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WO2020235615A1 - Batterie au magnésium - Google Patents

Batterie au magnésium Download PDF

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Publication number
WO2020235615A1
WO2020235615A1 PCT/JP2020/020028 JP2020020028W WO2020235615A1 WO 2020235615 A1 WO2020235615 A1 WO 2020235615A1 JP 2020020028 W JP2020020028 W JP 2020020028W WO 2020235615 A1 WO2020235615 A1 WO 2020235615A1
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group
carbon atoms
general formula
preferable
unsubstituted
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English (en)
Japanese (ja)
Inventor
和彦 里
水田　浩徳
訓明 岡本
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Fujifilm Wako Pure Chemical Corp
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Fujifilm Wako Pure Chemical Corp
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Priority to JP2021520831A priority Critical patent/JPWO2020235615A1/ja
Publication of WO2020235615A1 publication Critical patent/WO2020235615A1/fr
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • 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
    • H01M10/0567—Liquid materials characterised by the additives
    • 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
    • H01M10/0568—Liquid materials characterised by the solutes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
    • H01M4/46—Alloys based on magnesium or aluminium
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/54—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of silver
    • 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
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • 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 battery.
  • Magnesium has a large electric capacity per unit volume because its ions are multivalent ions. Magnesium has a higher melting point and is safer than lithium, and has the advantages of less bias in resource distribution on the earth, abundant resources, and low cost. Therefore, magnesium batteries with metallic magnesium as the negative electrode are attracting attention as next-generation batteries to replace lithium batteries.
  • magnesium batteries Although many examples of magnesium batteries have been reported to date, there are not many magnesium batteries that operate stably because it is difficult to diffuse magnesium ions after inserting the active material.
  • a magnesium battery capable of reversible insertion of magnesium ions a magnesium battery using a chevrel compound (Mo 6 S 8 ) as a positive electrode active material reported by Aurora et al. Is known (non-patented). Document 1).
  • Non-Patent Document 1 a magnesium battery in which charge transfer occurs through the movement of magnesium cations and halogen anions reported by Zhang et al. Is known (Non-Patent Document). 2).
  • the magnesium battery uses silver chloride (AgCl) as the positive electrode active material and operates at a high voltage of about 2.0 V (vs. Mg).
  • vs. Mg a silver chloride seawater cell using silver chloride as a positive electrode and a magnesium alloy as a negative electrode has been reported (Patent Document 1).
  • Non-Patent Document 3 a magnesium electrolyte using a non-nucleophilic magnesium salt
  • the magnesium battery described in Non-Patent Document 1 described above has a problem that the operating voltage is as low as about 1.1 V (vs. Mg), which is insufficient for practical use.
  • the magnesium battery described in Non-Patent Document 2 operates at a high voltage, there is a problem that the capacity decrease in each cycle is large when the charge / discharge rate is low.
  • the seawater battery described in Patent Document 1 has a problem that it is a primary battery in the first place and is not a battery (secondary battery) that can be repeatedly charged and discharged.
  • the magnesium battery using the electrolytic solution described in Non-Patent Document 3 did not have sufficient oxidative stability, and the battery operation was limited to an upper limit of about 1.7 V.
  • the present invention has been made in view of such circumstances, and an object of the present invention is to provide a magnesium battery that can be repeatedly charged and discharged with a high discharge capacity.
  • the present inventors have repeatedly produced a magnesium battery in which a positive electrode containing silver or a specific silver compound, a negative electrode containing a metallic magnesium or a magnesium alloy, and a specific electrolytic solution are combined. They have found that a high discharge capacity is maintained even when charging and discharging are performed, and have completed the present invention.
  • the present invention includes the following inventions [i] to [iv].
  • a magnesium battery provided with a positive electrode, a negative electrode, and an electrolytic solution.
  • the positive electrode contains silver or at least one silver compound selected from Ag O, Ag 2 O, Ag S or Ag 2 S.
  • the negative electrode contains metallic magnesium or a magnesium alloy and contains
  • the electrolytic solution is a mixture of a compound represented by any one of the following general formulas (I) to (IV), a Lewis acid or a compound represented by the following general formula (A), and a solvent.
  • a magnesium battery hereinafter, it may be abbreviated as the magnesium battery of the present invention: [In general formula (I), X 1 and X 2 independently represent chlorine or bromine atoms, respectively.
  • R 1 is -OMgCl group; -OMgBr group; alkyl group with 1 to 6 carbon atoms; alkoxy group with 1 to 6 carbon atoms; phenoxy group; 2 groups of -B (OMgCl) and -B (OMgBr) as substituents.
  • Y 1 represents a carbon atom or a silicon atom.
  • X 3 represents a chlorine atom or a bromine atom
  • R 2 represents an aryl group having 6 to 10 carbon atoms, which has a halogeno group, an alkyl group, a haloalkyl group or an alkoxy group as a substituent, or is unsubstituted.
  • R 3 and R 4 are independently -OMgCl group; -OMgBr group; having a halogeno group or an alkoxy group as a substituent, or an unsubstituted alkyl group having 1 to 6 carbon atoms; 2 to 6 carbon atoms.
  • Alkenyl group Alternatively, as a substituent, it represents an aryl group having 6 to 10 carbon atoms, which has a halogeno group, an alkyl group, a haloalkyl group or an alkoxy group, or is unsubstituted.
  • m 1 0 or 2
  • m 2 represents 2
  • X 4 represents a chlorine atom or a bromine atom
  • Two R 5 are each independently, -OMgCl group; -OMgBr group; as a substituent, having a halogeno group or alkoxy group, or unsubstituted, alkyl group having 1 to 6 carbon atoms; and 1 to 6 carbon atoms Alkoxy group; as a substituent, an aryl group having a halogeno group, an alkyl group, a haloalkyl group or an alkoxy group, or an unsubstituted, aryl group having 6 to 10 carbon atoms; as a substituent, a halogeno group, an alkyl group, a haloalkyl group or an alkoxy group.
  • a represents an integer of 1 to 3 and represents X 5 represents a chlorine atom or a bromine atom a number of R 6 each independently, -OMgCl group; -OMgBr group; as a substituent, having a halogeno group or alkoxy group, or unsubstituted, alkyl group having 1 to 6 carbon atoms; and 1 to 6 carbon atoms Alkoxy group; as a substituent, an aryl group having a halogeno group, an alkyl group, a haloalkyl group or an alkoxy group, or an unsubstituted, aryl group having 6 to 10 carbon atoms; or as a substituent, a halogeno group, an alkyl group, a haloalkyl group.
  • R 5 may form a following general formula (III-2): [In general formula (III-2), b represents an integer of 1 to 3, and R 6 is the same as above. ].
  • X 6 represents a chlorine atom or a bromine atom.
  • R 21 has a -SO 3 MgCl group or -SO 3 MgBr group as a substituent, or is an unsubstituted alkyl group having 1 to 10 carbon atoms; as a substituent, a -SO 3 MgCl group or -SO 3 MgBr Group- or unsubstituted haloalkyl group having 1 to 10 carbon atoms; as substituents, having a -SO 3 MgCl group, a -SO 3 MgBr group, a halogeno group, an alkyl group or an alkoxy group, or unsubstituted.
  • R 1 is -OMgCl group; -OMgBr group; alkyl group with 1 to 6 carbon atoms; alkoxy group with 1 to 6 carbon atoms; phenoxy group; 2 groups of -B (OMgCl) and -B (OMgBr) as substituents.
  • the magnesium battery of the present invention has an excellent effect of maintaining a high discharge capacity even when repeatedly charged and discharged.
  • the charge / discharge curves of the first, second, and third cycles in the charge / discharge test of Experimental Example 1 (1) are shown.
  • the charge / discharge curves of the first, second, and third cycles in the charge / discharge test of Experimental Example 1 (2) are shown.
  • the transition of the discharge capacity for each cycle in 1 to 10 cycles in the charge / discharge test of Experimental Example 1 (1) and Experimental Example 1 (2) is shown.
  • the charge / discharge curves of the first, second, and third cycles in the charge / discharge test of Experimental Example 2 (1) are shown.
  • the charge / discharge curves of the first, second, and third cycles in the charge / discharge test of Experimental Example 2 (2) are shown.
  • the transition of the discharge capacity for each cycle in 1 to 10 cycles in the charge / discharge test of Experimental Example 2 (1) and Experimental Example 2 (2) is shown.
  • the charge / discharge curves of the first, second, and third cycles in the charge / discharge test of Experimental Example 3 (1) are shown.
  • the charge / discharge curves of the first, second, and third cycles in the charge / discharge test of Experimental Example 3 (2) are shown.
  • the transition of the discharge capacity for each cycle in 1 to 10 cycles in the charge / discharge test of Experimental Example 3 (1) and Experimental Example 3 (2) is shown.
  • the charge / discharge curves of the first, second, and third cycles in the charge / discharge test of Experimental Example 4 (1) are shown.
  • the charge / discharge curves of the first, second, and third cycles in the charge / discharge test of Experimental Example 4 (2) are shown.
  • the transition of the discharge capacity for each cycle in 1 to 10 cycles in the charge / discharge test of Experimental Example 4 (1) and Experimental Example 4 (2) is shown.
  • the charge / discharge curves of the first, second, and third cycles in the charge / discharge test of Experimental Example 5 (1) are shown.
  • the charge / discharge curves of the first, second, and third cycles in the charge / discharge test of Experimental Example 5 (2) are shown.
  • the charge / discharge curves of the first, second, and third cycles in the charge / discharge test of Experimental Example 6 (1) are shown. Discharge every cycle in 1 to 10 cycles in the charge / discharge tests of Experimental Example 1 (1), Experimental Example 2 (1), Experimental Example 3 (1), Experimental Example 4 (1), and Experimental Example 6 (1). Shows the transition of capacity.
  • the positive electrode according to the present invention is used as the positive electrode of the magnesium battery of the present invention, and is silver or a silver compound selected from Ag O, Ag 2 O, Ag S or Ag 2 S (hereinafter referred to as silver or silver compound of the present invention). It may be abbreviated).
  • the positive electrode according to the present invention may contain only one type of silver or the silver compound of the present invention or may contain two or more types, and preferably contains only one type. Further, among the silver or silver compounds of the present invention, those containing a silver compound selected from Ag O, Ag 2 O, Ag S or Ag 2 S are preferable, and those containing Ag O, Ag 2 O, or a combination thereof are more preferable. ..
  • the silver or silver compound of the present invention may have an amorphous structure regardless of its crystal structure. Further, the crystal structure may be changed by physical or chemical treatment or occlusion / release of ions in the electrolytic solution, and it may be a part of the crystal structure instead of the whole. Further, the crystal structure may be changed and the peak position may be changed by the X-ray crystal structure analysis, or the process may be performed so that the change can be confirmed by XPS.
  • the particle size of the silver or silver compound of the present invention is not particularly limited, but is preferably 0.1 ⁇ m or more and 100 ⁇ m or less, and more preferably 1 ⁇ m or more and 50 ⁇ m or less.
  • a commercially available one or a compound appropriately synthesized by a method known per se may be used.
  • the positive electrode according to the present invention is a current collector, a conductive auxiliary agent, a binder, a supporting salt, and an ion conductor made of a substance other than the silver or the silver compound of the present invention, if necessary, in addition to the silver or the silver compound of the present invention. It may contain a sex polymer and / or other compounds. Specifically, the silver or silver compound of the present invention may be used as the positive electrode itself, or the silver of the present invention may be used as the positive electrode material layer having a current collector and a positive electrode material layer formed on the surface thereof.
  • a silver compound and, if necessary, a conductive auxiliary agent, a binder, a supporting salt, an ionic conductive polymer, and / or other compounds may be used.
  • those having the current collector and the positive electrode material layer formed on the surface thereof preferably contain the silver or silver compound of the present invention in the positive electrode material layer, and the positive electrode material layer of the present invention is used.
  • Those containing silver or a silver compound and a conductive auxiliary agent and a binder are preferable.
  • the content of silver or the silver compound of the present invention in the positive electrode according to the present invention is usually 30% by mass or more and 95% by mass or less, preferably 40% by mass or more and 90% by mass, based on the total mass of the materials forming the positive electrode material layer. It is mass% or less, more preferably 50 mass% or more and 85 mass% or less. When the positive electrode according to the present invention contains two or more kinds of silver or the silver compound of the present invention, the total mass thereof may be the content.
  • a known current collector usually used in this field can be used.
  • it is composed of conductive materials such as platinum, copper, stainless steel (SUS), hastelloy, aluminum, iron, chromium, nickel, titanium, inconel, molybdenum, graphite, and carbon, and is composed of plates, foils (sheets, etc.).
  • Examples thereof include current collectors having shapes such as paper), mesh, expanded grid (expanded metal), and punched metal.
  • the mesh opening, wire diameter, number of meshes, etc. of the current collector are not particularly limited.
  • the thickness of the current collector is not particularly limited, but is preferably 1 ⁇ m or more and 300 ⁇ m or less.
  • the size of the current collector is determined according to the intended use of the battery. If a large electrode used for a large battery is to be manufactured, a current collector having a large area is used, and if a small electrode is to be manufactured, a current collector having a small area is used.
  • a known conductive auxiliary agent usually used in this field can be used. Specific examples thereof include carbon blacks such as acetylene black, ketjen black, furnace black, and thermal black, and acetylene black is preferable.
  • the content of the conductive auxiliary agent is not particularly limited, but for example, it is usually 1% by mass or more and 50% by mass or less, preferably 5% by mass or more and 30% by mass or less, based on the total mass of the materials forming the positive electrode material layer. , More preferably 10% by mass or more and 20% by mass or less. When two or more kinds of conductive auxiliary agents are used in combination, the total mass of them may be the content.
