WO2020235615A1 - Magnesium battery - Google Patents

Abstract

 A magnesium battery according to the present invention is provided with: a positive electrode that contains silver or at least one substance selected from among AgO, Ag₂O, AgS and Ag₂S; a negative electrode that contains magnesium metal or a magnesium alloy; and an electrolyte solution that is obtained by mixing a compound represented by general formula (I) or the like, a Lewis acid or the like, and a solvent. (In general formula (I), each of X¹ and X² independently represents a chlorine atom or a bromine atom; and R¹ represents an –OmgCl group, an –OmgBr group, an alkyl group, an alkoxy group, a phenoxy group, an aryl group that is not substituted or has, as a substituent, a –B(OMgCl)₂ group, a –B(OMgBr)₂ group, a halogeno group, an alkyl group, an alkoxy group, a vinyl group, a phenyl group or a phenoxy group, or a monocyclic or bicyclic heterocyclic group that is not substituted or has, as a substituent, a –B(OMgCl)₂ group, a –B(OMgBr)₂ group, a halogeno group, an alkyl group, an alkoxy group, a vinyl group, a phenyl group or a phenoxy group.)

Description

Magnesium battery

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.

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. As an example of 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).

Further, as an example in which magnesium ions are not inserted into or desorbed from an active material, 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). In addition to this, 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).

Further, as an electrolytic solution for magnesium batteries, development of an electrolytic solution having high oxidative stability aimed at high-voltage magnesium batteries is required. For example, Wang et al. Have reported a magnesium electrolyte using a non-nucleophilic magnesium salt (Non-Patent Document 3).

Japanese Unexamined Patent Publication No. 2016-51519

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. On the other hand, although 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. Further, 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.
In addition, 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.

In view of the above situation, as a result of diligent studies, 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].
[I] 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. There is 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. ₂ groups, halogeno group, alkyl group, alkoxy group, vinyl group, phenyl group or phenoxy group, or unsubstituted, aryl group having 6 to 18 carbon atoms; or ₂ -B (OMgCl) groups as substituents , -B (OMgBr) Represents a monocyclic or bicyclic heterocyclic group having _two groups, a halogeno group, an alkyl group, an alkoxy group, a vinyl group, a phenyl group or a phenoxy group, or an substituent. ];

[In general formula (II), 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. ];

{In general formula (III), m ₁ represents 0 or 2,
When m ₁ = 0, m ₂ represents 2, and when m ₁ = 2, m ₂ represents 0 or 1.
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. An aryloxy group having 6 to 10 carbon atoms, which has a group or is not substituted; or represents a group represented by the following general formula (III-1):

[In general formula (III-1), 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. Alternatively, it represents an aryloxy group having 6 to 10 carbon atoms, which has an alkoxy group or is unsubstituted. ];
Two 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. ]. };

[In general formula (IV), 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. An aryl group having 6 to 14 carbon atoms; or a biphenyl group having a -SO ₃ MgCl group or a -SO ₃ MgBr group as a substituent, or an unsubstituted biphenyl group. ];

[In the general formula (A), 4 pieces of R ⁷ each independently represent an alkyl group, a perfluoroalkyl group having 1 to 6 carbon atoms, a phenyl group or a perfluorophenyl group having 1 to 6 carbon atoms. ].
[Ii] The magnesium battery according to the invention [i], wherein the positive electrode contains at least one silver compound selected from Ag O, Ag ₂ O, Ag S or Ag ₂ S.
[Iii] The magnesium battery according to the invention [i] or [ii], wherein the positive electrode contains Ag O, Ag ₂ O, or a combination thereof.
[Iv] In any one of the inventions [i] to [iii], wherein the electrolytic solution is a mixture of a compound represented by the following general formula (I), a Lewis acid, and a solvent. Magnesium batteries listed:

[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. ₂ groups, halogeno group, alkyl group, alkoxy group, vinyl group, phenyl group or phenoxy group, or unsubstituted, aryl group having 6 to 18 carbon atoms; or ₂ -B (OMgCl) groups as substituents , -B (OMgBr) ₂ group, with a halogeno group, an alkyl group, an alkoxy group, vinyl group, phenyl group or phenoxy group, or unsubstituted, a heterocyclic group of monocyclic or bicyclic. ].

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.

[Positive electrode according to the present invention]
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 μm or more and 100 μm or less, and more preferably 1 μm or more and 50 μm or less. As the silver or the silver compound of the present invention, 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. Alternatively, 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. Among them, 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.

As the current collector in the positive electrode according to the present invention, a known current collector usually used in this field can be used. Specifically, for example, 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 μm or more and 300 μm 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.

As the conductive auxiliary agent for the positive electrode according to the present invention, 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.

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. 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. Among them, 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.

Among the other compounds in the positive electrode according to the present invention, specific examples of 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 , Mg _0.5 Hf _0.5 Sc _1.0 (MoO ₄ ) ₃ , MgZrWO ₄ , MgFe ₂ O ₄ , MgMn ₂ O ₄ , MgNi ₂ O ₄ , MgCr _{2 O 4, MgCoSiO 4, MgFeSiO 4} , MgNiSiO 4, MgMnSiO 4, MgNi 0.9 Mn 0.1 SiO 4, MgVSiO 4, MgCuSiO 4, Mg 1.03 Mn 0.97 SiO 4, MgMnNiO 4, MgMn 1.15 Ni 0.6 Ti 0.25 O 4, Mg 0.75 Fe _{0.25 Ca (SiO 3) 2,} Mg 0.59 Co 0.41 CaSiO, Mg 0.71 Fe 1.29 (SiO 3) 2, Mg 1.88 Fe 0.12 (SiO 3) 2, MgAg 0.5 Fe 0.95 Nb 0.05 O 4, Mg 2 SiO 4, KMnO 4 , Mg (MnO ₄ ) ₂ , NiCl ₂ , CoCl ₂ , FeCl ₂ , CrCl ₂ , FeF ₃ , MnF ₃ , LaF ₃ , NiS, FeS, CuS, CoS, ZrS ₂ , WS ₂ , CoS ₂ , MoS ₂ , MnS _{2, NbS 2, NbS 3,} TiS 2, TiB 2, ZrB 2, MoB 2, VS 2, WSe 2, Cu 2 Se, Mo 9 Se 11, NiSSe, VBO 3, TiBO 3, MnBO 3, CoBO 3, V _0.5 Fe _0.5 BO Active material composed of ₃ , V _0.5 Ti _0.5 BO ₃ , V _0.5 Ti _0.3 Fe _0.2 BO ₃ , V ₂ O ₅ , MgCl ₂ , P ₂ O ₅ ; Fe ²⁺ , Cu ²⁺ , Ti ²⁺ , Cd active material having an amorphous structure synthesized from KMnO ₄ and hydrochloric acid; complex of TiNb ₂ O ₇ and graphene; the salts of metal cations and polysulfide of ^2+; Mg ₂ SiO ₄ boron (B) doped MoS ₂ And V ₂ O ₅ carbon composites; aerogel-like V ₂ O ₅ ; nanowire-like Mn ₃ O ₄ ; Mn O ₂ containing crystalline water; porous Mn ₃ O ₄ nanoparticles; nanotube-like TiS ₂ ; potassium Dope K-α MnO ₂ ; Prussian blue analogs and the like can be mentioned.

