolium; tetramethylphosphonium, tetraethylphosphonium, tetraoctylphospho Um, triethyl (methoxymethyl) phosphonium, diethyl methyl (methoxymethyl) phosphonium, trihexyl quaternary phosphonium cations such as (methoxyethyl) phosphonium; and the like.
Among these cation moieties, quaternary ammonium is preferable from the viewpoint of improving charge / discharge characteristics, tetraalkylammonium having 1 to 10 carbon atoms in each alkyl group is more preferable, and tetraethylammonium is more preferable.
　支持塩としては、非水溶媒であるイオン液体に溶解するマグネシウム塩を用いることができる。支持塩としては、マグネシウムビス（トリフルオロメチルスルホニル）アミド、マグネシウムビス（フルオロスルホニル）アミド、マグネシウムビス（ペンタフルオロエチルスルホニル）アミド、マグネシウム（フルオロスルホニル）（トリフルオロメチルスルホニル）アミド等が挙げられる。これらの支持塩の中でも、充放電特性を向上させる観点から、マグネシウムビス（トリフルオロメチルスルホニル）アミド及びマグネシウムビス（フルオロスルホニル）アミドが好ましい。 As the supporting salt, a magnesium salt that dissolves in an ionic liquid that is a non-aqueous solvent can be used. Examples of the supporting salt include magnesium bis (trifluoromethylsulfonyl) amide, magnesium bis (fluorosulfonyl) amide, magnesium bis (pentafluoroethylsulfonyl) amide, magnesium (fluorosulfonyl) (trifluoromethylsulfonyl) amide, and the like. Among these supporting salts, magnesium bis (trifluoromethylsulfonyl) amide and magnesium bis (fluorosulfonyl) amide are preferable from the viewpoint of improving charge / discharge characteristics.
（マグネシウム二次電池の形状等）
　マグネシウム二次電池の形状は特に制限されず、コイン型、円筒型、積層型等のいずれにも適用し得る。また、マグネシウムイオン二次電池内の電気的な接続形態（電極構造）は、非双極型（内部並列接続型）であっても双極型（内部直列接続型）であってもよい。 (Magnesium secondary battery shape, etc.)
The shape of the magnesium secondary battery is not particularly limited, and can be applied to any of a coin type, a cylindrical type, a stacked type, and the like. Further, the electrical connection form (electrode structure) in the magnesium ion secondary battery may be a non-bipolar type (internal parallel connection type) or a bipolar type (internal series connection type).
＜充放電方法＞
　本実施形態の充放電方法は、本実施形態のマグネシウム二次電池を用い、８５℃以上の作動温度で充放電を行うものである。作動温度を８５℃以上とすることにより、マグネシウム二次電池の放電容量をより向上させることができる。
　イオン液体のアニオン部がビス（トリフルオロメタンスルホニル）アミドである場合、マグネシウム二次電池の作動温度は８５℃～３００℃であることが好ましく、９０℃～２００℃であることがより好ましく、１３０℃～２００℃であることが更に好ましい。一方、イオン液体のアニオン部がビス（フルオロスルホニル）アミドである場合、マグネシウム二次電池の作動温度は８５℃～１００℃であることが好ましい。 <Charging / discharging method>
The charging / discharging method of this embodiment performs charging / discharging at the operating temperature of 85 degreeC or more using the magnesium secondary battery of this embodiment. By setting the operating temperature to 85 ° C. or higher, the discharge capacity of the magnesium secondary battery can be further improved.
When the anion portion of the ionic liquid is bis (trifluoromethanesulfonyl) amide, the operating temperature of the magnesium secondary battery is preferably 85 ° C. to 300 ° C., more preferably 90 ° C. to 200 ° C., and 130 ° C. More preferably, the temperature is -200 ° C. On the other hand, when the anion portion of the ionic liquid is bis (fluorosulfonyl) amide, the operating temperature of the magnesium secondary battery is preferably 85 ° C. to 100 ° C.
　以下、実施例により本発明を具体的に説明するが、本発明は実施例に限定されるものではない。 Hereinafter, the present invention will be specifically described by way of examples, but the present invention is not limited to the examples.