  • binder for the positive electrode As the binder for the positive electrode according to the present invention, a known binder usually used in this field can be used. Specifically, for example, polyvinylidene fluoride (PVDF), polytetrafluoroethylene (PTFE), carboxymethyl cellulose (CMC), styrene-butadiene copolymer (SBR), acrylonitrile-butadiene copolymer (NBR), polyacrylonitrile (PAN). , Ethylene vinyl alcohol copolymer (EVOH), polyurethane, polyacrylate, polyvinyl ether, polyamide, polyimide and other binders.
  • PVDF polyvinylidene fluoride
  • PTFE polytetrafluoroethylene
  • CMC carboxymethyl cellulose
  • SBR styrene-butadiene copolymer
  • NBR acrylonitrile-butadiene copolymer
  • PAN polyacrylonitrile
  • the content of the binder is not particularly limited, but for example, it is usually 1% by mass or more and 50% by mass or less, preferably 5% by mass or more and 30% by mass or less, based on the total mass of the materials forming the positive electrode material layer. , More preferably 10% by mass or more and 20% by mass or less. When two or more kinds of binders are used in combination, the total mass of them may be the content.
  • Examples of the supporting salt in the positive electrode according to the present invention include Li (C 2 F 5 SO 2 ) 2 N (LiBETI), LiPF 6 , LiBF 4 , LiClO 4 , LiAsF 6 , LiCF 3 SO 3 and the like.
  • Examples of the ion conductive polymer in the positive electrode according to the present invention include polyethylene oxide (PEO) -based polymers and polypropylene oxide (PPO) -based polymers.
  • Examples of other compounds in the positive electrode according to the present invention include known active materials that are usually used as active materials in magnesium batteries (particularly magnesium secondary batteries). Specifically, for example, cobalt, manganese, vanadium, aluminum, iron, silicon, phosphorus, nickel, molybdenum, titanium, tungsten, ruthenium, copper, chromium, lithium, sodium, potassium, rubidium, cesium, beryllium, calcium, strontium, Barium, niobium, lanthanoid elements, carbon, sulfur, magnesium, platinum, hafnium, scandium, zirconium, osmium, iridium, gold, mercury, tarium, lead, tin, antimony; these oxides, sulfides, serenes, tellurides , Cyanide, halide, boronic, siliceous oxide, phosphorus oxide, booxide, manganese oxide, sulfate; or a compound salt thereof and the like.
  • active materials that are usually used as active materials in
  • molybdenum molybdenum; molybdenum oxides, sulfides, serenes, tellurides, cyanides, halides, boronides, siliceous oxides, phosphorus oxides, booxides, manganese oxides, sulfates; or these.
  • Double salt is preferred.
  • the other compound may be a combination of a plurality of metals and a plurality of compounds, may be doped with metals such as magnesium and potassium, and may be doped with sulfur, boron, phosphorus and the like, and may be a hydrate. There may be.
  • the inorganic active material include Mo 6 S 8 , V 2 O 5 , MnO 2 , Mn 2 O 3 , Mn 3 O 4 , and RuO 2. , TiO 2 , Co 3 O 4 , MoO 3 , Co 3 O 4 , CoO, CoO 2 , WO 3 , PbO 2 , Pb 3 O 4 , NiFe (CN) 6 , CuFe (CN) 6 , Ni [Fe (CN) ) 6 ] 0.7 ⁇ 4.7H 2 O, Cu [Fe (CN) 6 ] 0.7 ⁇ 3.6H 2 O, MgMo 6 S 8 , MgVPO 4 F, MgFePO 4 F, MgMnPO 4 F, MgFePO 4 , Mg 0.1 V 2 O 5 , MgNiO 2 , MgCoO 2 , MgCo 2 O 4 , TiNb 2 O 7 , MgMo 6 S 8 , MgVPO 4 F, MgFe
  • the above other compounds include, for example, sulfur; organic sulfur compounds; radical compounds; organic compounds; polymer compounds; sulfur-containing polymer compounds; radical polymers, as active materials capable of storing and releasing magnesium or magnesium ions.
  • a functional compound; a material for forming an electric double layer such as layered carbon, porous carbon, or activated carbon may be contained.
  • Such a material may contain magnesium in an oxidized form, or may be a mixture of sulfur, phosphorus, boron and the like. Furthermore, it may be in a form in which a part is halogenated.
  • organic active material examples include rubian acid, 2,5-dimercapto-1,3,4-thiadiazole (DMcT), and trioxotriangulene.
  • TEMPO 2,2,6,6-tetramethyl-1-piperidinyloxy
  • dimethoxybenzoquinone (DMBQ) dimethoxybenzoquinone
  • DMBQ dimethoxybenzoquinone
  • 9,10-anthraquinone porphyrin, magnesium porphyrin, phthalocyanine, phthalocyanine magnesium, magnesium anthracene
  • Poly hydroquinoyl-benzoquinonyl sulfide
  • Carbyne polysulfide poly-2,2' -dithiodianiline (PDTDA)
  • the contents of the supporting salt, the ionic conductive polymer, and other compounds may be appropriately set with respect to the total mass of the material forming the positive electrode material layer according to the amount usually used in this field. ..
  • the current collector, the conductive auxiliary agent, the binder, the supporting salt, the ionic conductive polymer, and the other compounds may all be commercially available or appropriately synthesized by a method known per se.
  • the positive electrode according to the present invention may be produced according to a method known per se, and specific production methods include, for example, the silver or silver compound of the present invention, and if necessary, the above-mentioned conductive auxiliary agent and binder. , Supporting salt, ionic conductive polymer, and / or other compounds are appropriately mixed to prepare a composition for forming a positive electrode material layer, and then the composition is applied or pressure-bonded onto a current collector. It can be produced by drying and forming a positive electrode material layer on the current collector.
  • the composition may be made into a paste or a slurry by using an appropriate solvent when preparing the composition for forming the positive electrode material layer.
  • the solvent include water, N-methyl-2-pyrrolidone (NMP), dimethylformamide, dimethylacetamide, methylformamide, dimethyl sulfoxide, acetonitrile, tetrahydrofuran, ⁇ -butyrolactone, toluene, methylethylketone, ethyl acetate, dioxane and the like.
  • NMP N-methyl-2-pyrrolidone
  • dimethylformamide dimethylacetamide
  • methylformamide dimethyl sulfoxide
  • acetonitrile acetonitrile
  • tetrahydrofuran ⁇ -butyrolactone
  • toluene methylethylketone
  • ethyl acetate dioxane and the like.
  • Water and NMP are preferred.
  • the amount of the composition used for forming the positive electrode material layer may be appropriately set so that the positive electrode material layer after drying has a desired thickness.
  • the thickness of the positive electrode material layer (thickness of the coating layer on the current collector) in the positive electrode according to the present invention is not particularly limited, but is usually 1 ⁇ m or more and 1000 ⁇ m or less, preferably 1 ⁇ m or more and 500 ⁇ m or less, and 1 ⁇ m or more and 300 ⁇ m or less. More preferred.
  • the composition for forming the positive electrode material layer may be applied onto the current collector according to a method known per se, and specific application methods include, for example, self-propelled.
  • a mold coater, an inkjet method, a doctor blade method, a spray method, or a combination thereof may be used.
  • the composition for forming the positive electrode material layer may be dried according to a method known per se, and is usually heat-treated.
  • the drying conditions at the time of heating may be appropriately set according to the coating amount and the volatilization rate of the composition for forming the positive electrode material layer.
  • it is usually dried in a vacuum at 50 ° C. or higher and 150 ° C. or lower, preferably 70 ° C. or higher and 130 ° C. or lower, usually 1 hour or longer and 20 hours or shorter, preferably 3 hours or longer and 12 hours or shorter. Good.
  • a press treatment may be performed after drying.
  • the press treatment may be performed according to a method known per se, and specific press methods include, for example, a calendar roll method, a flat plate press, and the like, and the calendar roll method is preferable.
  • the negative electrode according to the present invention is used as a negative electrode in the magnesium battery of the present invention, and contains metallic magnesium or a magnesium alloy.
  • the negative electrode according to the present invention may contain only one type of metallic magnesium or magnesium alloy, or may contain two or more types, and preferably contains only one type. Further, those containing metallic magnesium are preferable.
  • the metallic magnesium or magnesium alloy may be used as a current collector or as a negative electrode active material.
  • the magnesium alloy in the negative electrode according to the present invention may be any material that can occlude and release magnesium ions, and a known magnesium alloy usually used in this field can be used. Specifically, for example, Mg-Bi alloy, Mg-Sb alloy, Mg-In alloy, Mg-Zn alloy, Mg-Zr alloy, Mg-Sn alloy, Mg-Cd alloy, Mg-Co alloy, Mg-Mn alloy.
  • Mg-Zn-Zr alloys examples include Mg-Zn-Zr alloys, Mg-In-Ni alloys, and alloys containing rare earth elements.
  • the negative electrode according to the present invention includes a current collector, a conductive auxiliary agent, a binder, a supporting salt, an ionic conductive polymer, and if necessary, a substance other than the metallic magnesium or the magnesium alloy, in addition to the metallic magnesium or the magnesium alloy. / Or other compounds may be included.
  • a metallic magnesium or magnesium alloy may be used as the negative electrode itself, or a metal magnesium or magnesium alloy may be used as the negative electrode material layer having a current collector and a negative electrode material layer formed on the surface thereof.
  • a conductive auxiliary agent, a binder, a supporting salt, an ionic conductive polymer, and / or other compounds may be used.
  • the content of the metallic magnesium or magnesium alloy in the negative electrode according to the present invention is at least 50% by mass or more with respect to the total mass of the materials forming the negative electrode material layer. It is preferably 80% by mass or more, more preferably 90% by mass or more.
  • the negative electrode according to the present invention contains two or more kinds of metallic magnesium or magnesium alloy, the total mass of them may be the content.
  • the method for producing the negative electrode according to the present invention may be the same as the method for producing the positive electrode according to the present invention.
  • X 1 and X 2 of the general formula (I) are chlorine atoms or bromine atoms, and chlorine atoms are preferable.
  • the alkyl group having 1 to 6 carbon atoms in R 1 of the general formula (I) may be any of linear, branched and cyclic, preferably linear and branched, and linear. The shape is more preferable. Further, among the alkyl groups having 1 to 6 carbon atoms, those having 1 to 4 carbon atoms are preferable, and those having 1 or 2 carbon atoms are more preferable. Specific examples thereof include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, n-pentyl group, n-hexyl group and the like.
  • Methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group are preferable, and methyl group, ethyl group, n-propyl group, n-butyl group are preferable.
  • a group is more preferable, a methyl group and an ethyl group are further preferable, and a methyl group is particularly preferable.
  • the alkoxy group having 1 to 6 carbon atoms in R 1 of the general formula (I) may be any of linear, branched and cyclic, preferably linear and branched, and linear. The shape is more preferable. Further, among the alkoxy groups having 1 to 6 carbon atoms, those having 1 to 4 carbon atoms are preferable, and those having 1 or 2 carbon atoms are more preferable. Specifically, for example, methoxy group, ethoxy group, n-propoxy group, isopropoxy group, n-butoxy group, isobutoxy group, sec-butoxy group, tert-butoxy group, n-pentyloxy group, n-hexyloxy group.
  • Etc. and methoxy group, ethoxy group, n-propoxy group, isopropoxy group, n-butoxy group, isobutoxy group, sec-butoxy group, tert-butoxy group are preferable, and methoxy group, ethoxy group, n-propoxy group , N-Butoxy group is more preferable, methoxy group and ethoxy group are more preferable, and methoxy group is particularly preferable.
  • Examples of the aryl group having 6 to 18 carbon atoms in R 1 of the general formula (I) include a phenyl group, a naphthyl group, an anthracenyl group and the like, and a phenyl group and a naphthyl group are preferable, and a phenyl group is more preferable.
  • halogeno group as a substituent of the aryl group having 6 to 18 carbon atoms in R 1 of the general formula (I) include a fluoro group, a chloro group, a bromo group and an iodo group, and a fluoro group is preferable.
  • the alkyl group as a substituent of the aryl group having 6 to 18 carbon atoms in R 1 of the general formula (I) is usually 1 to 6 carbon atoms, preferably 1 to 4 carbon atoms, and has 1 or 2 carbon atoms. The one is more preferable. Further, it may be linear, branched or cyclic, and linear or branched is preferable, and linear is more preferable. Specifically, the same examples as those of the alkyl group having 1 to 6 carbon atoms in R 1 of the general formula (I) can be mentioned, and the preferred ones are also the same.
  • the alkoxy group as a substituent of the aryl group having 6 to 18 carbon atoms in R 1 of the general formula (I) is usually 1 to 6 carbon atoms, preferably 1 to 4 carbon atoms, and has 1 or 2 carbon atoms. The one is more preferable. Further, it may be linear, branched or cyclic, and linear or branched is preferable, and linear is more preferable. Specifically, the same examples as the specific examples of the alkoxy groups having 1 to 6 carbon atoms in R 1 of the general formula (I) can be mentioned, and the preferred ones are also the same.
  • the substituent in R 1 of the general formula (I) has two -B (OMgCl) groups, two -B (OMgBr) groups, a halogeno group, an alkyl group, an alkoxy group, a vinyl group, a phenyl group or a phenoxy group.
  • Specific examples of the "unsubstituted aryl group having 6 to 18 carbon atoms” include, for example, the groups represented by the following general formulas (I-1) to (I-3), and the general formula (I-1). ) Or the group represented by (I-2) is preferable, and the group represented by the general formula (I-1) is more preferable.
  • R 8 represents two -B (OMgCl) groups, two -B (OMgBr) groups, a halogeno group, an alkyl group, an alkoxy group, a vinyl group, a phenyl group or a phenoxy group.
  • n 1 represents an integer from 0 to 5.