In addition, 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.

Among the other compounds in the positive electrode according to the present invention, specific examples of the organic active material include rubian acid, 2,5-dimercapto-1,3,4-thiadiazole (DMcT), and trioxotriangulene. , 2,2,6,6-tetramethyl-1-piperidinyloxy (TEMPO), 4-hydroxy-2,2,6,6-tetramethylpiperidinyloxy (4-hydroxy-TEMPO), dimethoxybenzoquinone (DMBQ), 9,10-anthraquinone, porphyrin, magnesium porphyrin, phthalocyanine, phthalocyanine magnesium, magnesium anthracene, polyaniline, polyquinone derivative, quinone polymer, Poly (hydroquinoyl-benzoquinonyl sulfide), Carbyne polysulfide, poly-2,2' -dithiodianiline (PDTDA), poly (4-methacryloyloxy-2,2,6,6-tetramethylpiperidine-N-oxyl) (PTMA), Poly (anthraquinonyl) sulfide, fullerene, S-BUMB18C6, S-UOEE, huh Examples thereof include graphite compound, graphite fluoride mixed with copper, graphene fluoride and the like.

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.

In the preparation of the positive electrode according to the present invention, 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. Examples of the solvent include water, N-methyl-2-pyrrolidone (NMP), dimethylformamide, dimethylacetamide, methylformamide, dimethyl sulfoxide, acetonitrile, tetrahydrofuran, γ-butyrolactone, toluene, methylethylketone, ethyl acetate, dioxane and the like. Water and NMP are preferred.

In the production of the positive electrode according to the present invention, 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 μm or more and 1000 μm or less, preferably 1 μm or more and 500 μm or less, and 1 μm or more and 300 μm or less. More preferred.

In the production of the positive electrode according to the present invention, 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.

In the production of the positive electrode according to the present invention, 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 (necessity of vacuum, drying time, drying temperature) may be appropriately set according to the coating amount and the volatilization rate of the composition for forming the positive electrode material layer. As a specific drying method, for example, 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.

In the production of the electrode of the present invention, if necessary, 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.

[Negative electrode according to the present invention]
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. Here, 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-Ga alloy, Mg-Pb alloy, Mg-Ni alloy, Mg-Cu alloy, Mg-Al alloy, Mg-Ca alloy, Mg-Li alloy, Mg-Bi-Sb alloy, Mg-Al-Zn alloy, 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. Specifically, 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. If desired, a conductive auxiliary agent, a binder, a supporting salt, an ionic conductive polymer, and / or other compounds may be used. Among them, those using metallic magnesium or magnesium alloy as the negative electrode itself are preferable. The current collector, conductive auxiliary agent, binder, supporting salt, ionic conductive polymer, and other compounds that can be contained in the negative electrode according to the present invention are the same as those that can be contained in the positive electrode according to the present invention. The same applies to the preferred ones.

When a metallic magnesium or magnesium alloy is used for the negative electrode material layer, 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. When 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.

When a metallic magnesium or a magnesium alloy is used for the negative electrode material layer, 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.

[Electrolytic solution according to the present invention: compound represented by the general formula (I)]

[In general formula (I), R ¹ , X ¹ and X ² are the same as above. ]

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.

Examples of the 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.

[In the general formula (I-1), 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. ]

[In general formula (I-2), n ₂ represents an integer from 0 to 7, and R ⁸ is the same as above. ]

[In general formula (I-3), n ₃ represents an integer from 0 to 9, and R ⁸ is the same as above. ]

The 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.

As 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.

As n ₂ of the general formula (I-2), an integer of 0 to 3 is preferable, and 0 is more preferable.

As 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. Phenyl group, difluorophenyl group, trifluorophenyl group; trill group, xsilyl group, mesityl group, ethylphenyl group, diethylphenyl group, triethylphenyl group; methoxyphenyl group, dimethoxyphenyl group, trimethoxyphenyl group, ethoxyphenyl group, Diethoxyphenyl group, triethoxyphenyl group; biphenyl group; phenoxyphenyl group, etc. include phenyl group, -C ₆ H _4- B (OMgCl) ₂ group, fluorophenyl group, difluorophenyl group, trill group, xsilyl group. , Phenylphenyl group, dimethoxyphenyl group, biphenyl group, phenoxyphenyl group are more preferable, and phenyl group is particularly preferable.

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. Naphtyl group, difluoronaphthyl group, trifluoronaphthyl group; methylnaphthyl group, dimethylnaphthyl group, trimethylnaphthyl group, ethylnaphthyl group, diethylnaphthyl group, triethylnaphthyl group; methoxynaphthyl group, dimethoxynaphthyl group, trimethoxynaphthyl group, ethoxy Examples thereof include a naphthyl group, a diethoxynaphthyl group, a triethoxynaphthyl group; a phenylnaphthyl group; a phenoxynaphthyl group, and a naphthyl group is more preferable.