［合成例１］
　炭酸ナトリウム２３．１３４ｇを二次蒸留水８００ｍＬに溶解し、水溶液を７０℃に加熱した。水溶液中に、１．０ｍｏｌ／Ｌ硝酸マグネシウム水溶液６１．７８ｍＬと１．０ｍｏｌ／Ｌ硝酸コバルト水溶液１１７．７４ｍＬとを添加し、７０℃で３０分間撹拌した。水溶液中のナトリウムとマグネシウム及びコバルトとのモル比は、Ｎａ／Ｍｇ＋Ｃｏ＝２．５であった。撹拌後、沈殿物を吸引濾過し、７０℃の水で洗浄した後、大気中、１００℃で２４時間乾燥させることにより、前駆体を得た。得られた前駆体を自動乳鉢で２４時間混合した後、大気中、３００℃で２４時間焼成することにより、マグネシウムコバルト複合酸化物を得た。焼成時の昇温速度は５℃／分とした。
　得られたマグネシウムコバルト複合酸化物について、誘導結合プラズマ発光分光分析装置（（株）島津製作所製、ＩＣＰＥ－９０００）により化学組成を分析したところ、Ｍｇ０．８５２Ｃｏ２．１４８Ｏ４の組成式であることが確認された。また、粉末Ｘ線回折装置（ＰＡＮａｌｙｔｉｃａｌ製、Ｘ’Ｐｅｒｔ　Ｐｒｏ）により結晶構造を分析したところ、良好な結晶性を有する、空間群Ｆｄ－３ｍのスピネル型構造であることが明らかとなった。 [Synthesis Example 1]
23.134 g of sodium carbonate was dissolved in 800 mL of secondary distilled water, and the aqueous solution was heated to 70 ° C. In the aqueous solution, 61.78 mL of 1.0 mol / L magnesium nitrate aqueous solution and 117.74 mL of 1.0 mol / L cobalt nitrate aqueous solution were added, and stirred at 70 ° C. for 30 minutes. The molar ratio of sodium to magnesium and cobalt in the aqueous solution was Na / Mg + Co = 2.5. After stirring, the precipitate was filtered by suction, washed with 70 ° C. water, and then dried in air at 100 ° C. for 24 hours to obtain a precursor. The obtained precursor was mixed in an automatic mortar for 24 hours, and then fired in the atmosphere at 300 ° C. for 24 hours to obtain a magnesium cobalt composite oxide. The heating rate during firing was 5 ° C./min.
The obtained magnesium-cobalt composite oxide, inductively coupled plasma emission spectrometer (manufactured by Shimadzu Corporation, ICPE-9000) Analysis of the chemical composition, the composition formula Mg 0.852 Co 2.148 O 4 It was confirmed that. Further, when the crystal structure was analyzed by a powder X-ray diffractometer (manufactured by PANalytical, X'Pert Pro), it was found that the spinel structure of the space group Fd-3m had good crystallinity.
［合成例２］
　炭酸ナトリウム１９．９５８ｇを二次蒸留水８００ｍＬに溶解し、水溶液を８０℃に加熱した。水溶液中に、１．０ｍｏｌ／Ｌ硝酸ニッケル水溶液２８．２２ｍＬと１．０ｍｏｌ／Ｌ硝酸マンガン水溶液３０．２８ｍＬとを添加し、空気を吹き込みながら８０℃で１２時間撹拌した。撹拌後、沈殿物を吸引濾過し、二次蒸留水で洗浄した後、大気中、１００℃で２４時間乾燥させた。乾燥後の沈殿物６．９４ｇと硝酸マグネシウム六水和物７．６１８ｇとを乳鉢で混合し、前駆体を得た。得られた前駆体を、大気中、５００℃で５時間仮焼成した後、９５０℃で１５時間焼成することにより、マグネシウムニッケルマンガン複合酸化物（ＭｇＮｉＭｎＯ４）を得た。仮焼成時及び焼成時の昇温速度は５℃／分とした。
　得られたマグネシウムニッケルマンガン複合酸化物について、粉末Ｘ線回折装置（ＰＡＮａｌｙｔｉｃａｌ製、Ｘ’Ｐｅｒｔ　Ｐｒｏ）により結晶構造を分析したところ、良好な結晶性を有する、空間群Ｆｄ－３ｍのスピネル型構造であることが明らかとなった。 [Synthesis Example 2]
19.958 g of sodium carbonate was dissolved in 800 mL of secondary distilled water, and the aqueous solution was heated to 80 ° C. In the aqueous solution, 28.22 mL of 1.0 mol / L nickel nitrate aqueous solution and 30.28 mL of 1.0 mol / L manganese nitrate aqueous solution were added, and the mixture was stirred at 80 ° C. for 12 hours while blowing air. After stirring, the precipitate was filtered by suction, washed with secondary distilled water, and then dried in the atmosphere at 100 ° C. for 24 hours. 6.94 g of the precipitate after drying and 7.618 g of magnesium nitrate hexahydrate were mixed in a mortar to obtain a precursor. The obtained precursor was calcined at 500 ° C. for 5 hours in the air, and then calcined at 950 ° C. for 15 hours to obtain a magnesium nickel manganese composite oxide (MgNiMnO 4 ). The rate of temperature increase during pre-firing and firing was 5 ° C./min.