  • n 2 represents an integer from 0 to 7
  • R 8 is the same as above.
  • n 3 represents an integer from 0 to 9, and R 8 is the same as above.
  • halogeno group, alkyl group and alkoxy group in R 8 of the general formulas (I-1) to (I-3) are used as the substituent of the aryl group having 6 to 18 carbon atoms in R 1 of the general formula (I). The same ones are mentioned, and so are the preferred ones.
  • R 8 of the general formulas (I-1) to (I-3) includes 2 -B (OMgCl) groups, 2 -B (OMgBr) groups, a halogeno group, an alkyl group having 1 to 6 carbon atoms, and 1 carbon group.
  • Alkoxy group, vinyl group, phenyl group, phenoxy group of ⁇ 6 are preferable; -B (OMgCl) 2 group, -B (OMgBr) 2 group, fluoro group, chloro group, bromo group, iodo group, linear carbon Alkoxy groups with 1 to 4 alkyl groups, linear alkoxy groups with 1 to 4 carbon atoms, vinyl groups, phenyl groups, and phenoxy groups are more preferable; -B (OMgCl) 2 groups, -B (OMgBr) 2 groups, fluoro Groups, methyl groups, ethyl groups, methoxy groups, ethoxy groups, phenyl groups, phenoxy groups are more preferred; -B (OMgCl) 2 groups, fluoro groups, methyl groups, methoxy groups, phenyl groups, phenoxy groups are particularly preferred.
  • n 1 of the general formula (I-1) an integer of 0 to 3 is preferable, an integer of 0 to 2 is more preferable, and 0 is particularly preferable.
  • n 2 of the general formula (I-2) an integer of 0 to 3 is preferable, and 0 is more preferable.
  • n 3 of the general formula (I-3) an integer of 0 to 3 is preferable, and 0 is more preferable.
  • Preferred specific examples of the group represented by the general formula (I-1) include, for example, phenyl group; -C 6 H 4 -B (OMgCl) 2 groups, -C 6 H 4 -B (OMgBr) 2 groups; fluoro.
  • Preferred specific examples of the group represented by the general formula (I-2) include, for example, a naphthyl group; -C 10 H 6 -B (OMgCl) 2 groups, -C 10 H 6 -B (OMgBr) 2 groups; fluoro.
  • Preferred specific examples of the group represented by the general formula (I-3) include, for example, anthrasenyl group; -C 14 H 8 -B (OMgCl) 2 group, -C 14 H 8 -B (OMgBr) 2 group; fluoro.
  • Anthracenyl group difluoroanthrasenyl group, trifluoroanthrasenyl group; methylanthrasenyl group, dimethylanthrasenyl group, trimethylanthrasenyl group, ethylanthrasenyl group, diethylanthrasenyl group, triethylanthrase Nyl group; methoxyanthrasenyl group, dimethoxyanthrasenyl group, trimethoxyanthrasenyl group, ethoxyanthrasenyl group, diethoxyanthrasenyl group, triethoxyanthrasenyl group; phenylanthrasenyl group; phenoxyanthra Examples thereof include a senyl group, and an anthrasenyl group is more preferable.
  • Examples of the monocyclic heterocyclic group in R 1 of the general formula (I) include a 5- to 6-membered monocyclic heterocyclic group.
  • Examples of the hetero atom contained in the monocyclic heterocyclic group include a nitrogen atom, an oxygen atom, a sulfur atom and the like, and an oxygen atom and a sulfur atom are preferable, and an oxygen atom is more preferable.
  • the number of heteroatoms contained in the monocyclic heterocyclic group is 1 or more, preferably 1 to 2, and more preferably 1.
  • a 5-membered heterocyclic group having one heteroatom such as furan, thiophene, pyrrole, 2H-pyrrole, 1-pyrrolin, 2-pyrrolin, 3-pyrrolin, pyrrolidine; oxazole, isooxazole. , Thiazol, isothiazole, imidazole, pyrazole, imidazoline, imidazolidine, 1-pyrazolin, 2-pyrazolin, 3-pyrazolin, pyrazolidine, etc.
  • 5-membered heterocyclic group with two heteroatoms Frazan, triazole, oxa 5-membered heterocyclic group with 3 heteroatoms such as diazole, thiadiazol; 5-membered heterocyclic group with 4 heteroatoms such as tetrazole; 2H-pyran, 4H-pyran, thiopyran, pyridine , 6-membered ring heterocyclic group having 1 heteroatom such as piperidine; 6-membered ring heterocyclic group having 2 heteroatoms such as pyridazine, pyrimidine, pyrazine, piperazine, morpholin; 3 such as triazine Examples thereof include a 6-membered heterocyclic group having the above heteroatom.
  • a 5- to 6-membered heterocyclic group having 1 to 2 heteroatoms is preferable, and a 5- to 6-membered unsaturated ring having 1 to 2 heteroatoms (having a double bond) is preferable.
  • Heterocyclic groups are more preferred, furans, thiophenes, pyrroles, oxazoles, isoxazoles, thiazoles, isothiazoles, imidazoles, pyrazoles, pyridines, pyridazines, pyrimidines, pyrazines are even more preferred, furans, thiophenes, pyrroles, pyridines are even more preferred.
  • Furan is particularly preferred.
  • the bicyclic heterocyclic group in R 1 of the general formula (I) is a bicyclic heterocyclic group in which 5- to 6-membered monocyclic heterocycles are condensed with each other, and a 5- to 6-membered monocyclic heterocyclic group.
  • Examples thereof include a bicyclic heterocyclic group in which a ring and benzene are condensed.
  • the hetero atom contained in the bicyclic heterocyclic group include a nitrogen atom, an oxygen atom, a sulfur atom and the like, and an oxygen atom and a sulfur atom are preferable, and an oxygen atom is more preferable.
  • the number of heteroatoms contained in the bicyclic heterocyclic group is 1 or more, preferably 1 to 2, and more preferably 1.
  • a 5-membered monocyclic ring having one heteroatom such as benzofuran, isobenzofuran, 1-benzothiophene, 2-benzothiophene, indol, isoindole, indolin, isoindrin, and indridin.
  • a bicyclic heterocycle in which a 5-membered monocyclic heterocycle having one heteroatom and benzene are condensed is preferable, and benzofuran, isobenzofuran, 1-benzothiophene, 2-benzothiophene, indole, and isoindole are preferable. Is more preferred, and benzofuran is particularly preferred.
  • the bicyclic heterocyclic group contains a benzene ring, the substituent is preferably located on the benzene ring.
  • the substituent in R 1 of the general formula (I) has two -B (OMgCl) groups, two -B (OMgBr) groups, a halogeno group, an alkyl group, an alkoxy group, a vinyl group, a phenyl group or a phenoxy group.
  • Specific examples of the "unsubstituted, monocyclic or bicyclic heterocyclic group” include groups represented by the following general formulas (I-4) to (I-7), and the general formula (I-) can be mentioned. 4), The group represented by (I-5) or (I-7) is preferable, the group represented by the general formula (I-4) or (I-5) is more preferable, and the group represented by the general formula (I-4) is preferable.
  • R 9 represents two -B (OMgCl) groups, two -B (OMgBr) groups, a halogeno group, an alkyl group, an alkoxy group, a vinyl group, a phenyl group or a phenoxy group.
  • Y 2 represents an oxygen atom, a sulfur atom or a -NR 10 -group (R 10 represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms), and n 4 represents an integer of 0 to 3.
  • n 5 represents an integer from 0 to 4, and R 9 is the same as above.
  • n 6 represents an integer from 0 to 5, and R 9 and Y 2 are the same as above.
  • n 7 represents an integer from 0 to 5, and R 9 and Y 2 are the same as above.
  • halogeno group, alkyl group, alkoxy group, vinyl group, phenyl group and phenoxy group in R 9 of the general formulas (I-4) to (I-7) have 6 to 6 carbon atoms in R 1 of the general formula (I).
  • substituents on the 18 aryl groups are mentioned, and so are the preferred ones.
  • R 9 in the general formulas (I-4) to (I-7) include the same preferred ones in R 8 in the general formulas (I-1) to (I-3).
  • the alkyl group having 1 to 6 carbon atoms in R 10 in the -NR 10 -group has the carbon number in R 1 of the general formula (I).
  • the same as the alkyl groups 1 to 6 can be mentioned, and the preferred ones are also the same.
  • R 10 in the -NR 10 -group a hydrogen atom, a methyl group and an ethyl group are preferable, and a hydrogen atom and a methyl group are more preferable.
  • a hydrogen atom is particularly preferred. That is, as the -NR 10 -group in Y 2 of the general formulas (I-4) to (I-7), -NH- group, -NCH 3- group, and -NC 2 H 5- group are preferable, and -NH. -Group, -NCH 3 -group is more preferable, and -NH- group is particularly preferable.
  • an oxygen atom and a sulfur atom are preferable, and an oxygen atom is more preferable.
  • n 4 of the general formula (I-4) an integer of 0 to 2 is preferable, and 0 is more preferable.
  • n 5 of the general formula (I-5) an integer of 0 to 2 is preferable, and 0 is more preferable.
  • n 6 in the general formula (I-6) an integer of 0 to 2 is preferable, and 0 is more preferable.
  • n 7 of the general formula (I-7) an integer of 0 to 2 is preferable, and 0 is more preferable.
  • Preferred specific examples of the groups represented by the general formulas (I-4) to (I-7) include groups represented by the following general formulas (I-4') to (I-7').
  • the group represented by the general formula (I-4'), (I-5') or (I-7') is preferable, and the group represented by the general formula (I-4') or (I-5') is more preferable.
  • the group represented by the general formula (I-4') is particularly preferable.
  • Y 2 is the same as above.
  • R 1 of the general formula (I) includes a -OMgCl group, a -OMgBr group, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, a phenoxy group, and general formulas (I-1) to (I).
  • the groups represented by -3) and the groups represented by the general formulas (I-4) to (I-7) are preferable; -OMgCl group, -OMgBr group, linear alkyl group having 1 to 4 carbon atoms, direct group. Alkoxy groups having 1 to 4 carbon atoms in a chain, phenoxy groups, groups represented by general formulas (I-1) to (I-3), represented by general formulas (I-4') to (I-7').
  • -OMgCl group -OMgBr group
  • methoxy group ethoxy group, n-propoxy group, n-butoxy group
  • phenoxy group phenyl.
  • -OMgCl group methyl group, ethyl group, methoxy group, ethoxy group, phenoxy group, phenyl group, -C 6 H 4 -B (OMgCl) 2 group, fluorophenyl group, difluorophenyl group, trill Group, xsilyl group, methoxyphenyl group, dimethoxyphenyl group, biphenyl group, phenoxyphenyl group, naphthyl group, anthracenyl group, the following groups are preferable; -OMgCl group, phenyl group is more preferable; -OMgCl group is particularly preferable.
  • Preferred specific examples of the compound represented by the general formula (I) include, for example, the compound represented by the following general formula (I').
  • R 11 is a -OMgCl group, a -OMgBr group, a linear alkyl group having 1 to 4 carbon atoms, a linear alkoxy group having 1 to 4 carbon atoms, a phenoxy group, and the like.
  • X 1 and X 2 are as described above. the same.
  • a methyl group and an ethyl group are preferable, and a methyl group is more preferable.
  • a methoxy group and an ethoxy group are preferable, and a methoxy group is more preferable.
  • R 11 of the general formula (I') includes -OMgCl group, methyl group, ethyl group, methoxy group, ethoxy group, phenoxy group, phenyl group, -C 6 H 4 -B (OMgCl) 2 group, fluorophenyl group. , Difluorophenyl group, trill group, xsilyl group, methoxyphenyl group, dimethoxyphenyl group, biphenyl group, phenoxyphenyl group, naphthyl group, anthracenyl group, the following groups are preferable; -OMgCl group, phenyl group is more preferable; -OMgCl Groups are particularly preferred.
  • Specific examples of the compound represented by the general formula (I') include the following compounds, among which B (OMgCl) 3 , C 6 H 5 B (OMgCl) 2 are preferable, and B (OMgCl) 3 Is more preferable.
  • Y 1 of the general formula (II) is a carbon atom or a silicon atom, and a silicon atom is preferable.
  • X 3 of the general formula (II) is a chlorine atom or a bromine atom, and a chlorine atom is preferable.
  • Examples of the alkyl group having 1 to 6 carbon atoms in R 3 and R 4 of the general formula (II) include the same alkyl group having 1 to 6 carbon atoms in R 1 of the general formula (I), and preferable ones are also used. It is the same.
  • halogeno group as a substituent of the alkyl group having 1 to 6 carbon atoms in R 3 and R 4 of the general formula (II) include a fluoro group, a chloro group, a bromo group and an iodo group, and the fluoro group is included. preferable.
  • Alkyl groups having 1 to 6 carbon atoms having a halogeno group as a substituent in R 3 and R 4 of the general formula (II) are those in which 1 to 13 hydrogen atoms on the alkyl group are substituted with a halogeno group.
  • 1 to 3 or all hydrogen atoms are preferably substituted with a halogeno group, more preferably 1 or all hydrogen atoms are substituted with a halogeno group, and all hydrogen atoms are substituted with a halogeno group.
  • Those substituted with (perhaloalkyl group) are particularly preferable.
  • the halogeno group may be bonded to any of the carbon atoms constituting the alkyl group, and those bonded to the carbon atom at the end of the alkyl group are preferable.
  • alkyl group having 1 to 6 carbon atoms having a halogeno group as a substituent in R 3 and R 4 of the general formula (II) include, for example, a trifluoromethyl group, a pentafluoroethyl group, and a heptafluoro-n-.
  • Examples thereof include a group, a fluoroisopropyl group, a fluoro-n-butyl group, a fluoroisobutyl group, a fluoro-sec-butyl group, and a fluoro-tert-butyl group.