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. Specifically, for example, 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. Among them, 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. Examples of 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. Further, the number of heteroatoms contained in the bicyclic heterocyclic group is 1 or more, preferably 1 to 2, and more preferably 1. Specifically, for example, a 5-membered monocyclic ring having one heteroatom such as benzofuran, isobenzofuran, 1-benzothiophene, 2-benzothiophene, indol, isoindole, indolin, isoindrin, and indridin. A bicyclic heterocyclic group in which a heterocycle and benzene are condensed; one heteroatom such as 2H-chromen, 4H-chromen, 1H-isochromen, 3H-isochromen, chroman, isochroman, quinoline, isoquinoline, 4H-quinolidine, etc. A bicyclic heterocyclic group in which a 6-membered monocyclic heterocycle and benzene are condensed; a 5-membered monocyclic heterocycle having two heteroatoms such as benzoimidazole, benzothiazole, and 1H-indazole. Bicyclic heterocyclic group fused with benzene; a 6-membered monocyclic heterocycle having two heteroatoms such as cinnoline, quinazoline, quinoxaline, 1,8-naphthylidine, and phthalazine, and benzene fused with two. Cyclic heterocyclic groups and the like can be mentioned. Among them, 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.
When 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. The groups shown are particularly preferred.

[In the general formula (I-4), 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. ]

[In general formula (I-5), n ₅ represents an integer from 0 to 4, and R ⁹ is the same as above. ]

[In general formula (I-6), n ₆ represents an integer from 0 to 5, and R ⁹ and Y ² are the same as above. ]

[In general formula (I-6), n ₇ represents an integer from 0 to 5, and R ⁹ and Y ² are the same as above. ]

The 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). The same as those as substituents on the 18 aryl groups are mentioned, and so are the preferred ones.

Preferred examples of 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).

In Y ² of the general formulas (I-4) to (I-7), 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.

In Y ² of the general formulas (I-4) to (I-7), as 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.

As Y ² of the general formulas (I-4) to (I-7), an oxygen atom and a sulfur atom are preferable, and an oxygen atom is more preferable.

As n ₄ of the general formula (I-4), an integer of 0 to 2 is preferable, and 0 is more preferable.

As n ₅ of the general formula (I-5), an integer of 0 to 2 is preferable, and 0 is more preferable.

As n _{6 in the} general formula (I-6), an integer of 0 to 2 is preferable, and 0 is more preferable.

As 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. Preferably, the group represented by the general formula (I-4') is particularly preferable.

[In the general formulas (I-4') to (I-7'), Y ² is the same as above. ]

Specific examples of the group represented by the general formula (I-4') include the following groups and the like.

Specific examples of the group represented by the general formula (I-5') include the following groups.

Specific examples of the group represented by the general formula (I-6') include the following groups and the like.

Among the above specific examples, the following groups are preferable.

Specific examples of the group represented by the general formula (I-7') include the following groups and the like.

Among the above specific examples, the following groups are preferable.

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'). Is more preferred. Specifically, for example, -OMgCl group, -OMgBr group; methyl group, ethyl group, n-propyl group, n-butyl group; methoxy group, ethoxy group, n-propoxy group, n-butoxy group; phenoxy group; phenyl. Group, -C ₆ H ₄ -B (OMgCl) ₂ groups, -C ₆ H ₄ -B (OMgBr) ₂ groups, fluorophenyl group, difluorophenyl group, trifluorophenyl group, trill group, xylyl group, mesityl group, Ethylphenyl group, diethylphenyl group, triethylphenyl group, methoxyphenyl group, dimethoxyphenyl group, trimethoxyphenyl group, ethoxyphenyl group, diethoxyphenyl group, triethoxyphenyl group, biphenyl group, phenoxyphenyl group; naphthyl group; anthracenyl Group; The following groups can be mentioned.

Among the above specific examples, -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').

[In the 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. Represents a group represented by the above general formulas (I-1) to (I-3) or a group represented by the above general formulas (I-4') to (I-7'), and X ¹ and X ² are as described above. the same. ]

As the linear alkyl group having 1 to 4 carbon atoms in R ¹¹ of the general formula (I'), a methyl group and an ethyl group are preferable, and a methyl group is more preferable.

As the linear alkoxy group having 1 to 4 carbon atoms in R ¹¹ of the general formula (I'), 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.

As the compound represented by the general formula (I), in addition to the above-mentioned specific examples, specific examples and preferable compounds described in International Publication WO2016 / 084924 can be appropriately used.

[Electrolytic solution according to the present invention: compound represented by the general formula (II)]

[In general formula (II), Y ¹ , X ³ and R ² to R ⁴ are the same as above. ]

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.

Examples of the 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. Yes, 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.

Specific examples of the 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-. Propyl group, heptafluoroisopropyl group, perfluoro-n-butyl group, perfluoroisobutyl group, perfluoro-sec-butyl group, perfluoro-tert-butyl group, fluoromethyl group, fluoroethyl group, fluoro-n-propyl 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. Among them, 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.

Specific examples of 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. Propoxymethyl group, n-butoxymethyl group, isobutoxymethyl group, sec-butoxymethyl group, tert-butoxymethyl group, methoxyethyl group, ethoxyethyl group, n-propoxyethyl group, isopropoxyethyl group, n-butoxyethyl group Group, isobutoxyethyl group, sec-butoxyethyl group, tert-butoxyethyl group, methoxy-n-propyl group, ethoxy-n-propyl group, n-propoxy-n-propyl group, isopropoxy-n-propyl group, n-butoxy-n-propyl group, isobutoxy-n-propyl group, sec-butoxy-n-propyl group, tert-butoxy-n-propyl group, methoxy-n-butyl group, ethoxy-n-butyl group, n- Propoxy-n-butyl group, isopropoxy-n-butyl group, n-butoxy-n-butyl group, isobutoxy-n-butyl group, sec-butoxy-n-butyl group, tert-butoxy-n-butyl group, etc. Can be mentioned. Of these, 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.

In R ³ and R ⁴ of the general formula (II), 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.

Specific examples of "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 ³ and R ⁴ of the general formula (II) include, for example, a methyl group. Ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, 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; methoxymethyl group, ethoxymethyl group, methoxyethyl group, ethoxyethyl group, methoxy-n -Propyl group, ethoxy-n-propyl group, methoxy-n-butyl group, ethoxy-n-butyl group and the like can be mentioned. Of these, 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. Specifically, for example, vinyl group, allyl group, 1-propenyl group, isopropenyl group, 3-butenyl group, 2-butenyl group, 1-butenyl group, 1,3-butadienyl group, 4-pentenyl group, 3- Examples thereof include a penthenyl group, a 2-pentenyl group, a 1-pentenyl group, a 1-methyl-1-butenyl group, a 5-hexenyl group, a 4-hexenyl group, a 3-hexenyl group, a 2-hexenyl group, a 1-hexenyl group and the like. , 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.