When the crystal structure of the obtained magnesium nickel manganese composite oxide was analyzed by a powder X-ray diffractometer (manufactured by PANalytical, X'Pert Pro), the spinel structure of the space group Fd-3m having good crystallinity was obtained. It became clear that there was.
［実施例１］
　合成例１で得たマグネシウムコバルト複合酸化物（正極活物質）９０質量部と、ポリイミド（結着剤）５質量部と、気相法炭素繊維（導電助剤）２質量部と、ケッチェンブラック（導電助剤）３質量部とを混合し、Ｎ－メチル－２－ピロリドンを加えてペースト化し、正極合剤ペーストを得た。この正極合剤ペーストを、塗工厚みが２０μｍとなるようにカーボンコートアルミニウム箔（集電体、厚さ２１μｍ）に塗工し、３００℃で乾燥させた。乾燥後、１６ｍｍφに打ち抜いて正極を作製した。正極中の正極活物質の量は０．８４２ｍｇであった。
　また、金属マグネシウム板（（株）ニラコ製、純度９９．９％、厚さ０．１０ｍｍ）を１６ｍｍφに打ち抜いて負極を作製した。 [Example 1]
90 parts by mass of the magnesium cobalt composite oxide (positive electrode active material) obtained in Synthesis Example 1, 5 parts by mass of polyimide (binder), 2 parts by mass of vapor grown carbon fiber (conducting aid), and ketjen black (Conductive auxiliary agent) 3 parts by mass were mixed, and N-methyl-2-pyrrolidone was added to make a paste to obtain a positive electrode mixture paste. This positive electrode mixture paste was coated on a carbon-coated aluminum foil (current collector, thickness 21 μm) so that the coating thickness was 20 μm, and dried at 300 ° C. After drying, a positive electrode was produced by punching out to 16 mmφ. The amount of the positive electrode active material in the positive electrode was 0.842 mg.
Further, a metal magnesium plate (manufactured by Niraco Co., Ltd., purity 99.9%, thickness 0.10 mm) was punched out to 16 mmφ to produce a negative electrode.
　セパレータとしては、ガラスペーパー（日本板硝子（株）製、ＴＧＰ－００８Ｆ）を準備した。
　非水電解液の非水溶媒としては、アニオン部がビス（トリフルオロメタンスルホニル）アミドであり、カチオン部がテトラエチルアンモニウムであるイオン液体を準備した。また、非水電解液の支持塩としては、マグネシウムビス（トリフルオロメタンスルホニル）アミドを準備した。イオン液体と支持塩とを９０：１０のモル比で混合して非水電解液を調製し、正極及びセパレータに溶融含浸させた。 As a separator, glass paper (manufactured by Nippon Sheet Glass Co., Ltd., TGP-008F) was prepared.
As a non-aqueous solvent for the non-aqueous electrolyte, an ionic liquid was prepared in which the anion portion was bis (trifluoromethanesulfonyl) amide and the cation portion was tetraethylammonium. Further, magnesium bis (trifluoromethanesulfonyl) amide was prepared as a supporting salt for the non-aqueous electrolyte. The ionic liquid and the supporting salt were mixed at a molar ratio of 90:10 to prepare a nonaqueous electrolytic solution, and the positive electrode and the separator were melt impregnated.