  • trifluoromethyl group pentafluoroethyl group, heptafluoro-n-propyl group, heptafluoroisopropyl group, perfluoro-n-butyl group, perfluoroisobutyl group, perfluoro-sec-butyl group, perfluoro-tert -Butyl group is preferable, trifluoromethyl group, pentafluoroethyl group, heptafluoro-n-propyl group and perfluoro-n-butyl group are more preferable, and trifluoromethyl group is particularly preferable.
  • the alkoxy group as a substituent of the alkyl group having 1 to 6 carbon atoms in R 3 and R 4 of the general formula (II) is usually 1 to 6 carbon atoms, preferably 1 to 4 carbon atoms, and 1 carbon atom. Or 2 is more preferable. Further, it may be linear, branched or cyclic, and linear or branched is preferable, and linear is more preferable. Specifically, the same examples as the specific examples of the alkoxy groups having 1 to 6 carbon atoms in R 1 of the general formula (I) can be mentioned, and the preferred ones are also the same.
  • the number of substituents of the alkyl group having 1 to 6 carbon atoms having an alkoxy group as the substituent in R 3 and R 4 of the general formula (II) is usually 1 to 3, preferably 1.
  • the alkoxy group may be bonded to any of the carbon atoms constituting the alkyl group, and is preferably bonded to the carbon atom at the end of the alkyl group.
  • an alkyl group having 1 to 6 carbon atoms having an alkoxy group as a substituent in R 3 and R 4 of the general formula (II) include, for example, a methoxymethyl group, an ethoxymethyl group, an n-propoxymethyl group, and an iso.
  • methoxymethyl group, ethoxymethyl group, methoxyethyl group, ethoxyethyl group, methoxy-n-propyl group, ethoxy-n-propyl group, methoxy-n-butyl group and ethoxy-n-butyl group are preferable, and methoxymethyl A group, an ethoxymethyl group, a methoxyethyl group, and an ethoxyethyl group are more preferable.
  • the "alkyl group having 1 to 6 carbon atoms having a halogeno group or an alkoxy group as a substituent or not substituted" includes a halogeno group or carbon as a substituent.
  • Preferred is an alkyl group having 1 to 6 carbon atoms which has an alkoxy group of 1 to 6 or is unsubstituted; the substituent has a fluoro group or a linear alkoxy group having 1 to 4 carbon atoms or is not substituted.
  • Substitutable alkyl groups with 1 to 6 carbon atoms are more preferred; unsubstituted alkyl groups with 1 to 6 carbon atoms are even more preferred; unsubstituted alkyl groups with 1 to 4 carbon atoms are particularly preferred.
  • an alkyl group having 1 to 6 carbon atoms having a halogeno group or an alkoxy group as a substituent or not substituted include, for example, a methyl group.
  • methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group and tert-butyl group are preferable, and methyl group, ethyl group, n-propyl group and n-butyl group are preferable.
  • a group is more preferable, a methyl group and an ethyl group are further preferable, and a methyl group is particularly preferable.
  • the alkenyl group having 2 to 6 carbon atoms in R 3 and R 4 of the general formula (II) may be any of linear, branched and cyclic, preferably linear and branched. , Linear is more preferable. Further, among the alkenyl groups having 2 to 6 carbon atoms, those having 2 to 3 carbon atoms are preferable.
  • Vinyl group, allyl group, 1-propenyl group, isopropenyl group are preferable, and allyl group is more preferable.
  • Examples of the aryl group having 6 to 10 carbon atoms in R 2 to R 4 of the general formula (II) include a phenyl group and a naphthyl group, and a phenyl group is preferable.
  • halogeno group as a substituent of the aryl group having 6 to 10 carbon atoms in R 2 to R 4 of the general formula (II) include a fluoro group, a chloro group, a bromo group and an iodo group, and the fluoro group is included. preferable.
  • the alkyl group as a substituent of the aryl group having 6 to 10 carbon atoms in R 2 to R 4 of the general formula (II) is usually 1 to 6 carbon atoms, preferably 1 to 4 carbon atoms, and 1 carbon atom. Or 2 is more preferable. Further, it may be linear, branched or cyclic, and linear or branched is preferable, and linear is more preferable. Specifically, the same examples as those of the alkyl group having 1 to 6 carbon atoms in R 1 of the general formula (I) can be mentioned, and the preferred ones are also the same.
  • the haloalkyl group as a substituent of the aryl group having 6 to 10 carbon atoms in R 2 to R 4 of the general formula (II) usually has 1 to 6 carbon atoms, preferably 1 to 4 carbon atoms, and 1 carbon atom. Or 2 is more preferable. Further, it may be linear, branched or cyclic, and linear or branched is preferable, and linear is more preferable.
  • a fluoroalkyl group examples thereof include a fluoroalkyl group, a chloroalkyl group, a bromoalkyl group and an iodoalkyl group, and a fluoroalkyl group is preferable, among which a perfluoroalkyl group and a monofluoroalkyl group are more preferable, and a perfluoroalkyl group is preferable. Especially preferable. More specifically, the same examples as those of the alkyl group having 1 to 6 carbon atoms having a halogeno group as the substituent in R 3 and R 4 of the general formula (II) can be mentioned, and the preferred ones are also the same.
  • the alkoxy group as a substituent of the aryl group having 6 to 10 carbon atoms in R 2 to R 4 of the general formula (II) is usually 1 to 6 carbon atoms, preferably 1 to 4 carbon atoms, and 1 carbon atom. Or 2 is more preferable. Further, it may be linear, branched or cyclic, and linear or branched is preferable, and linear is more preferable. Specifically, the same examples as the specific examples of the alkoxy groups having 1 to 6 carbon atoms in R 1 of the general formula (I) can be mentioned, and the preferred ones are also the same.
  • the number of substituents of the "aryl group having 6 to 10 carbon atoms having a halogeno group, an alkyl group, a haloalkyl group or an alkoxy group as the substituent" in R 2 to R 4 of the general formula (II) is usually 1. It is ⁇ 7, preferably 1-5, more preferably 1-2, and particularly preferably 1.
  • the aryl group may have a substituent at any position.
  • the aryl group is a phenyl group
  • the phenyl group may have a substituent at any of the ortho-position, meta-position, and para-position; when the phenyl group has one substituent.
  • the one having a substituent at the para position is preferable; when the phenyl group has two substituents, the one having a substituent at the meta position is preferable.
  • R 2 to R 4 of the general formula (II) the "aryl group having a halogeno group, an alkyl group, a haloalkyl group or an alkoxy group as a substituent, or an unsubstituted aryl group having 6 to 10 carbon atoms" is a substituent.
  • a phenyl group having a halogeno group, an alkyl group having 1 to 6 carbon atoms, a haloalkyl group having 1 to 6 carbon atoms or an alkoxy group having 1 to 6 carbon atoms, or an unsubstituted phenyl group is preferable; as a substituent, a fluoro group , A phenyl group having an alkyl group having 1 to 4 carbon atoms, a perfluoroalkyl group having 1 to 4 carbon atoms or an alkoxy group having 1 to 4 carbon atoms, or being unsubstituted is more preferable; as a substituent, a fluoro group, A phenyl group having a linear alkyl group having 1 to 4 carbon atoms or a linear alkoxy group having 1 to 4 carbon atoms or having no substituent is more preferable; an unsubstituted phenyl group is particularly preferable.
  • an aryl group having 6 to 10 carbon atoms which has a halogeno group, an alkyl group, a haloalkyl group or an alkoxy group as a substituent, or is unsubstituted
  • R 2 to R 4 of the general formula (II) a group represented by the following general formula (II-1) can be mentioned.
  • R 12 represents a halogeno group, an alkyl group having 1 to 6 carbon atoms, a haloalkyl group having 1 to 6 carbon atoms, or an alkoxy group having 1 to 6 carbon atoms
  • n 8 is 0. Represents an integer of ⁇ 5.
  • halogeno group, alkyl group, haloalkyl group and alkoxy group in R 12 of the general formula (II-1) can be used as a substituent of the aryl group having 6 to 10 carbon atoms in R 2 to R 4 of the general formula (II-1). The same ones are mentioned, and so are the preferred ones.
  • a fluoro group, an alkyl group having 1 to 4 carbon atoms, a perfluoroalkyl group having 1 to 4 carbon atoms, and an alkoxy group having 1 to 4 carbon atoms are preferable; a fluoro group, A linear alkyl group having 1 to 4 carbon atoms and a linear alkoxy group having 1 to 4 carbon atoms are more preferable; a fluoro group, a methyl group, an ethylphenyl group, a methoxy group and an ethoxy group are further preferable.
  • n 8 of the general formula (II-1) an integer of 0 to 3 is preferable, an integer of 0 to 2 is more preferable, and 0 is particularly preferable.
  • Preferred specific examples of the group represented by the general formula (II-1) include, for example, phenyl group; fluorophenyl group, difluorophenyl group; trill group, ethylphenyl group, n-propylphenyl group, n-butylphenyl group, and the like.
  • Xylyl group diethylphenyl group, di-n-propylphenyl group, di-n-butylphenyl group, mesityl group; methoxyphenyl group, ethoxyphenyl group, n-propoxyphenyl group, n-butoxyphenyl group, dimethoxyphenyl group, Examples thereof include diethoxyphenyl group, di-n-propoxyphenyl group, di-n-butoxyphenyl group, phenyl group, fluorophenyl group, difluorophenyl group, trill group, ethylphenyl group, xsilyl group, diethylphenyl group, A methoxyphenyl group, an ethoxyphenyl group, a dimethoxyphenyl group, and a diethoxyphenyl group are more preferable, and a phenyl group is particularly preferable.
  • R 3 and R 4 of the general formula (II) include -OMgCl group; -OMgBr group; unsubstituted alkyl group having 1 to 6 carbon atoms; alkenyl group having 2 to 6 carbon atoms; and halogeno group as the substituent.
  • An alkyl group having 1 to 6 carbon atoms, a haloalkyl group having 1 to 6 carbon atoms or an alkoxy group having 1 to 6 carbon atoms, or an unsubstituted phenyl group is preferable, and a -OMgCl group; a -OMgBr group; an unsubstituted Alkyl group having 1 to 4 carbon atoms; Alkenyl group having 2 to 3 carbon atoms; Fluoro group, alkyl group having 1 to 4 carbon atoms, perfluoroalkyl group having 1 to 4 carbon atoms or 1 to 4 carbon atoms as substituents.
  • a phenyl group having or not substituted of the alkoxy group of is more preferable.
  • -OMgCl group -OMgBr group
  • methyl group ethyl group, n-propyl group, n-butyl group, vinyl group, allyl group, 1-propenyl group, isopropenyl group, phenyl group, fluorophenyl.
  • difluorophenyl group trill group, ethylphenyl group, n-propylphenyl group, n-butylphenyl group, xsilyl group, diethylphenyl group, di-n-propylphenyl group, di-n-butylphenyl group, mesityl group , Methoxyphenyl group, ethoxyphenyl group, n-propoxyphenyl group, n-butoxyphenyl group, dimethoxyphenyl group, diethoxyphenyl group, di-n-propoxyphenyl group, di-n-butoxyphenyl group and the like.
  • -OMgCl group methyl group, ethyl group, allyl group, phenyl group, fluorophenyl group, difluorophenyl group, trill group, ethylphenyl group, xsilyl group, diethylphenyl group, methoxyphenyl group, ethoxyphenyl group, dimethoxyphenyl A group and a diethoxyphenyl group are preferable, and a -OMgCl group, a methyl group, an allyl group, a phenyl group, a fluorophenyl group, a trill group, a xsilyl group, a methoxyphenyl group and a dimethoxyphenyl group are more preferable.
  • Preferred specific examples of the compound represented by the general formula (II) include, for example, the compound represented by the following general formula (II').
  • R 13 and R 14 are independently -OMgCl group, -OMgBr group, unsubstituted alkyl group having 1 to 4 carbon atoms, alkenyl group having 2 to 3 carbon atoms, or the above.
  • the unsubstituted alkyl groups having 1 to 4 carbon atoms in R 13 and R 14 of the general formula (II') include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group and sec. -Butyl group, tert-butyl group and the like can be mentioned, with methyl group, ethyl group, n-propyl group and n-butyl group being preferable, methyl group and ethyl group being more preferable, and methyl group being particularly preferable.
  • Examples of the alkenyl group having 2 to 3 carbon atoms in R 13 and R 14 of the general formula (II') include a vinyl group, an allyl group, a 1-propenyl group, an isopropenyl group and the like, and an allyl group is preferable.
  • R 13 and R 14 of the general formula (II') include -OMgCl group, methyl group, ethyl group, allyl group, phenyl group, fluorophenyl group, difluorophenyl group, trill group, ethylphenyl group, xsilyl group, diethyl group.
  • Phenyl group, methoxyphenyl group, ethoxyphenyl group, dimethoxyphenyl group, diethoxyphenyl group are preferable, and -OMgCl group, methyl group, allyl group, phenyl group, fluorophenyl group, trill group, xsilyl group, methoxyphenyl group and dimethoxy Phenyl groups are more preferred.
  • M 1 of the general formula (III) is 0 or 2, preferably 2.
  • X 4 of the general formula (III) is a chlorine atom or a bromine atom, and a chlorine atom is preferable.
  • an alkyl group having 1 to 6 carbon atoms having a halogeno group or an alkoxy group as a substituent or not substituted in R 5 of the general formula (III), R 3 and R 4 of the general formula (II)
  • the same as the "alkyl group having 1 to 6 carbon atoms having a halogeno group or an alkoxy group or not substituted" can be mentioned, and the preferred one is also the same.
  • Examples of the alkoxy group having 1 to 6 carbon atoms in R 5 of the general formula (III) include the same alkoxy group having 1 to 6 carbon atoms in R 1 of the general formula (I), and the preferred one is also the same. ..