Examples of the 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. Specific 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. For example, when 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.

In 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.

As a specific example of "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). For example, a group represented by the following general formula (II-1) can be mentioned.

[In the general formula (II-1), 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, and n ₈ is 0. Represents an integer of ~ 5. ]

The 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.

As R ¹² of the general formula (II-1), 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.

As 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. Specifically, for example, -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. 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, 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. Among them, -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').

[In the 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. Represents the group represented by the general formula (II-1), and Y ¹ , X ³ , R ¹² and n ₈ are the same as 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.

Specific examples of the compound represented by the general formula (II') include the following compounds.

Among the above specific examples, the following compounds are preferable.

As the compound represented by the general formula (II), in addition to the specific examples described above, specific examples of the compounds described in International Publication WO2017 / 170976 and preferable compounds can be appropriately used.

[Electrolytic solution according to the present invention: compound represented by the general formula (III)]

[In general formula (III), m ₁ , m ₂ , X ⁴ and R ⁵ are the same as above. ]

M ₁ of the general formula (III) is 0 or 2, preferably 2.

M ₂ of the general formula (III) is ₂ when m ₁ = 0, 0 or 1 when m ₁ = 2, and 1 is preferable.

X ⁴ of the general formula (III) is a chlorine atom or a bromine atom, and a chlorine atom is preferable.

As "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) As the substituent in the above, 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. ..

In 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. For example, if 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.

As a specific example of "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).

[In the general formula (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, and n ₉ is 0. Represents an integer of ~ 5. ]

The 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.

As R ¹⁵ of the general formula (III-3), 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.

As 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. , Dimethylphenoxy group, diethylphenoxy group, di-n-propylphenoxy group, di-n-butylphenoxy group; methoxyphenoxy group, ethoxyphenoxy group, n-propoxyphenoxy group, n-butoxyphenoxy group, dimethoxyphenoxy group, di Examples thereof include an ethoxyphenoxy group, a di-n-propoxyphenoxy group, a di-n-butoxyphenoxy group, a phenoxy group, a fluorophenoxy group, a difluorophenoxy group, a methylphenoxy group, an ethylphenoxy group, a dimethylphenoxy group and a diethylphenoxy group. , Methoxyphenoxy group, ethoxyphenoxy group, dimethoxyphenoxy group, diethoxyphenoxy group are more preferable, and phenoxy group is particularly preferable.

[In general formula (III-1), R ⁶ , X ⁵ and a are the same as above. ]

[In general formula (III-2), R ⁶ and b are the same as above. ]

As a in the general formula (III-1), 1 or 2 is preferable, and 1 is more preferable.

As b in the general formula (III-2), 1 or 2 is preferable, and 2 is more preferable.

X ⁵ of the general formula (III-1) is a chlorine atom or a bromine atom, and a chlorine atom is preferable.

As the "alkyl group having 1 to 6 carbon atoms having a halogeno group or an alkoxy group as a substituent or not substituted" in R ⁶ of the general formulas (III-1) and (III-2), the general formula ( The same as the "alkyl group having 1 to 6 carbon atoms having a halogeno group or an alkoxy group or not being substituted" in R ³ and R ⁴ of II) can be mentioned, and the preferred one is also the same.

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" in 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.

"As a substituent, an aryloxy group having a halogeno group, an alkyl group, a haloalkyl group or an alkoxy group, or an unsubstituted aryloxy group having 6 to 10 carbon atoms" in R ⁶ of the general formulas (III-1) and (III-2). Is the same as "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, or an unsubstituted group" in R ⁵ of the general formula (III). The same applies to 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. Alkoxy groups with 1 to 6 carbon atoms; Alkoxy groups with 1 to 6 carbon atoms; Alkoxy groups with 1 to 6 carbon atoms, alkyl groups with 1 to 6 carbon atoms, or alkoxy groups with 1 to 6 carbon atoms as substituents. 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. An alkyl group of 1 to 4 or a linear alkoxy group having 1 to 4 carbon atoms or an unsubstituted phenyl group; as a substituent, a fluoro group, a linear alkyl group having 1 to 4 carbon atoms or A linear phenoxy group having 1 to 4 carbon atoms or having no substituent is more preferable, and a -OMgCl group; an unsubstituted alkyl group having 1 to 4 carbon atoms; an alkoxy group having 1 to 4 carbon atoms. Unsubstituted phenyl group; unsubstituted phenoxy group is more preferable; -OMgCl group; unsubstituted and linear alkyl group having 1 to 4 carbon atoms; linear alkoxy group having 1 to 4 carbon atoms; no Substituted phenyl groups; unsubstituted phenoxy groups are particularly preferred. Specific examples thereof 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, phenoxy group and the like. Therefore, -OMgCl group, methyl group, ethyl group, methoxy group, ethoxy group, phenyl group and phenoxy group are preferable, and -OMgCl group is more preferable.

Specific examples of the group represented by the general formula (III-1) include the group represented by the following general formula (III-4).

[In the 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. Represents the group represented by the general formula (II-1) or the group represented by the general formula (III-3), and X ⁵ and a are the same as above. ]

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.

Among the groups represented by the general formula (III-4), the group represented by the following formula (III-5) is preferable.

When two R ^5s in the general formula (III) form the general formula (III-2), the general formula (III) has a ring structure represented by the following general formula (III-6).

[In general formula (III-6), m ₃ represents 0 or 1, and R ⁶ , X ⁴ and b are the same as above. ]

M ₃ of the general formula (III-6) is 0 or 1, preferably 1.

Specific examples of the general formula (III-2) include the following general formula (III-7).

[In general formula (III-7), R ¹⁶ and b are the same as above. ]

Among the general formulas (III-7), the following formula (III-8) is preferable.