　その後、正極、セパレータ、負極の順に耐熱性ステンレスセル（宝泉（株）製、ＨＳ２セル）内に積層し、試験用のマグネシウム二次電池を作製した。 Thereafter, a positive electrode, a separator, and a negative electrode were sequentially laminated in a heat-resistant stainless steel cell (HS2 cell, manufactured by Hosen Co., Ltd.) to produce a magnesium secondary battery for testing.
［比較例１］
　実施例１と同様にして正極を作製した。正極中の正極活物質の量は０．７７０ｍｇであった。
　また、金属マグネシウム板（（株）ニラコ製、純度９９．９％、厚さ０．２５ｍｍ）を１６ｍｍφに打ち抜いて負極を作製した。 [Comparative Example 1]
A positive electrode was produced in the same manner as in Example 1. The amount of the positive electrode active material in the positive electrode was 0.770 mg.
Further, a metal magnesium plate (manufactured by Niraco Co., Ltd., purity 99.9%, thickness 0.25 mm) was punched out to 16 mmφ to produce a negative electrode.
　セパレータとしては、ガラスペーパー（日本板硝子（株）製、ＴＧＰ－００８Ｆ）を準備した。
　非水電解液の非水溶媒としては、実施例１で用いたイオン液体の代わりに、スルホランを準備した。また、非水電解液の支持塩としては、マグネシウムビス（トリフルオロメタンスルホニル）アミドを準備した。支持塩の濃度が０．５ｍｏｌ／Ｌとなるようにスルホラン中に溶解して非水電解液を調製し、正極及びセパレータに溶融含浸させた。 As a separator, glass paper (manufactured by Nippon Sheet Glass Co., Ltd., TGP-008F) was prepared.
As a nonaqueous solvent for the nonaqueous electrolytic solution, sulfolane was prepared instead of the ionic liquid used in Example 1. Further, magnesium bis (trifluoromethanesulfonyl) amide was prepared as a supporting salt for the non-aqueous electrolyte. A non-aqueous electrolyte was prepared by dissolving in sulfolane so that the concentration of the supporting salt was 0.5 mol / L, and the positive electrode and the separator were melt impregnated.
　その後、正極、セパレータ、負極の順に耐熱性ステンレスセル（宝泉（株）製、ＨＳ２セル）内に積層し、試験用のマグネシウム二次電池を作製した。 Thereafter, a positive electrode, a separator, and a negative electrode were sequentially laminated in a heat-resistant stainless steel cell (HS2 cell, manufactured by Hosen Co., Ltd.) to produce a magnesium secondary battery for testing.
［評価］
　実施例１及び比較例１のマグネシウム二次電池について、恒温槽内で充放電試験を行った。詳細には、電流密度１０ｍＡ／ｇ（０．０４６Ｃ相当）で充電を行い、電位が上がらなくなった時点で放電に切り替え、電位が０Ｖ（ｖｓ．Ｍｇ／Ｍｇ２＋）に達するまで、電流密度１０ｍＡ／ｇで放電を続けた。
　なお、実施例１のマグネシウム二次電池については、作動温度が１５０℃となるように恒温槽内の温度を設定した。一方、比較例１のマグネシウム二次電池については、非水電解液に用いているスルホランの耐熱性が低く、１５０℃の高温で作動させることができないため、作動温度が８０℃となるように恒温槽内の温度を設定した。 [Evaluation]
About the magnesium secondary battery of Example 1 and Comparative Example 1, the charge / discharge test was done in the thermostat. Specifically, charging is performed at a current density of 10 mA / g (equivalent to 0.046 C), and when the potential stops increasing, switching is performed to discharge, and the current density of 10 mA / g until the potential reaches 0 V (vs. Mg / Mg 2+ ). Discharge continued at g.
In addition, about the magnesium secondary battery of Example 1, the temperature in a thermostat was set so that operating temperature might be 150 degreeC. On the other hand, for the magnesium secondary battery of Comparative Example 1, since the heat resistance of sulfolane used in the non-aqueous electrolyte is low and cannot be operated at a high temperature of 150 ° C., the constant temperature is set so that the operating temperature becomes 80 ° C. The temperature in the tank was set.