  • R 5 of the general formula (III) the "aryl group having a halogeno group, an alkyl group, a haloalkyl group or an alkoxy group as a substituent, or an unsubstituted aryl group having 6 to 10 carbon atoms" is defined as the general formula (II).
  • the same as the "substituted group having a halogeno group, an alkyl group, a haloalkyl group or an alkoxy group, or an unsubstituted aryl group having 6 to 10 carbon atoms" in R 2 to R 4 of the above can be mentioned, and preferable ones are also mentioned. It is the same.
  • Examples of the aryloxy group having 6 to 10 carbon atoms in R 5 of the general formula (III) include a phenoxy group and a naphthyloxy group, and a phenoxy group is preferable.
  • the halogeno group, alkyl group, haloalkyl group and alkoxy group as substituents of the aryloxy group having 6 to 10 carbon atoms in R 5 of the general formula (III) are the carbons in R 2 to R 4 of the general formula (II).
  • the same ones as those as substituents of the aryl groups of numbers 6 to 10 are mentioned, and the preferred ones are also the same.
  • the number of substituents of "aryloxy group having 6 to 10 carbon atoms having a halogeno group, an alkyl group, a haloalkyl group or an alkoxy group as a substituent" in R 5 of the general formula (III) is usually 1 to 7.
  • the number is preferably 1 to 5, more preferably 1 to 2, and particularly preferably 1.
  • the aryloxy group may have a substituent at any position.
  • the aryloxy group is a phenoxy group
  • the phenoxy group may have a substituent at any of the ortho, meta or para positions; the phenoxy group has one substituent. In this case, the one having a substituent at the para position is preferable; when the phenoxy group has two substituents, the one having a substituent at the meta position is preferable.
  • the "aryloxy group having 6 to 10 carbon atoms having a halogeno group, an alkyl group, a haloalkyl group or an alkoxy group as a substituent" in R 5 of the general formula (III) includes a halogeno group and a carbon number as a substituent. Phenoxy groups having 1 to 6 alkyl groups, 1 to 6 carbon haloalkyl groups or 1 to 6 carbon alkoxy groups, or unsubstituted are preferred; as substituents, fluorogroups, 1 to 4 carbon atoms.
  • a phenoxy group having an alkyl group, a perfluoroalkyl group having 1 to 4 carbon atoms or an alkoxy group having 1 to 4 carbon atoms or being unsubstituted is more preferable; as a substituent, a fluoro group or a linear group having 1 carbon number of carbon atoms is preferable.
  • a phenoxy group having an alkyl group of to 4 or a linear alkoxy group having 1 to 4 carbon atoms or which is unsubstituted is more preferable; an unsubstituted phenoxy group is particularly preferable.
  • an aryloxy group having 6 to 10 carbon atoms having a halogeno group, an alkyl group, a haloalkyl group or an alkoxy group as a substituent in R 5 of the general formula (III), for example, the following general formula ( Examples thereof include the groups represented by III-3).
  • R 15 represents a halogeno group, an alkyl group having 1 to 6 carbon atoms, a haloalkyl group having 1 to 6 carbon atoms, or an alkoxy group having 1 to 6 carbon atoms
  • n 9 is 0. Represents an integer of ⁇ 5.
  • halogeno group, alkyl group, haloalkyl group and alkoxy group in R 15 of the general formula (III-3) are used as substituents of the aryl group having 6 to 10 carbon atoms in R 2 to R 4 of the general formula (II). The same ones are mentioned, and so are the preferred ones.
  • a fluoro group, an alkyl group having 1 to 4 carbon atoms, a perfluoroalkyl group having 1 to 4 carbon atoms, and an alkoxy group having 1 to 4 carbon atoms are preferable; a fluoro group, A linear alkyl group having 1 to 4 carbon atoms and a linear alkoxy group having 1 to 4 carbon atoms are more preferable; a fluoro group, a methyl group, an ethylphenyl group, a methoxy group and an ethoxy group are further preferable.
  • n 9 of the general formula (III-3) an integer of 0 to 3 is preferable, an integer of 0 to 2 is more preferable, and 0 is particularly preferable.
  • Preferred specific examples of the group represented by the general formula (III-3) include, for example, a phenoxy group; a fluorophenoxy group, a difluorophenoxy group; a methylphenoxy group, an ethylphenoxy group, an n-propylphenoxy group, and an n-butylphenoxy group.
  • Methoxyphenoxy group, ethoxyphenoxy group, dimethoxyphenoxy group, diethoxyphenoxy group are more preferable, and phenoxy group is particularly preferable.
  • X 5 of the general formula (III-1) is a chlorine atom or a bromine atom, and a chlorine atom is preferable.
  • Examples of the alkoxy group having 1 to 6 carbon atoms in R 6 of the general formula (III-1) and (III-2) include the same alkoxy group having 1 to 6 carbon atoms in R 1 of the general formula (I). And so are the preferred ones.
  • Aaryl group having 6 to 10 carbon atoms which has a halogeno group, an alkyl group, a haloalkyl group or an alkoxy group as a substituent, or is unsubstituted
  • R 6 of the general formulas (III-1) and (III-2). Is the same as "an aryl group having 6 to 10 carbon atoms, which has a halogeno group, an alkyl group, a haloalkyl group or an alkoxy group as a substituent, or is unsubstituted" in R 2 to R 4 of the general formula (II). The same is true for the preferred ones.
  • R 6 of the general formulas (III-1) and (III-2) includes -OMgCl group; -OMgBr group; as a substituent, which has a halogeno group or an alkoxy group having 1 to 6 carbon atoms, or is unsubstituted.
  • Group-bearing or unsubstituted, phenyl group as substituents, having or not having a halogeno group, an alkyl group having 1 to 6 carbon atoms, a haloalkyl group having 1 to 6 carbon atoms or an alkoxy group having 1 to 6 carbon atoms.
  • Substituted phenoxy groups are preferred, -OMgCl groups; -OMgBr groups; unsubstituted alkyl groups with 1 to 6 carbon atoms; alkoxy groups with 1 to 6 carbon atoms; fluoro groups as substituents, linear carbon atoms.
  • Specific examples of the group represented by the general formula (III-1) include the group represented by the following general formula (III-4).
  • a R 16s are independently -OMgCl group, -OMgBr group, unsubstituted alkyl group having 1 to 6 carbon atoms, alkoxy group having 1 to 6 carbon atoms, respectively.
  • Examples of the unsubstituted alkyl group having 1 to 6 carbon atoms in R 16 of the general formula (III-4) include the same alkyl group having 1 to 6 carbon atoms in R 1 of the general formula (I), which is preferable. The same is true for things.
  • Examples of the alkoxy group having 1 to 6 carbon atoms in R 16 of the general formula (III-4) include the same alkoxy group having 1 to 6 carbon atoms in R 1 of the general formula (I), and the preferred one is also the same. Is.
  • R 16 of the general formula (III-4) includes -OMgCl group, methyl group, ethyl group, n-propyl group, n-butyl group, methoxy group, ethoxy group, n-propoxy group, n-butoxy group and phenyl.
  • a group and a phenoxy group are preferable, a -OMgCl group, a methyl group, an ethyl group, a methoxy group, an ethoxy group, a phenyl group and a phenoxy group are more preferable, and a -OMgCl group is particularly preferable.
  • M 3 of the general formula (III-6) is 0 or 1, preferably 1.
  • R 5 of the general formula (III) includes -OMgCl group; -OMgBr group; as a substituent, an alkyl group having a halogeno group or an alkoxy group having 1 to 6 carbon atoms, or an unsubstituted alkyl group having 1 to 6 carbon atoms.
  • Phenyl group as a substituent, a halogeno group, an alkyl group having 1 to 6 carbon atoms, a haloalkyl group having 1 to 6 carbon atoms or an alkoxy group having 1 to 6 carbon atoms, or an unsubstituted phenoxy group; general formula.
  • R 5 is preferably two R 5 form a general formula (III-7), -OMgCl group;; (III-4) a group represented by -OMgBr group; unsubstituted alkyl having 1 to 6 carbon atoms Group; Alkoxy group having 1 to 6 carbon atoms; As a substituent, it has a fluoro group, a linear alkyl group having 1 to 4 carbon atoms, or a linear alkoxy group having 1 to 4 carbon atoms, or is unsubstituted.
  • Phenyl group as a substituent, a fluoro group, a linear alkyl group having 1 to 4 carbon atoms or a linear alkoxy group having 1 to 4 carbon atoms, or an unsubstituted phenoxy group; general formula ( more preferably the two R 5 form a general formula (III-7), -OMgCl group; a group represented by III-4) carbon atoms, alkyl group of unsubstituted C 1-4 Alkoxy groups 1 to 4; linear alkyl groups having 1 to 4 carbon atoms or linear alkoxy groups having 1 to 4 carbon atoms or unsubstituted, phenyl groups; linear carbon atoms 1 An unsubstituted phenoxy group having an alkyl group of to 4 or a linear alkoxy group having 1 to 4 carbon atoms; a group represented by the formula (III-5); two R 5s of the formula (III-8).
  • -OMgCl group methyl group, ethyl group, n-propyl group, n-butyl group, methoxy group, ethoxy group, n-propoxy group, n-butoxy group, phenyl group, methoxyphenyl group, ethoxy.
  • Preferred specific examples of the compound represented by the general formula (III) include, for example, the compound represented by the following general formula (III'-1) or (III'-2).
  • R 17 , R 19 and R 20 are independently -OMgCl group, -OMgBr group, and unsubstituted alkyl having 1 to 6 carbon atoms.
  • R 17 of the general formula (III'-1) includes -OMgCl group, methyl group, ethyl group, n-propyl group, n-butyl group, methoxy group, ethoxy group, n-propoxy group, n-butoxy group, Phenyl group, methoxyphenyl group, ethoxyphenyl group, n-propoxyphenyl group, n-butoxyphenyl group, phenoxy group, formula (III-8) formed by R 17 and R 18 is preferable, -OMgCl group, methyl
  • the formula (III-8) formed of a group, an ethyl group, a methoxy group, an ethoxy group, a phenyl group, a methoxyphenyl group, an ethoxyphenyl group, a phenoxy group, and R 17 and R 18 is more preferable, and a -OMgCl group and a methyl group are used.
  • R 18 of the general formula (III'-1) includes -OMgCl group, methyl group, ethyl group, n-propyl group, n-butyl group, methoxy group, ethoxy group, n-propoxy group, n-butoxy group, A phenyl group, a methoxyphenyl group, an ethoxyphenyl group, an n-propoxyphenyl group, an n-butoxyphenyl group, a phenoxy group, a group represented by the formula (III-5), and a formula (III) formed by R 17 and R 18.
  • -8) is preferable, and -OMgCl group, methyl group, ethyl group, methoxy group, ethoxy group, phenyl group, methoxyphenyl group, ethoxyphenyl group, phenoxy group, group represented by the formula (III-5), R 17 and The formula (III-8) formed with R 18 is more preferable, and the -OMgCl group, methyl group, phenyl group, methoxyphenyl group, phenoxy group, and group represented by the formula (III-5) are particularly preferable.
  • R 19 and R 20 of the general formula (III'-2) include -OMgCl group, methyl group, ethyl group, n-propyl group, n-butyl group, methoxy group, ethoxy group, n-propoxy group, n- Butoxy group, phenyl group, methoxyphenyl group, ethoxyphenyl group, n-propoxyphenyl group, n-butoxyphenyl group, phenoxy group are preferable, and -OMgCl group, methyl group, ethyl group, methoxy group, ethoxy group, phenyl group, A methoxyphenyl group, an ethoxyphenyl group, and a phenoxy group are more preferable, and a -OMgCl group, a methyl group, a phenyl group, a methoxyphenyl group, and a phenoxy group are particularly preferable.
  • X 6 of the general formula (IV) is a chlorine atom or a bromine atom, and a chlorine atom is preferable.
  • the alkyl group having 1 to 10 carbon atoms in R 21 of the general formula (IV) may be any of linear, branched and cyclic, preferably linear and branched, and linear. The shape is more preferable. Further, among the alkyl groups having 1 to 10 carbon atoms, those having 1 to 6 carbon atoms are preferable, those having 1 to 4 carbon atoms are more preferable, and those having 1 or 2 carbon atoms are further preferable.
  • methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, n-pentyl group, n-hexyl group, n- Heptyl group, n-octyl group, n-nonyl group, n-decyl group and the like include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert.
  • -Butyl group, n-pentyl group, n-hexyl group are preferable, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group and tert-butyl group are more preferable.
  • Methyl group, ethyl group, n-propyl group, n-butyl group are more preferable, and methyl group and ethyl group are particularly preferable.
  • the haloalkyl group having 1 to 10 carbon atoms in R 21 of the general formula (IV) may be any of linear, branched and cyclic, preferably linear and branched, and linear. The shape is more preferable. Further, among the haloalkyl groups having 1 to 10 carbon atoms, those having 1 to 6 carbon atoms are preferable, and those having 1 to 4 carbon atoms are more preferable. Specific examples thereof include a fluoroalkyl group having 1 to 10 carbon atoms, a chloroalkyl group having 1 to 10 carbon atoms, a bromoalkyl group having 1 to 10 carbon atoms, and an iodoalkyl group having 1 to 10 carbon atoms.
  • a fluoroalkyl group having 1 to 10 carbon atoms is preferable, a perfluoroalkyl group having 1 to 6 carbon atoms and a monofluoroalkyl group having 1 to 6 carbon atoms are more preferable, and a perfluoroalkyl group having 1 to 4 carbon atoms is further preferable.
  • haloalkyl group having 1 to 10 carbon atoms in R 21 of the general formula (IV) include, for example, a trifluoromethyl group, a pentafluoroethyl group, a heptafluoro-n-propyl group, a heptafluoroisopropyl group, and a perfluoro group.