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. Alkoxy group having 1 to 6 carbon atoms; as a substituent, it has 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 is unsubstituted. , 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. 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; unsubstituted and linear alkyl group having 1 to 4 carbon atoms; linear alkoxy group having 1 to 4 carbon atoms; linear carbon number 1 to 1 ~ having 4 alkoxy group, or an unsubstituted phenyl group; a group represented by formula (III-5);; unsubstituted phenoxy group two R ⁵ form a formula (III-8) Is particularly preferable. Specifically, for example, -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. Phenyl group, n-propoxyphenyl group, n-butoxyphenyl group, dimethoxyphenyl group, diethoxyphenyl group, di-n-propoxyphenyl group, di-n-butoxyphenyl group, phenoxy group, formula (III-5) groups represented, two R ⁵ in the formed formula (III-8), and the like, -OMgCl group, a methyl group, an ethyl group, a methoxy group, an ethoxy group, a phenyl group, methoxyphenyl group, ethoxyphenyl group , dimethoxyphenyl group, diethoxy phenyl group, a phenoxy group, a group represented by the formula (III-5), preferably two R ⁵ in the formed formula (III-8), -OMgCl group, methyl group, phenyl A group, a methoxyphenyl group, a phenoxy group, and a group represented by the formula (III-5) are particularly preferable.

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).

[In the general formulas (III'-1) and (III'-2), R ¹⁷ , R ¹⁹ and R ²⁰ are independently -OMgCl group, -OMgBr group, and unsubstituted alkyl having 1 to 6 carbon atoms. A group, an alkoxy group having 1 to 6 carbon atoms, a group represented by the above general formula (II-1) or a group represented by the above general formula (III-3), and R ¹⁸ is a -OMgCl group or a -OMgBr group. , An unsubstituted alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, a group represented by the above general formula (II-1), a group represented by the above general formula (III-3) or the above general. Representing the group represented by the formula (III-4), R ¹⁷ and R ¹⁸ may form the above general formula (III-7), and X ⁴ is the same as the above. ]

As the unsubstituted alkyl group having 1 to 6 carbon atoms in R ¹⁷ to R ²⁰ of the general formula (III'-1) and (III'-2), the carbon number 1 to 6 in R ¹ of the general formula (I) The same as the alkyl group of, and the preferred one is also the same.

As the alkoxy group having 1 to 6 carbon atoms in R ¹⁷ to R ²⁰ of the general formula (III'-1) and (III'-2), the alkoxy group having 1 to 6 carbon atoms in R ¹ of the general formula (I) The same is mentioned, and the preferred one is also the same.

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. A group, a phenyl group, a methoxyphenyl group, and a phenoxy group are particularly preferable.

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.

Specific examples of the compound represented by the general formula (III'-1) include the following compounds.

Among the above specific examples, the following compounds are preferable.

Among the above specific examples, the following compounds are more preferable.

Specific examples of the compound represented by the general formula (III'-2) include the following compounds.

Among the above specific examples, the following compounds are preferable.

Among the above specific examples, the following compounds are more preferable.

As the compound represented by the general formula (III), in addition to the specific examples described above, specific examples of the compounds described in International Publication WO2017 / 204322 and preferable compounds can be appropriately used.

[Electrolytic solution according to the present invention: compound represented by the general formula (IV)]

[In general formula (IV), X ⁶ and R ²¹ are the same as above. ]

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. Specifically, for example, 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.

Specific examples of the 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-n -Nonyl group, fluoro-n-decyl group, trichloromethyl group, pentachloroethyl group, heptachloro-n-propyl group, perchloro-n-butyl group, perchloro-n-pentyl group, perchloro-n-hexyl group, perchloro- n-Heptyl group, perchloro-n-octyl group, perchloro-n-nonyl group, perchloro-n-decyl group, tribromomethyl group, pentabromoethyl group, heptabromo-n-propyl group, perbromo-n-butyl group, Perbromo-n-pentyl group, perbromo-n-hexyl group, perbromo-n-heptyl group, perbromo-n-octyl group, perbromo-n-nonyl group, perbromo-n-decyl group, triiodomethyl group, pentaiodoethyl Group, heptaiodo-n-propyl group, periode-n-butyl group, periode-n-pentyl group, periodo-n-hexyl group, periodo-n-heptyl group, periode-n-octyl group, periode-n-nonyl group , Propyl-n-decyl group and the like. Among them, 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. Among them, one in which 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. When 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. Further, 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.

In 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,- Preferably an alkyl group having 1 to 6 carbon atoms having a SO ₃ MgCl group or a -SO ₃ MgBr group or not substituted; having a -SO ₃ MgCl group as a substituent or having an substituent of 1 to 6 carbon atoms. 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. Specifically, for example, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-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, etc. include 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.

The "haloalkyl group having 1 to 10 carbon atoms having a -SO ₃ MgCl group or a -SO ₃ MgBr group as a substituent" in R ²¹ of the general formula (IV) 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. Specifically, for example, 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.

Substituents of "aryl groups 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 as substituents" in R ²¹ of the general formula (IV). 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. For example, when 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.

"As a substituent in 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. As 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. Is preferable; as the substituent, 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. Specifically, for example, 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. 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, 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. Is more preferable, a phenyl group, a -C ₆ H ₄ -SO ₃ MgCl group is further preferable, and a phenyl group is particularly preferable.

"As a substituent, having -SO ₃ MgCl group or -SO ₃ MgBr group, or an unsubstituted biphenyl group" in R ²¹ of the general formula (IV) as has the -SO ₃ MgCl group as substituent or An unsubstituted biphenyl group is preferable, and an unsubstituted biphenyl group is more preferable.

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. Group: 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. Substituent alkyl groups with 1 to 6 carbon atoms; unsubstituted fluoroalkyl groups with 1 to 10 carbon atoms; as substituents, -SO ₃ MgCl group, -SO ₃ MgBr group, fluoro group, 1 to 4 carbon atoms 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. , A substituent having a -SO ₃ MgCl group or an unsubstituted, alkyl group having 1 to 6 carbon atoms; an unsubstituted fluoroalkyl group having 1 to 6 carbon atoms; having or not having a -SO ₃ MgCl group as a substituent. or unsubstituted biphenyl group having -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).

[In the general formulas (IV'-1) and (IV'-2), X ⁷ represents a chlorine atom or a bromine atom, and R ²² is an unsubstituted alkyl group having 1 to 6 carbon atoms; an unsubstituted carbon. Haloalkyl group of number 1 to 10; as a substituent, 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; or an unsubstituted biphenyl group 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.