　実施例１及び比較例１のマグネシウム二次電池の初回充放電曲線をそれぞれ図１Ａ、図１Ｂに示す。実施例１のマグネシウム二次電池は、１５０℃の高温で作動させることができ、４３９ｍＡｈ／ｇという高い放電容量を示した。一方、比較例１のマグネシウム二次電池は、１５０℃の高温で作動させることができず、放電容量は１０３ｍＡｈ／ｇであった。 1A and 1B show initial charge / discharge curves of the magnesium secondary batteries of Example 1 and Comparative Example 1, respectively. The magnesium secondary battery of Example 1 could be operated at a high temperature of 150 ° C. and showed a high discharge capacity of 439 mAh / g. On the other hand, the magnesium secondary battery of Comparative Example 1 could not be operated at a high temperature of 150 ° C., and the discharge capacity was 103 mAh / g.
［実施例２］
　合成例１で得たマグネシウムコバルト複合酸化物の代わりに合成例２で得たマグネシウムニッケルマンガン複合酸化物を用いたほかは、実施例１と同様にして正極を作製した。正極中の正極活物質の量は１．４０４ｍｇであった。
　作製した正極を用いて、実施例１と同様にして試験用のマグネシウム二次電池を作製した。 [Example 2]
A positive electrode was produced in the same manner as in Example 1 except that the magnesium nickel manganese composite oxide obtained in Synthesis Example 2 was used instead of the magnesium cobalt composite oxide obtained in Synthesis Example 1. The amount of the positive electrode active material in the positive electrode was 1.404 mg.
Using the produced positive electrode, a test magnesium secondary battery was produced in the same manner as in Example 1.
［比較例２］
　合成例１で得たマグネシウムコバルト複合酸化物の代わりに合成例２で得たマグネシウムニッケルマンガン複合酸化物を用いたほかは、実施例１と同様にして正極を作製した。正極中の正極活物質の量は１．３８ｍｇであった。
　作製した正極を用いて、比較例１と同様にして試験用のマグネシウム二次電池を作製した。 [Comparative Example 2]
A positive electrode was produced in the same manner as in Example 1 except that the magnesium nickel manganese composite oxide obtained in Synthesis Example 2 was used instead of the magnesium cobalt composite oxide obtained in Synthesis Example 1. The amount of the positive electrode active material in the positive electrode was 1.38 mg.
Using the produced positive electrode, a magnesium secondary battery for test was produced in the same manner as in Comparative Example 1.
［評価］
　実施例２及び比較例２のマグネシウム二次電池について、恒温槽内で充放電試験を行った。詳細には、電流密度１０ｍＡ／ｇ（０．０３８Ｃ相当）で充電を行い、電位が上がらなくなった時点で放電に切り替え、電位が０Ｖ（ｖｓ．Ｍｇ／Ｍｇ２＋）に達するまで、電流密度１０ｍＡ／ｇで放電を続けた。
　なお、実施例２のマグネシウム二次電池については、作動温度が１５０℃となるように恒温槽内の温度を設定した。一方、比較例２のマグネシウム二次電池については、非水電解液に用いているスルホランの耐熱性が低く、１５０℃の高温で作動させることができないため、作動温度が８０℃となるように恒温槽内の温度を設定した。 [Evaluation]
About the magnesium secondary battery of Example 2 and Comparative Example 2, the charge / discharge test was done in the thermostat. Specifically, charging is performed at a current density of 10 mA / g (equivalent to 0.038 C), switching to discharging when the potential stops increasing, and until the potential reaches 0 V (vs. Mg / Mg 2+ ), the current density is 10 mA / g. Discharge continued at g.
In addition, about the magnesium secondary battery of Example 2, the temperature in a thermostat was set so that operating temperature might be 150 degreeC. On the other hand, for the magnesium secondary battery of Comparative Example 2, since the heat resistance of sulfolane used in the non-aqueous electrolyte is low and cannot be operated at a high temperature of 150 ° C., the constant temperature is set so that the operating temperature becomes 80 ° C. The temperature in the tank was set.