  • -n-butyl group perfluoroisobutyl group, perfluoro-sec-butyl group, perfluoro-tert-butyl group, perfluoro-n-pentyl group, perfluoro-n-hexyl group, perfluoro-n-heptyl group , Perfluoro-n-octyl group, perfluoro-n-nonyl group, perfluoro-n-decyl group, fluoromethyl group, fluoroethyl group, fluoro-n-propyl group, fluoroisopropyl group, fluoro-n-butyl group , Fluoroisobutyl group, Fluoro-sec-butyl group, Fluoro-tert-butyl group, Fluoro-n-pentyl group, Fluoro-n-hexyl group, Fluoro-n-heptyl group, Fluoro-n-octyl group, Fluoro
  • trifluoromethyl group pentafluoroethyl group, heptafluoro-n-propyl group, heptafluoroisopropyl group, perfluoro-n-butyl group, perfluoroisobutyl group, perfluoro-sec-butyl group, perfluoro-tert -Butyl group is preferable, and trifluoromethyl group, pentafluoroethyl group, heptafluoro-n-propyl group and perfluoro-n-butyl group are more preferable.
  • alkyl group having 1 to 10 carbon atoms having a -SO 3 MgCl group or -SO 3 MgBr group as a substituent and "-SO 3 MgCl group or -SO 3 MgBr as a substituent” in R 21 of the general formula (IV)
  • a "haloalkyl group having a group and having 1 to 10 carbon atoms” is one in which one or more hydrogen atoms on an alkyl group or a haloalkyl group are substituted with a -SO 3 MgCl group or a -SO 3 MgBr group.
  • one hydrogen atom is substituted with a -SO 3 MgCl group or -SO 3 MgBr group is preferable, and one in which one hydrogen atom is substituted with a -SO 3 MgCl group is more preferable.
  • a plurality of hydrogen atoms are substituted, those all substituted with -SO 3 MgCl group or all substituted with -SO 3 MgBr group are preferable, and all are substituted with -SO 3 MgCl group. Is more preferable.
  • the -SO 3 MgCl group or the -SO 3 MgBr group may be bonded to any of the carbon atoms constituting the alkyl group or the haloalkyl group, and is bonded to the carbon atom at the end of the alkyl group or the haloalkyl group. Is preferable.
  • R 21 of the general formula (IV) as "an alkyl group having a -SO 3 MgCl group or -SO 3 MgBr group as a substituent, or an unsubstituted alkyl group having 1 to 10 carbon atoms", as a substituent,-
  • Alkyl groups are more preferred; alkyl groups having 1 to 4 carbon atoms, having or not substituted with a -SO 3 MgCl group, are even more preferred.
  • methyl group, ethyl group, n-propyl group, n-butyl group, -CH 2 -SO 3 MgCl group, -C 2 H 4 -SO 3 MgCl group, -C 3 H 6 -SO 3 MgCl group, -C 4 H 7 -SO 3 MgCl group are preferable, and methyl group, ethyl group, -CH 2 -SO 3 MgCl groups, -C 2 H 4 -SO 3 MgCl groups are more preferred.
  • haloalkyl group having 1 to 10 carbon atoms having a -SO 3 MgCl group or a -SO 3 MgBr group as a substituent has an unsubstituted carbon number.
  • a haloalkyl group of 1 to 10 is preferable, an unsubstituted fluoroalkyl group having 1 to 10 carbon atoms is more preferable, an unsubstituted fluoroalkyl group having 1 to 6 carbon atoms is further preferable, and an unsubstituted fluoroalkyl group having 1 to 4 carbon atoms is preferable.
  • Perfluoroalkyl groups are particularly preferred.
  • trifluoromethyl group pentafluoroethyl group, heptafluoro-n-propyl group, heptafluoroisopropyl group, perfluoro-n-butyl group, perfluoroisobutyl group, perfluoro-sec-butyl group
  • examples thereof include perfluoro-tert-butyl group, and trifluoromethyl group, pentafluoroethyl group, heptafluoro-n-propyl group and perfluoro-n-butyl group are preferable.
  • Examples of the aryl group having 6 to 14 carbon atoms in R 21 of the general formula (IV) include a phenyl group, a naphthyl group, an anthracenyl group and the like, and a phenyl group and a naphthyl group are preferable, and a phenyl group is more preferable.
  • the halogeno group, alkyl group and alkoxy group as substituents of the aryl group having 6 to 14 carbon atoms in R 21 of the general formula (IV) have 6 to 10 carbon atoms in R 2 to R 4 of the general formula (II).
  • the same as those as substituents on the aryl group of the above are mentioned, and so are the preferred ones.
  • the number is usually 1 to 3, preferably 1 to 2, and more preferably 1.
  • the aryl group may have a substituent at any position.
  • the aryl group is a phenyl group
  • the phenyl group may have a substituent at any of the ortho-position, meta-position, and para-position; when the phenyl group has one substituent.
  • the one having a substituent at the para position is preferable; when the phenyl group has two substituents, the one having a substituent at the meta position is preferable.
  • R 21 of the general formula (IV) an aryl group having 6 to 14 carbon atoms having a -SO 3 MgCl group, a -SO 3 MgBr group, a halogeno group, an alkyl group or an alkoxy group, or an unsubstituted group.
  • a substituent a -SO 3 MgCl group, a -SO 3 MgBr group, a halogeno group, an alkyl group having 1 to 6 carbon atoms or an alkoxy group having 1 to 6 carbon atoms, or an unsubstituted phenyl group.
  • a -SO 3 MgCl group, a -SO 3 MgBr group a fluoro group, an alkyl group having 1 to 4 carbon atoms or an alkoxy group having 1 to 4 carbon atoms, or an unsubstituted phenyl group is used. More preferably; as a substituent, a -SO 3 MgCl group or a -SO 3 MgBr group, or an unsubstituted, phenyl group is more preferable; as a substituent, a -SO 3 MgCl group or an unsubstituted phenyl group is further preferable. More preferred; unsubstituted phenyl groups are particularly preferred.
  • phenyl group -C 6 H 4 -SO 3 MgCl group, -C 6 H 4 -SO 3 MgBr group, fluorophenyl group, difluorophenyl group, trill group, ethyl phenyl group, n-propyl phenyl.
  • n-butylphenyl group xsilyl group, diethylphenyl group, di-n-propylphenyl group, di-n-butylphenyl group, methoxyphenyl group, ethoxyphenyl group, n-propoxyphenyl group, n-butoxyphenyl group , dimethoxyphenyl group, diethoxy phenyl group, di -n- propoxyphenyl group, di -n- butoxyphenyl group and the like, a phenyl group, -C 6 H 4 -SO 3 MgCl group, -C 6 H 4 - SO 3 MgBr group, fluorophenyl group, trill group, ethylphenyl group, methoxyphenyl group, ethoxyphenyl group are preferable, phenyl group, -C 6 H 4 -SO 3 MgCl group, -C 6 H 4 -SO 3 MgBr group, flu
  • R 21 of the general formula (IV) has a -SO 3 MgCl group or a -SO 3 MgBr group as a substituent, or is an unsubstituted alkyl group having 1 to 6 carbon atoms; an unsubstituted alkyl group having 1 to 6 carbon atoms.
  • Haloalkyl group of 10 as a substituent, a phenyl having a -SO 3 MgCl group, a -SO 3 MgBr group, a halogeno group, an alkyl group having 1 to 6 carbon atoms or an alkoxy group having 1 to 6 carbon atoms, or unsubstituted.
  • the substituent has a -SO 3 MgCl group or a -SO 3 MgBr group, or an unsubstituted biphenyl group is preferable, and the substituent has a -SO 3 MgCl group or a -SO 3 MgBr group, or no group.
  • An alkyl group or an alkoxy group having 1 to 4 carbon atoms or an unsubstituted phenyl group; as a substituent, a -SO 3 MgCl group or a -SO 3 MgBr group or an unsubstituted biphenyl group is more preferable.
  • -SO 3 MgCl group is more preferable as a substituent group, of having or unsubstituted a -SO 3 MgCl group as a substituent, an alkyl group having 1 to 4 carbon atoms; a phenyl group substituted unsubstituted Substituent perfluoroalkyl groups having 1 to 4 carbon atoms; unsubstituted phenyl groups; unsubstituted biphenyl groups are particularly preferred.
  • Preferred specific examples of the compound represented by the general formula (IV) include, for example, the compound represented by the following general formula (IV'-1) or (IV'-2).
  • X 7 represents a chlorine atom or a bromine atom
  • R 22 is an unsubstituted alkyl group having 1 to 6 carbon atoms; an unsubstituted carbon.
  • R 23 represents an unsubstituted alkylene group having 1 to 6 carbon atoms, an unsubstituted phenylene group or an unsubstituted biphenylene group, and X 6 is the same as above.
  • Examples of the unsubstituted alkyl group having 1 to 6 carbon atoms in R 22 of the general formula (IV'-1) include the same alkyl group having 1 to 6 carbon atoms in R 1 of the general formula (I). The preferred ones are the same.
  • Examples of the unsubstituted haloalkyl group having 1 to 10 carbon atoms in R 22 of the general formula (IV'-1) include the same haloalkyl group having 1 to 10 carbon atoms in R 21 of the general formula (IV'-1). The preferred ones are the same.
  • the alkyl group and the alkoxy group As the halogeno group as the substituent of the phenyl group in R 22 of the general formula (IV'-1), the alkyl group and the alkoxy group, the aryl group having 6 to 10 carbon atoms in R 2 to R 4 of the general formula (II) The same as those as substituents for are mentioned, and so are the preferred ones.
  • the number of substituents of "a phenyl group having a halogeno group, an alkyl group having 1 to 6 carbon atoms or an alkoxy group having 1 to 6 carbon atoms as a substituent" in R 22 of the general formula (IV'-1) Usually 1 to 3, preferably 1 to 2, and more preferably 1.
  • the phenyl group may have a substituent at any of the ortho, meta, and para positions; when the phenyl group has one substituent, it preferably has a substituent at the para position; When the phenyl group has two substituents, the one having a substituent at the meta position is preferable.
  • the "phenyl group having a halogeno group, an alkyl group having 1 to 6 carbon atoms or an alkoxy group having 1 to 6 carbon atoms as a substituent" in R 22 of the general formula (IV'-1) is used.
  • a fluoro group, an alkyl group having 1 to 4 carbon atoms or an alkoxy group having 1 to 4 carbon atoms, or an unsubstituted phenyl group is preferable; an unsubstituted phenyl group is more preferable.
  • phenyl group fluorophenyl group, difluorophenyl group, trill group, ethylphenyl group, n-propylphenyl group, n-butylphenyl group, xsilyl group, diethylphenyl group, di-n-propylphenyl group.
  • Di-n-butylphenyl group methoxyphenyl group, ethoxyphenyl group, n-propoxyphenyl group, n-butoxyphenyl group, dimethoxyphenyl group, diethoxyphenyl group, di-n-propoxyphenyl group, di-n- Examples thereof include a phenyl group, a phenyl group, a fluorophenyl group, a trill group, an ethylphenyl group, a methoxyphenyl group and an ethoxyphenyl group, and a phenyl group is more preferable.
  • R 22 of the general formula (IV'-1) includes an unsubstituted alkyl group having 1 to 6 carbon atoms; an unsubstituted fluoroalkyl group having 1 to 10 carbon atoms; and a fluoro group and 1 to 10 carbon atoms as substituents.
  • Fluoroalkyl group having 1 to 6 carbon atoms; unsubstituted phenyl group; unsubstituted biphenyl group is more preferable, unsubstituted alkyl group having 1 to 4 carbon atoms; unsubstituted perfluoroalkyl group having 1 to 4 carbon atoms.
  • Groups; unsubstituted phenyl groups; unsubstituted biphenyl groups are more preferred.
  • Ethylphenyl group methoxyphenyl group, ethoxyphenyl group, biphenyl group and the like include methyl group, ethyl group, n-propyl group, n-butyl group, trifluoromethyl group, pentafluoroethyl group and heptafluoro-n-.
  • a propyl group, a perfluoro-n-butyl group, a phenyl group, and a biphenyl group are preferable.
  • X 7 of the general formula (IV'-2) is a chlorine atom or a bromine atom, and a chlorine atom is preferable.
  • R 23 of the general formula (IV'-2) As the unsubstituted alkylene group having 1 to 6 carbon atoms in R 23 of the general formula (IV'-2), a linear group or a branched group is preferable, and a linear group is more preferable. Further, among the alkylene groups having 1 to 6 carbon atoms, those having 1 to 4 carbon atoms are preferable, and those having 1 or 2 carbon atoms are more preferable.
  • methylene group examples thereof include a methylene group, an ethylene group, a trimethylene group, a tetramethylene group, a pentamethylene group, a hexamethylene group and the like, and a methylene group, an ethylene group, a trimethylene group and a tetramethylene group are preferable, and a methylene group and an ethylene group are preferable. Groups are more preferred.
  • an unsubstituted linear alkylene group having 1 to 6 carbon atoms, an unsubstituted phenylene group, and an unsubstituted biphenylene group are preferable, and a methylene group, an ethylene group, and the like.
  • a trimethylene group and a tetramethylene group are preferable, and a methylene group and an ethylene group are more preferable.
  • Electrolytic solution according to the present invention compounds represented by general formulas (I) to (IV)
  • the compounds represented by the general formulas (I) to (IV) may form a coordinate, for example, the compounds represented by the general formulas (I) to (IV) and the electrolytic solution according to the present invention described later.
  • a coordinator may be formed with the solvent in.
  • the compounds represented by the general formulas (I) to (IV) form a coordinate with tetrahydrofuran (THF), it is presumed to form the following coordinate.