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. As the substituent, 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. Specifically, for example, 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. An unsubstituted phenyl group having an alkyl group of 4 or an alkoxy group having 1 to 4 carbon atoms; an unsubstituted biphenyl group is preferable as a substituent, and an unsubstituted alkyl group having 1 to 6 carbon atoms; an unsubstituted group. 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. Specifically, for example, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, 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, phenyl group, fluorophenyl group, trill group, 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.

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. Specific 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.

As R ²³ of the general formula (IV'-2), 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.

Specific examples of the compound represented by the general formula (IV'-1) include the following compounds.

Specific examples of the compound represented by the general formula (IV'-2) include the following compounds.

Among the above specific examples, the following compounds are preferable.

Among the above specific examples, the following compounds are more preferable.

As the compound represented by the general formula (IV), in addition to the specific examples described above, specific examples of the compounds described in Japanese Patent Application No. 2018-246327 and preferable compounds can be appropriately used.

[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. Specifically, for example, when the compounds represented by the general formulas (I) to (IV) form a coordinate with tetrahydrofuran (THF), it is presumed to form the following coordinate.

[In the above formula, R ¹ to R ⁵ , R ²¹ , X ¹ to X ⁴ , X ⁶ , Y ¹ , m ₁ and m ₂ are the same as above. ]

Further, 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. In this case, 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. ]

As the compounds represented by the general formulas (I) to (IV), commercially available compounds or compounds appropriately synthesized by a method known per se may be used. For example, WO2016 / 084924, WO2017 / 170976. A compound appropriately synthesized by the production method described in Japanese Patent Application Laid-Open No. WO2017 / 204322, Japanese Patent Application No. 2018-246327, etc. may be used.

[Electrolytic solution according to the present invention: 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. Specifically, 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), tin bromide (IV), Tin compounds such as tin (II) chloride and tin (II) trifurate; titanium compounds such as titanium fluoride (IV), titanium chloride (IV), titanium bromide (IV), titanium iodide (IV); chromium fluoride (II), chromium fluoride (III), chromium chloride (II), chromium chloride (III), chromium bromide (II), chromium bromide (III), chromium iodide (II), chromium iodide (III) Chromium compounds such as: Iron compounds such as iron (II) fluoride, iron (II) chloride, iron (III) chloride, iron bromide (II), iron iodide (II); cobalt fluoride (II), chloride Examples thereof include cobalt compounds such as cobalt (II), cobalt bromide (II), and cobalt iodide (II), and boron compounds and aluminum compounds are preferable, and aluminum compounds are more preferable. Among such compounds, boron chloride (III), aluminum chloride (III), methylaluminum dichloride, dimethylaluminum chloride and triphenylaluminum are preferable, and aluminum chloride (III) (AlCl ₃ ) is particularly preferable.

[Electrolytic solution according to the present invention: compound represented by the general formula (A)]

[In the general formula (A), R ⁷ is the same as above. ]

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. Specifically, for example, 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, perfluoroisohexyl group, perfluoro- sec-hexyl group, perfluoro-tert-hexyl group, perfluoro-2-methylpentyl group, perfluoro-1,2-dimethylbutyl group, perfluoro-2,3-dimethylbutyl group, perfluoro-1-ethylbutyl Examples include a group, a perfluorocyclohexyl group, and the like, such as a trifluoromethyl group, a pentafluoroethyl group, a heptafluoro-n-propyl group, a heptafluoroisopropyl group, a perfluoro-n-butyl group, a perfluoroisobutyl group, and a perfluoro-. 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 four R ⁷ in general formula (A), an alkyl group having 1 to 6 carbon atoms, preferably a perfluoroalkyl group having 1 to 6 carbon atoms, more preferably a perfluoroalkyl group having 1 to 6 carbon atoms. Specifically, for example, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, 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; phenyl group; perfluorophenyl group, etc. 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). Imide, magnesium bis (n-butane sulfonyl) imide, magnesium bis (isobutan sulfonyl) imide, magnesium bis (sec-butane sulfonyl) imide, magnesium bis (tert-butan sulfonyl) imide, magnesium bis (cyclobutane sulfonyl) imide, magnesium bis (n-pentanesulfonyl) imide, magnesium bis (isopentanesulfonyl) imide, magnesium bis (sec-pentanesulfonyl) imide, magnesium bis (tert-pentanesulfonyl) imide, magnesium bis (neopentansulfonyl) imide, magnesium bis (2- Methylbutanesulfonyl) imide, magnesium bis (1,2-dimethylpropanesulfonyl) imide, magnesium bis (1-ethylpropanesulfonyl) imide, magnesium bis (cyclopentanesulfonyl) imide, magnesium bis (n-hexanesulfonyl) imide, magnesium Bis (isohexanesulfonyl) imide, magnesium bis (sec-hexanesulfonyl) imide, magnesium bis (tert-hexanesulfonyl) imide, magnesium bis (neohexanesulfonyl) imide, magnesium bis (2-methylpentanesulfonyl) imide, magnesium bis (1,2-Dimethylbutanesulfonyl) imide, magnesium bis (2,3-dimethylbutanesulfonyl) imide, magnesium bis (1-ethylbutanesulfonyl) imide, magnesium bis (cyclohexanesulfonyl) imide, etc. with 2 to 12 carbon atoms Magnesium bis (alcan sulfonyl) imide; magnesium bis (trifluoromethanesulfonyl) imide, magnesium bis (pentafluoroethanesulfonyl) imide, magnesium bis (heptafluoro-n-propanesulfonyl) imide, magnesium bis (heptafluoroisopropanesulfonyl) imide , Magnesium bis (perfluoro-n-butanesulfonyl) imide, Magnesium bis (perfluoroisobutanesulfonyl) imide, Magnesium bis (perfluoro-sec-butans) Luhonyl) imide, magnesium bis (perfluoro-tert-butanesulfonyl) imide, magnesium bis (perfluorocyclobutanesulfonyl) imide, magnesium bis (perfluoro-n-pentanesulfonyl) imide, magnesium bis (perfluoroisopentanesulfonyl) imide, Magnesium bis (perfluoro-sec-pentanesulfonyl) imide, magnesium bis (perfluoro-tert-pentanesulfonyl) imide, magnesium bis (perfluoroneopentansulfonyl) imide, magnesium bis (perfluoro-2-methylbutanesulfonyl) imide , Magnesium bis (perfluoro-1,2-dimethylpropanesulfonyl) imide, Magnesium bis (perfluoro-1-ethylpropanesulfonyl) imide, Magnesium bis (perfluorocyclopentanesulfonyl) imide, Magnesium bis (perfluoro-n-) Hexansulfonyl) imide, magnesium bis (perfluoroisohexanesulfonyl) imide, magnesium bis (perfluoro-sec-hexanesulfonyl) imide, magnesium bis (perfluoro-tert-hexanesulfonyl) imide, magnesium bis (perfluoroneohexanesulfonyl) imide ) Imide, magnesium bis (perfluoro-2-methylpentanesulfonyl) imide, magnesium bis (perfluoro-1,2-dimethylbutanesulfonyl) imide, magnesium bis (perfluoro-2,3-dimethylbutanesulfonyl) imide, magnesium Magnesium bis (perfluoroalkanesulfonyl) imide having 2 to 12 carbon atoms such as bis (perfluoro-1-ethylbutanesulfonyl) imide and magnesium bis (perfluorocyclohexanesulfonyl) imide; magnesium bis (phenylsulfonyl) imide; magnesium bis (Perfluorophenylsulfonyl) imide and the like can be mentioned.