　実施例２及び比較例２のマグネシウム二次電池の初回充放電曲線をそれぞれ図２Ａ、図２Ｂに示す。実施例２のマグネシウム二次電池は、１５０℃の高温で作動させることができ、２４６ｍＡｈ／ｇという高い放電容量を示した。一方、比較例２のマグネシウム二次電池は、１５０℃の高温で作動させることができず、放電容量は１０３ｍＡｈ／ｇであった。 2A and 2B show initial charge / discharge curves of the magnesium secondary batteries of Example 2 and Comparative Example 2, respectively. The magnesium secondary battery of Example 2 could be operated at a high temperature of 150 ° C. and showed a high discharge capacity of 246 mAh / g. On the other hand, the magnesium secondary battery of Comparative Example 2 could not be operated at a high temperature of 150 ° C., and the discharge capacity was 103 mAh / g.
　２０１５年３月６日に出願された日本出願２０１５－０４４８１０の開示はその全体が参照により本明細書に取り込まれる。
　本明細書に記載された全ての文献、特許出願、及び技術規格は、個々の文献、特許出願、及び技術規格が参照により取り込まれることが具体的かつ個々に記された場合と同程度に、本明細書中に参照により取り込まれる。 The disclosure of Japanese application 2015-044810 filed on March 6, 2015 is incorporated herein by reference in its entirety.
All documents, patent applications, and technical standards mentioned in this specification are to the same extent as if each individual document, patent application, and technical standard were specifically and individually stated to be incorporated by reference, Incorporated herein by reference.

Claims (5)

  1. 　次式：ＭｇｘＭ３－ｘＯ４（式中、ＭはＣｏ、Ｎｉ、Ｍｎ、Ｔｉ、Ｖ、Ｃｒ、Ｆｅ、Ｃｕ、Ｒｕ、Ｇｅ、Ｍｏ、Ｓｉ、Ａｌ、Ｚｒ、及びＢからなる群より選ばれる少なくとも１種の元素であり、０．７≦ｘ≦１．２である。）で表される正極活物質を含む正極と、
    　負極と、
    　アニオン部がビス（トリフルオロメタンスルホニル）アミド又はビス（フルオロスルホニル）アミドであるイオン液体を含む非水電解液と、を有するマグネシウム二次電池。     The following formula: Mg x M 3-x O 4 (wherein M is a group consisting of Co, Ni, Mn, Ti, V, Cr, Fe, Cu, Ru, Ge, Mo, Si, Al, Zr, and B) A positive electrode containing a positive electrode active material represented by: at least one element selected from the group consisting of 0.7 ≦ x ≦ 1.2;
    A negative electrode,
    And a non-aqueous electrolyte containing an ionic liquid whose anion portion is bis (trifluoromethanesulfonyl) amide or bis (fluorosulfonyl) amide.
  2. 　前記式中のＭがＣｏ、Ｎｉ、及びＭｎからなる群より選ばれる少なくとも１種の元素である、請求項１に記載のマグネシウム二次電池。 The magnesium secondary battery according to claim 1, wherein M in the formula is at least one element selected from the group consisting of Co, Ni, and Mn.
  3. 　前記イオン液体のカチオン部が第４級アンモニウムである、請求項１又は請求項２に記載のマグネシウム二次電池。 The magnesium secondary battery according to claim 1 or 2, wherein the cation portion of the ionic liquid is quaternary ammonium.
  4. 　前記イオン液体のカチオン部がテトラエチルアンモニウムである、請求項１～請求項３のいずれか１項に記載のマグネシウム二次電池。 The magnesium secondary battery according to any one of claims 1 to 3, wherein a cation portion of the ionic liquid is tetraethylammonium.
  5. 　請求項１～請求項４のいずれか１項に記載のマグネシウム二次電池を用い、８５℃以上の作動温度で充放電を行う充放電方法。 A charge / discharge method using the magnesium secondary battery according to any one of claims 1 to 4 to perform charge / discharge at an operating temperature of 85 ° C or higher.
PCT/JP2016/056667 2015-03-06 2016-03-03 Magnesium secondary battery and charge/discharge method WO2016143675A1 (en)

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