  • THF tetrahydrofuran
  • the compounds represented by the general formulas (I) to (IV) may form an aggregate in which a plurality of coordinators are aggregated, and for example, an aggregate in which two coordinators are aggregated is formed.
  • it is estimated that it will be as follows. [In the above formula, R 2 to R 5 , R 21 , X 3 , X 4 , X 6 , Y 1 , m 1 and m 2 are the same as above. ]
  • Lewis acid The Lewis acids in the electrolytic solution according to the present invention are beryllium (Be), boron (B), aluminum (Al), silicon (Si), tin (Sn), titanium (Ti), chromium (Cr), and iron (Fe). , Or cobalt (Co) as an element.
  • beryllium compounds such as beryllium fluoride (II), beryllium chloride (II), beryllium bromide (II); boron fluoride (III), boron chloride (III), boron bromide (III), tri Boron compounds such as phenoxyborane, phenyldichloroborane, triphenylboran; aluminum chloride (III), aluminum bromide (III), aluminum iodide (III), dimethylaluminum chloride, diethylaluminum chloride, methylaluminum dichloride, ethylaluminum dichloride , Aluminum compounds such as trimethylaluminum, triethylaluminum, triphenylaluminum; silyl compounds such as trimethylsilyltriflate, trimethylsilyliodo, tert-butyldimethylsilyltriflate, triisopropylsilyltriflate; tin chloride (IV),
  • boron chloride (III), aluminum chloride (III), methylaluminum dichloride, dimethylaluminum chloride and triphenylaluminum are preferable, and aluminum chloride (III) (AlCl 3 ) is particularly preferable.
  • Examples of the alkyl group having 1 to 6 carbon atoms in R 7 of the general formula (A) include the same alkyl group having 1 to 6 carbon atoms in R 1 of the general formula (I), and the same is preferable. ..
  • the perfluoroalkyl group having 1 to 6 carbon atoms in R 7 of the general formula (A) may be any of linear, branched and cyclic, preferably linear and branched. Linear is more preferable. Further, among the perfluoroalkyl groups having 1 to 6 carbon atoms, those having 1 to 4 carbon atoms are preferable, and those having 1 or 2 carbon atoms are more preferable.
  • a trifluoromethyl group a pentafluoroethyl group, a heptafluoro-n-propyl group, a heptafluoroisopropyl group, a perfluoro-n-butyl group, a perfluoroisobutyl group, a perfluoro-sec-butyl group, Perfluoro-tert-butyl group, perfluorocyclobutyl group, perfluoro-n-pentyl group, perfluoroisopentyl group, perfluoro-sec-pentyl group, perfluoro-tert-pentyl group, perfluoroneopentyl group, Perfluoro-2-methylbutyl group, perfluoro-1,2-dimethylpropyl group, perfluoro-1-ethylpropyl group, perfluorocyclopentyl group, perfluoro-n-hexyl group, perfluorois
  • the sec-butyl group and perfluoro-tert-butyl group are preferable, and the trifluoromethyl group, pentafluoroethyl group, heptafluoro-n-propyl group and perfluoro-n-butyl group are more preferable, and the trifluoromethyl group and penta A fluoroethyl group is more preferred, and a trifluoromethyl group is particularly preferred.
  • Formula (A) four of R 7 in may be independently identical or different, but preferably all four are the same.
  • the methyl group, ethyl group, n-propyl group, n-butyl group, trifluoromethyl group, pentafluoroethyl group, heptafluoro-n-propyl group, perfluoro-n-butyl group are preferable, and the trifluoromethyl group is preferable.
  • Pentafluoroethyl group is more preferable, and trifluoromethyl group is particularly preferable.
  • Specific examples of the compound represented by the general formula (A) include magnesium bis (methanesulfonyl) imide, magnesium bis (ethanesulfonyl) imide, magnesium bis (n-propanesulfonyl) imide, and magnesium bis (isopropanesulfonyl).
  • magnesium bis (alkanesulfonyl) imide having 2 to 12 carbon atoms and magnesium bis (perfluoroalkanesulfonyl) imide having 2 to 12 carbon atoms are preferable, and magnesium bis (methanesulfonyl) imide and magnesium bis (ethane) are preferable.
  • Sulfonyl) imide magnesium bis (n-propanesulfonyl) imide, magnesium bis (n-butanesulfonyl) imide; magnesium bis (trifluoromethanesulfonyl) imide, magnesium bis (pentafluoroethanesulfonyl) imide, magnesium bis (heptafluoro-n) -Propanesulfonyl) imide, magnesium bis (perfluoro-n-butanesulfonyl) imide are more preferable, magnesium bis (trifluoromethanesulfonyl) imide, magnesium bis (pentafluoroethanesulfonyl) imide are more preferable, and magnesium bis (trifluoromethanesulfonyl) imide is more preferable. ) Imide is particularly preferred.
  • a compound represented by any one of the general formulas (I) to (IV) and / or a solvent capable of dissolving a Lewis acid or a compound represented by the general formula (A) can be used.
  • a solvent include an ether solvent, a halogenated hydrocarbon solvent, a carbonate solvent, a nitrile solvent, a sulfone solvent, and the like, and even if two or more kinds of these solvents are mixed. Good.
  • ether solvent examples include diethyl ether, tetrahydrofuran, 2-methyltetrahydrofuran, diisopropyl ether, 1,2-dimethoxyethane, diethylene glycol dimethyl ether (diglime), triethylene glycol dimethyl ether (triglime), and tetraethylene glycol dimethyl ether (tetraglyme). ), Cyclopentyl methyl ether, tert-butyl methyl ether, 1,4-dioxane and the like.
  • halogenated hydrocarbon solvent examples include dichloromethane, chloroform, carbon tetrachloride, 1,2-dichloroethane and the like.
  • Examples of the carbonate-based solvent include dimethyl carbonate, diethyl carbonate, ethyl methyl carbonate, propylene carbonate and the like.
  • Examples of the nitrile solvent include acetonitrile, propionitrile, butyronitrile, succinonitrile, pimeronitrile, methoxypropionitrile and the like.
  • sulfone-based solvent examples include sulfolane, dimethyl sulfone, ethyl methyl sulfone, methyl-n-propyl sulfone, methyl isopropyl sulfone, n-butyl-methyl sulfone, isobutyl methyl sulfone, sec-butyl methyl sulfone, and tert-butyl methyl.
  • an ether solvent and a sulfone solvent are preferable, and an ether solvent is more preferable.
  • these solvents tetrahydrofuran, 1,2-dimethoxyethane, diglime, triglime, tetraglime and sulfolane are preferable, tetrahydrofuran, diglime, triglime and tetraglime are more preferable, and tetrahydrofuran and triglime are particularly preferable.
  • the electrolytic solution according to the present invention is formed by mixing a compound represented by any one of the general formulas (I) to (IV), a Lewis acid or a compound represented by the general formula (A), and a solvent.
  • a compound represented by any one of the general formulas (I) to (IV), a Lewis acid, and a solvent are preferably mixed; the compound represented by the general formula (I) and the Lewis A mixture of an acid and a solvent is more preferable; a mixture of a compound represented by the general formula (I'), an aluminum compound, and an ether solvent is further preferable.
  • Examples thereof include a mixture of one kind of ether-based solvent; B (OMgCl) 3 or C 6 H 5 B (OMgCl) 2 , aluminum chloride (III), tetrahydrofuran, triglime, or a mixture of these two kinds.
  • a mixture of a solvent is preferable; a mixture of B (OMgCl) 3 , aluminum chloride (III), tetrahydrofuran, triglime, or a mixed solvent of these two types is particularly preferable.
  • Magnetic TM B01 B (OMgCl) 3- AlCl 3 complex (1: 6) / triglime solution
  • Maglution TM B02 B (OMgCl) 3- AlCl 3 complex (1: 6) / triglime-tetrahydrofuran (50:50 vol%) solution
  • the concentration of the compound represented by any one of the general formulas (I) to (IV) in the electrolytic solution according to the present invention is usually 0.01 mol / L or more and 5 mol / L or less, preferably 0.05 mol / L or more and 3 mol / L. Hereinafter, it is more preferably 0.1 mol / L or more and 1 mol / L or less.
  • the amount of the Lewis acid or the compound represented by the general formula (A) used in the electrolytic solution according to the present invention is usually the number of moles of the compound represented by any one of the general formulas (I) to (IV). 0.5 equivalents or more and 36 equivalents or less, preferably 1 equivalent or more and 18 equivalents or less. More specifically, the amount of the Lewis acid or the compound represented by the general formula (A) used in the electrolytic solution according to the present invention is such that the compound represented by any one of the general formulas (I) to (IV) is contained in the molecule. It is proportional to the total number of -OMgCl and -OMgBr groups in.
  • the amount of Lewis acid or the compound represented by the general formula (A) to be used is the -OMgCl group or -OMgBr group 1 that the compound represented by any one of the general formulas (I) to (IV) has in the molecule.
  • the amount is usually 0.5 equivalents or more and 4 equivalents or less, preferably 1 equivalent or more and 2 equivalents or less, relative to the number of mols of the compound represented by any one of the general formulas (I) to (IV).
  • the amount of Lewis acid or the compound represented by the general formula (A) to be used is that of the -OMgCl group and the -OMgBr group that the compound represented by any one of the general formulas (I) to (IV) has in the molecule.
  • the total number is 2, it is usually 1 equivalent or more and 8 equivalents or less, preferably 2 equivalents or more and 4 equivalents or less, relative to the number of mols of the compound represented by any one of the general formulas (I) to (IV).
  • the total number of -OMgCl groups and -OMgBr groups contained in the molecule is 3, usually 1.5 equivalents or more with respect to the number of mols of the compound represented by any one of the general formulas (I) to (IV) 12 Equivalent or less, preferably 3 equivalents or more and 6 equivalents or less.
  • the electrolytic solution according to the present invention has additives such as a film forming agent, an overcharge inhibitor, an oxygen scavenger, a dehydrating agent and a flame retardant, and a coordinating property such as crown ether, which are usually used in this field. It may contain an additive.
  • the electrolytic solution according to the present invention can be used for a magnesium battery, and in the case of a magnesium secondary battery, it exhibits high oxidative stability and can be used stably and repeatedly.
  • a compound represented by any one of the general formulas (I) to (IV) and a Lewis acid or a compound represented by the general formula (A) are dissolved (mixed) in a solvent.
  • a solvent 0.5 to 36 mol of a Lewis acid or a compound represented by the general formula (A) is used for 1 mol of the compound represented by any one of the general formulas (I) to (IV), and these are used as described above. It is produced by adding it to a solvent to a concentration and mixing.
  • the mixture may be heated or cooled in the range of ⁇ 78 to 300 ° C., preferably in the range of 0 to 150 ° C.
  • the electrolytic solution according to the present invention may contain a compound represented by any one of the general formulas (I) to (IV), a Lewis acid or a compound represented by the general formula (A), and a solvent, for example.
  • the above-mentioned coordinator is also included in the present invention. That is, the electrolytic solution according to the present invention also includes a mixture of the above-mentioned coordinator, a Lewis acid or a compound represented by the general formula (A), and if necessary, a solvent.
  • any one of the general formulas (I) to (IV) constituting the coordinator is formed.
  • the amount of the Lewis acid, the compound represented by the general formula (A), and the solvent used may be appropriately adjusted with respect to the amount (mol number) of the compound represented by the above.
  • the magnesium battery of the present invention includes a positive electrode, a negative electrode, and an electrolytic solution according to the present invention.
  • the "magnesium battery” includes everything that involves a magnesium reaction at the negative electrode.
  • the magnesium reaction includes dissolution / precipitation of magnesium at the interface between a magnesium metal and an electrolytic solution, an intercalation reaction of magnesium ions with a carbon-based material, and alloying of an element such as bismuth with magnesium.
  • Specific examples of the type of magnesium battery include a primary battery, a secondary battery, an air battery, an electric double layer capacitor, and the like, and a secondary battery is preferable.
  • the magnesium battery of the present invention may further have a separator in addition to the positive electrode, the negative electrode and the electrolytic solution according to the present invention.
  • the separator may be one that electrically insulates the positive electrode and the negative electrode and allows magnesium ions to pass through, and examples thereof include microporous polymers such as glass fiber and porous polyolefin. Be done.
  • specific examples of the porous polyolefin include, for example, porous polyethylene alone or one in which porous polyethylene and porous polypropylene are laminated to form a plurality of layers.
  • the positive electrode contains at least one silver compound selected from AgO, Ag 2 O, Ag S or Ag 2 S, and the negative electrode contains metallic magnesium or a magnesium alloy, and the electrolytic solution.
  • a magnesium battery is preferably a mixture of a compound represented by any one of the general formulas (I) to (IV), Lewis acid, and a solvent; the positive electrode is AgO, Ag 2.
  • the negative electrode contains a silver compound selected from O, Ag S or Ag 2 S, the negative electrode contains a metallic magnesium or a magnesium alloy, and the electrolytic solution contains a compound represented by the general formula (I), Lewis acid, and a solvent.
  • mixing are those comprising, more preferably magnesium battery; the positive electrode, AgO, Ag 2 comprises O, or a combination thereof, wherein the negative electrode comprises a metal magnesium, the electrolyte has the general formula (I ' ), An aluminum compound, and an ether-based solvent are mixed, and a magnesium battery is more preferable.
  • Specific examples thereof include a magnesium battery composed of a combination of specific examples exemplified in the positive electrode, the negative electrode and the electrolytic solution according to the present invention described above; the positive electrode contains Ag O or Ag 2 O and is described above.
  • the negative electrode contains metallic magnesium, and the electrolytic solution is a mixture of B (OMgCl) 3 or C 6 H 5 B (OMgCl) 2 , aluminum chloride (III), tetrahydrofuran, triglime, or a mixed solvent of these two types.