Among the above specific examples, 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.

[Electrolytic solution according to the present invention: solvent]
As the solvent in the electrolytic solution according to the present invention, 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. preferable. Examples of such 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.

Examples of the ether solvent 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.
Examples of the halogenated hydrocarbon solvent 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.
Examples of the sulfone-based solvent 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. Sulfone, diethyl sulfone, ethyl-n-propyl sulfone, ethyl isopropyl sulfone, n-butyl ethyl sulfone, isobutyl ethyl sulfone, sec-butyl ethyl sulfone, tert-butyl ethyl sulfone, di-n-propyl sulfone, diisopropyl sulfone, n- Examples thereof include butyl-n-propyl sulfone and di-n-butyl sulfone.

Among the above specific examples, an ether solvent and a sulfone solvent are preferable, and an ether solvent is more preferable.
Among 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.

[Electrolytic solution according to the present invention]
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. Is. Among them, 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.
Specifically, for example, B (OMgCl) ₃ , CH ₃ B (OMgCl) ₂ , C ₂ H ₅ B (OMgCl) ₂ , CH ₃ OB (OMgCl) ₂ , C ₂ H ₅ OB (OMgCl) ₂ , C ₆ H ₅ OB (OMgCl) ₂ , C ₆ H ₅ B (OMgCl) ₂ , C ₆ H ₄ [B (OMgCl) ₂ ] ₂ , (C ₆ H ₄ F) B (OMgCl) ₂ , (C ₆ H ₃ F) ₂ ) B (OMgCl) ₂ , [C ₆ H ₄ (CH ₃ )] B (OMgCl) ₂ , [C ₆ H ₃ (CH ₃ ) ₂ ] B (OMgCl) ₂ , [C ₆ H ₄ (OCH ₃ ) ] B (OMgCl) ₂ , [C ₆ H ₃ (OCH ₃ ) ₂ ] B (OMgCl) ₂ , [C ₆ H ₄ (C ₆ H ₅ )] B (OMgCl) ₂ , [C ₆ H ₄ (OC ₆₎ H ₅ )] B (OMgCl) ₂ , C ₁₀ H ₇ B (OMgCl) ₂ , C ₁₄ H ₉ B (OMgCl) ₂ , (C ₄ H ₃ O) B (OMgCl) ₂ , (C ₄ H ₃ S) At least one selected from B (OMgCl) ₂ , (C ₄ H ₃ NH) B (OMgCl) ₂ , (C ₅ H ₄ N) B (OMgCl) ₂ or (C ₈ H ₅ O) B (OMgCl) ₂ And at least one aluminum compound selected from boron (III) chloride, aluminum (III) chloride, methylaluminum dichloride, dimethylaluminum chloride or triphenylaluminum, and at least selected from tetrahydrofuran, jigglime, triglime or tetraglime. 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. More specifically, "Maglution ^TM B01" (B (OMgCl) _3- AlCl ₃ complex (1: 6) / triglime solution) and "Maglution ^TM B02" (B (OMgCl)) manufactured by Fujifilm Wako Pure Chemical Industries, Ltd. ) _3- AlCl ₃ complex (1: 6) / triglime-tetrahydrofuran (50:50 vol%) solution) is preferred.

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. That is, 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). For example, 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. When 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). , When 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.

In addition to the above, 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.

In the electrolytic solution according to the present invention, 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. Manufactured by More specifically, 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. When 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. Moreover, you may perform filtration if necessary after mixing.

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.

When the compound represented by any one of the general formulas (I) to (IV) forms a coordinator, 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.

[Magnesium Battery of the Present Invention]
The magnesium battery of the present invention includes a positive electrode, a negative electrode, and an electrolytic solution according to the present invention.
In the present invention, the "magnesium battery" includes everything that involves a magnesium reaction at the negative electrode. Specifically, 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. This means a reaction in which magnesium ions are stored and released at a low potential such as 1 V or less in a battery material such as titanium oxide. 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.

Further, 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.

In the magnesium battery of the present invention, 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. However, 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. 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.

Hereinafter, the present invention will be described in detail with reference to Examples and Comparative Examples, but the present invention is not limited thereto.

[Production Example 1: Preparation of positive electrode 1 containing silver (I) oxide]
Add 15 parts by mass of acetylene black (conductive aid: Denka Co., Ltd.) to 70 parts by mass of silver oxide (I) (Ag ₂ O) (silver compound: manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) to make a planetary ball mill. It was crushed and mixed for 1.5 hours at a rotation speed of 200 rpm. Next, add an N-methyl-2-pyrrolidone (NMP) solution of polyvinylidene fluoride (PVDF) (binding agent: manufactured by Kureha Corporation, concentration 5 wt%) so that PVDF is 15 parts by mass, and further add NMP. In addition, 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.

[Production Example 2: Preparation of positive electrode 2 containing silver (II) oxide]
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.

[Production Example 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.