  • B (OMgCl) 3 or C 6 H 5 B (OMgCl) 2 aluminum chloride (III), tetrahydrofuran, triglime, or a mixed solvent of these two types.
  • Magnesium batteries are particularly preferred.
  • the magnesium battery of the present invention thus obtained exhibits an excellent effect that it exhibits a high operating voltage and a high initial discharge capacity with respect to magnesium, and can be repeatedly charged and discharged with a high discharge capacity.
  • the mixture was mixed at a rotation speed of 200 rpm for 10 minutes to obtain a composition for forming a positive electrode material layer.
  • the obtained composition for forming a positive electrode material layer is applied to carbon paper (current collector: manufactured by Toray Industries, Inc.) and vacuum dried at 80 ° C. for 1 hour and 120 ° C. for 3 hours.
  • Positive electrode 1 Ag 2 O Electrodes were made.
  • Positive electrode 2 AgO electrode by the same method as in Production Example 1 except that silver (II) oxide (AgO) (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) was used instead of silver (I) oxide as the silver compound. was produced.
  • silver (II) oxide AgO
  • Positive electrode 3 Preparation of positive electrode 3 containing silver (I) sulfide
  • Positive electrode 3 By the same method as in Production Example 1 except that silver sulfide (I) (Ag 2 S) (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) was used instead of silver oxide (I) as the silver compound. An Ag 2 S electrode was prepared.
  • Comparative positive electrode 2 AgCl by the same method as in Production Example 1 except that silver chloride (I) (AgCl) (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) was used instead of silver (I) oxide as the silver compound. Electrodes were made.
  • the obtained solution was concentrated to 10 mL, and the resulting powder was washed with a mixed solvent of 10 mL of THF and 40 mL of diisopropyl ether.
  • the collected powder was vacuum dried at 80 ° C. to obtain magnesium borate trichloride (B (OMgCl) 3 ).
  • B (OMgCl) 3 magnesium borate trichloride
  • Example 1 Preparation of magnesium battery 1
  • the positive electrode 1 obtained in Production Example 1 is used as the positive electrode
  • Mg-Al-Zn alloy AZ31 manufactured by Nakagawa Metal Co., Ltd.
  • glass fiber manufactured by ADVANTEC
  • Product name Glass filter paper GA-100
  • Product name Battery evaluation resin 2-pole cell SB8, Positive electrode / negative electrode diameter: 16 mm
  • a magnesium battery 1 was produced using the electrolytic solution 1 obtained in Example 1.
  • Example 2 Preparation of magnesium battery 2
  • the magnesium battery 2 was produced in the same manner as in Example 1 except that the positive electrode 2 obtained in Production Example 2 was used instead of the positive electrode 1.
  • Example 3 Preparation of magnesium battery 3
  • the magnesium battery 3 was produced in the same manner as in Example 1 except that the positive electrode 3 obtained in Production Example 3 was used instead of the positive electrode 1.
  • Example 4 Preparation of magnesium battery 4
  • a magnesium battery 4 was produced in the same manner as in Example 1 except that a silver foil (manufactured by Nirako Co., Ltd., purity 99.98%, thickness 0.01 mm) was used instead of the positive electrode 1.
  • the silver foil is used as the positive electrode 4.
  • Example 1 except that, instead of the combination of the positive electrode 1 and the electrolytic solution 1, the positive electrodes 1 to 4, the comparative positive electrodes 1 and 2, the electrolytic solution 1 and the comparative electrolytic solution 2 were used as shown in Table 1. Magnesium batteries 101 to 107 were produced in the same manner as in the above.
  • Table 1 below shows the combinations of the magnesium batteries produced in Examples 1 to 4 and Comparative Examples 1 to 7 and the positive electrode and electrolytic solution used.
  • Example 1 Charge / discharge test of magnesium battery 1 and magnesium battery 103
  • (1) Charging / Discharging Test of Magnesium Battery 1 Using the magnesium battery 1 obtained in Example 1, the cutoff potential is 1.0 to 3.0 V (vs. negative electrode) in a glove box filled with argon gas at room temperature. , The charge / discharge test was carried out at a rate of 0.05C. An electrochemical measurement system (manufactured by Bio-Logic Science Instruments) was used for the test. The obtained charge / discharge curves of the first, second, and third cycles are shown in FIG.
  • the horizontal axis (mAh / g) in the figure represents the capacity per unit weight of Ag 2 O
  • the vertical axis (V) in the figure represents the potential of the positive electrode with reference to the potential of the negative electrode.
  • the solid line in the figure represents the result of the first cycle
  • the dotted line in the figure represents the result of the second cycle
  • the broken line in the figure represents the result of the third cycle.
  • the positive electrode 1 containing the silver or the silver compound Ag 2 O of the present invention is used in combination with the electrolytic solution 1 which is the electrolytic solution according to the present invention, as compared with the case where it is used in combination with the comparative electrolytic solution 1. It was found that it can be repeatedly charged and discharged with a high discharge capacity.
  • Example 2 Charging / Discharging Test of Magnesium Battery 2 and Magnesium Battery 104
  • a charge / discharge test was carried out in the same manner as in Experimental Example 1 (1) except that the magnesium battery 2 obtained in Example 2 was used instead of the magnesium battery 1. did.
  • the obtained charge / discharge curves of the first, second, and third cycles are shown in FIG.
  • the horizontal axis (mAh / g) in the figure represents the capacity per unit weight of AgO
  • the vertical axis (V) in the figure represents the potential of the positive electrode with reference to the potential of the negative electrode.
  • the solid line in the figure represents the result of the first cycle
  • the dotted line in the figure represents the result of the second cycle
  • the broken line in the figure represents the result of the third cycle.
  • the positive electrode 2 containing the silver or AgO which is a silver compound of the present invention is higher when used in combination with the electrolytic solution 1 which is the electrolytic solution according to the present invention than when used in combination with the comparative electrolytic solution 1. It was found that the discharge capacity can be repeatedly charged and discharged.
  • Example 3 Charging / Discharging Test of Magnesium Battery 3 and Magnesium Battery 105
  • a charge / discharge test was carried out in the same manner as in Experimental Example 1 (1) except that the magnesium battery 3 obtained in Example 3 was used instead of the magnesium battery 1. did.
  • the obtained charge / discharge curves of the first, second, and third cycles are shown in FIG.
  • the horizontal axis (mAh / g) in the figure represents the capacity per unit weight of Ag 2 S
  • the vertical axis (V) in the figure represents the potential of the positive electrode with reference to the potential of the negative electrode.
  • the solid line in the figure represents the result of the first cycle
  • the dotted line in the figure represents the result of the second cycle
  • the broken line in the figure represents the result of the third cycle.
  • the positive electrode 3 containing the silver or the silver compound Ag 2 S of the present invention is used in combination with the electrolytic solution 1 which is the electrolytic solution according to the present invention, as compared with the case where it is used in combination with the comparative electrolytic solution 1. It was found that it can be repeatedly charged and discharged with a high discharge capacity.
  • Example 4 Charging / Discharging Test of Magnesium Battery 4 and Magnesium Battery 106
  • Charging / discharging test of magnesium battery 4 The same as in Experimental Example 1 (1) except that the charging / discharging test was started from charging by using the magnesium battery 4 obtained in Example 4 instead of the magnesium battery 1.
  • a charge / discharge test was performed by the method.
  • the obtained charge / discharge curves of the first, second, and third cycles are shown in FIG.
  • the horizontal axis (mAh / g) in the figure represents the capacity per unit weight of Ag
  • the vertical axis (V) in the figure represents the potential of the positive electrode with reference to the potential of the negative electrode.
  • the solid line in the figure represents the result of the first cycle
  • the dotted line in the figure represents the result of the second cycle
  • the broken line in the figure represents the result of the third cycle.
  • the positive electrode 4 containing the silver or Ag, which is a silver compound of the present invention is higher when used in combination with the electrolytic solution 1 which is the electrolytic solution according to the present invention, than when used in combination with the comparative electrolytic solution 1. It was found that the discharge capacity can be repeatedly charged and discharged.
  • the horizontal axis (mAh / g) in the figure represents the capacity per unit weight of Mo 6 S 8
  • the vertical axis (V) in the figure represents the potential of the positive electrode with reference to the potential of the negative electrode.
  • the solid line in the figure represents the result of the first cycle
  • the dotted line in the figure represents the result of the second cycle
  • the broken line in the figure represents the result of the third cycle.
  • the magnesium battery using the positive electrodes 1 to 4 containing the silver or silver compound of the present invention used the comparative positive electrode 1 containing no silver or silver compound of the present invention (including Mo 6 S 8 which is a chevrel compound). It was found to operate at a higher voltage than magnesium batteries.
  • FIG. 16 shows the transition of the discharge capacity for each cycle in 1 to 10 cycles.
  • the horizontal axis in the figure represents the number of cycles in the charge / discharge test, and the vertical axis (mAh / g) in the figure represents the discharge capacity of each cycle.
  • the solid line in the figure is the result of the magnesium battery 1 of Experimental Example 1 (1)
  • the broken line in the figure is the result of the magnesium battery 2 of Experimental Example 2 (1)
  • the alternate long and short dash line in the figure is Experimental Example 3 ( The result of the magnesium battery 3 in 1)
  • the long two-dot chain line in the figure shows the result of the magnesium battery 4 of Experimental Example 4 (1)
  • the dotted line in the figure shows the result of the magnesium battery 102 of Experimental Example 6 (1).
  • the positive electrodes 1 to 4 containing the silver or silver compound of the present invention are initially higher than the comparative positive electrode 2 which does not contain the silver or silver compound of the present invention (containing AgCl which does not correspond to the silver or silver compound of the present invention). It was found that it has a discharge capacity and can be repeatedly charged and discharged with a high discharge capacity.

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Abstract

 Une batterie au magnésium selon la présente invention comprend : une électrode positive qui contient de l'argent ou au moins une substance choisie parmi AgO, Ag2O, AgS et Ag2S ; une électrode négative qui contient un métal de magnésium ou un alliage de magnésium ; et une solution électrolytique qui est obtenue par mélange d'un composé représenté par la formule générale (I) ou similaire, d'un acide de Lewis ou similaire, et un solvant. (Dans la formule générale (I), chacun de X1 et X2 représente indépendamment un atome de chlore ou un atome de brome ; et R1 représente un groupe –OmgCl, un groupe –OmgBr, un groupe alkyle, un groupe alkoxy, un groupe phenoxy, un groupe aryle qui n'est pas substitué ou a, en tant que substituant, un groupe –B(OMgCl)2, un groupe –B(OMgBr)2, un groupe halogène, un groupe alkyle, un groupe alkoxy, un groupe vinyle, un groupe phényle ou un groupe phenoxy, ou un groupe monocyclique ou un groupe bicyclique hétérocyclique qui n'est pas substitué ou a, en tant que substituant, un groupe –B(OMgCl)2, un groupe –B(OMgBr)2, un groupe halogène, un groupe alkyle, un groupe alkoxy, un groupe vinyle, un groupe phényle ou un groupe phenoxy.)
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Publication number Priority date Publication date Assignee Title
WO2025163918A1 (fr) * 2024-02-02 2025-08-07 Ｎｔｔ株式会社 Batterie secondaire

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JP2000353543A (ja) * 1999-06-08 2000-12-19 Matsushita Electric Ind Co Ltd 非水電解液二次電池
WO2013157187A1 (fr) * 2012-04-16 2013-10-24 パナソニック株式会社 Électrolyte non aqueux pour élément électrochimique, procédé de production associé, et élément électrochimique utilisant cet électrolyte
JP2014521195A (ja) * 2011-08-05 2014-08-25 トヨタ自動車株式会社 マグネシウム電池用電解液
WO2017170976A1 (fr) * 2016-04-01 2017-10-05 和光純薬工業株式会社 Solution électrolytique contenant des ions magnésium
WO2018235828A1 (fr) * 2017-06-21 2018-12-27 株式会社村田製作所 Matériau de sulfure de magnésium, matériau composite de sulfure de magnésium, élément d'électrode positive pour accumulateurs, matériau semi-conducteur à large bande interdite, accumulateur au magnésium et procédé de production de sulfure de magnésium de zinc
WO2019013165A1 (fr) * 2017-07-12 2019-01-17 株式会社村田製作所 Batterie rechargeable au magnésium, solution électrolytique et procédé de fabrication d'une solution électrolytique

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Publication number Priority date Publication date Assignee Title
JP2000353543A (ja) * 1999-06-08 2000-12-19 Matsushita Electric Ind Co Ltd 非水電解液二次電池
JP2014521195A (ja) * 2011-08-05 2014-08-25 トヨタ自動車株式会社 マグネシウム電池用電解液
WO2013157187A1 (fr) * 2012-04-16 2013-10-24 パナソニック株式会社 Électrolyte non aqueux pour élément électrochimique, procédé de production associé, et élément électrochimique utilisant cet électrolyte
WO2017170976A1 (fr) * 2016-04-01 2017-10-05 和光純薬工業株式会社 Solution électrolytique contenant des ions magnésium
WO2018235828A1 (fr) * 2017-06-21 2018-12-27 株式会社村田製作所 Matériau de sulfure de magnésium, matériau composite de sulfure de magnésium, élément d'électrode positive pour accumulateurs, matériau semi-conducteur à large bande interdite, accumulateur au magnésium et procédé de production de sulfure de magnésium de zinc
WO2019013165A1 (fr) * 2017-07-12 2019-01-17 株式会社村田製作所 Batterie rechargeable au magnésium, solution électrolytique et procédé de fabrication d'une solution électrolytique

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2025163918A1 (fr) * 2024-02-02 2025-08-07 Ｎｔｔ株式会社 Batterie secondaire

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