[Production Example 4: Preparation of Comparative Positive Electrode 1 Containing Mo ₆ S ₈ ]
Instead of silver (I) oxide, which is a silver compound, Mo ₆ S ₈ was prepared according to the method described in the literature (J. Electrochem. Soc., 2014, vol.161 (4), p.A593-A598). A comparative positive electrode 1: Mo ₆ S ₈ electrode was prepared in the same manner as in Preparation Example 1 except that the above was used.

[Production Example 5: Preparation of Comparative Positive Electrode 2 Containing Silver (I) Chloride]
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.

[Preparation Example 1: Preparation of Electrolyte Solution 1]
In a glove box filled with argon gas, 1.24 g (20 mmol) of boric acid (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) and 10 mL of tetrahydrofuran (THF) were added to the flask. Next, 30.2 mL (60.4 mmol) of a THF solution of ethylmagnesium chloride (EtMgCl) (manufactured by Tokyo Chemical Industry Co., Ltd., concentration 2M) was added dropwise at 0 ° C. or lower, and the mixture was stirred at room temperature for 30 minutes. 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 ). To 2.38 g (10 mmol) of the obtained magnesium borate trichloride, add 20 mL of triglime (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.), and further add aluminum chloride (AlCl ₃ ) (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) 8.00 g ( 60 mmol) was added, and the mixture was heated and stirred at 80 ° C. for 3 days. After cooling, the solution to which 20 mL of triglime was further added was filtered to obtain an electrolytic solution 1: B (OMgCl) _3- AlCl ₃ / triglime solution.

[Preparation Example 2: Preparation of Comparative Electrolyte Solution 1]
In a glove box filled with argon gas, 3.76 g (40 mmol) of phenol (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) and 20 mL of THF were added to the flask. Then, 20 mL (40 mmol) of a THF solution of EtMgCl (manufactured by Tokyo Chemical Industry Co., Ltd., concentration 2M) was added dropwise at 0 ° C. or lower, and the mixture was stirred at room temperature for 1 hour. The precipitated crystals were collected by filtration and vacuum dried at 60 ° C. to obtain phenoxymagnesium chloride (PhOMgCl). To 0.61 g (4 mmol) of the obtained phenoxymagnesium chloride, 16 mL of triglime (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) was added, and further, 0.53 g (4 mmol) of aluminum chloride (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) was added. , Stirred at room temperature for 3 hours to obtain a comparative electrolyte 1: PhOMgCl-AlCl ₃ / triglime solution.

[Example 1: Preparation of magnesium battery 1]
In a glove box filled with argon gas, 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.) is used as the negative electrode, and glass fiber (manufactured by ADVANTEC) is used as the separator. , Product name: Glass filter paper GA-100) is set in a polyphenylene sulfide resin cell (manufactured by EC Frontier Co., Ltd., Product name: Battery evaluation resin 2-pole cell SB8, Positive electrode / negative electrode diameter: 16 mm) and prepared as an electrolytic solution. 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.

[Comparative Examples 1 to 7: Fabrication of Magnesium Batteries 101 to 107]
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.

[Experimental 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, and 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, and the broken line in the figure represents the result of the third cycle.

(2) Charge / Discharge Test of Magnesium Battery 103 A charge / discharge test was carried out in the same manner as in Experimental Example 1 (1) except that the magnesium battery 103 obtained in Comparative 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 O, and 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, and the broken line in the figure represents the result of the third cycle.

(3) Comparison of Changes in Discharge Capacity Based on the results obtained in the charge / discharge tests of (1) and (2), the changes in discharge capacity for each cycle in 1 to 10 cycles are shown in FIG.
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 represents the result of the magnesium battery 1 of Experimental Example 1 (1), and the dotted line in the figure represents the result of the magnesium battery 103 of Experimental Example 1 (2).
From FIG. 3, it was found that the magnesium battery 1 using the positive electrode 1 and the electrolytic solution 1 in combination maintains a higher discharge capacity than the magnesium battery 103 using the positive electrode 1 and the comparative electrolytic solution 1 in combination. That is, 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.

[Experimental Example 2: Charging / Discharging Test of Magnesium Battery 2 and Magnesium Battery 104]
(1) Charge / discharge test of magnesium battery 2 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, and 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, and the broken line in the figure represents the result of the third cycle.

(2) Charging / Discharging Test of Magnesium Battery 104 A charging / discharging test was carried out in the same manner as in Experimental Example 1 (1) except that the magnesium battery 104 obtained in Comparative Example 4 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, and 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, and the broken line in the figure represents the result of the third cycle.

(3) Comparison of Changes in Discharge Capacity Based on the results obtained in the charge / discharge tests of (1) and (2), the changes in discharge capacity for each cycle in 1 to 10 cycles are shown in FIG.
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 represents the result of the magnesium battery 2 of Experimental Example 2 (1), and the dotted line in the figure represents the result of the magnesium battery 104 of Experimental Example 2 (2).
From FIG. 6, it was found that the magnesium battery 2 using the positive electrode 2 and the electrolytic solution 1 in combination maintains a higher discharge capacity than the magnesium battery 104 using the positive electrode 2 and the comparative electrolytic solution 1 in combination. That is, 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.

[Experimental Example 3: Charging / Discharging Test of Magnesium Battery 3 and Magnesium Battery 105]
(1) Charge / discharge test of magnesium battery 3 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, and 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, and the broken line in the figure represents the result of the third cycle.

(2) Charge / discharge test of 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 105 obtained in Comparative Example 5 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, and 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, and the broken line in the figure represents the result of the third cycle.

(3) Comparison of Changes in Discharge Capacity Based on the results obtained in the charge / discharge tests of (1) and (2), the changes in discharge capacity for each cycle in 1 to 10 cycles are shown in FIG.
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 represents the result of the magnesium battery 3 of Experimental Example 3 (1), and the dotted line in the figure represents the result of the magnesium battery 105 of Experimental Example 3 (2).
From FIG. 9, it was found that the magnesium battery 3 using the positive electrode 3 and the electrolytic solution 1 in combination maintains a higher discharge capacity than the magnesium battery 105 using the positive electrode 3 and the comparative electrolytic solution 1 in combination. That is, 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.

[Experimental Example 4: Charging / Discharging Test of Magnesium Battery 4 and Magnesium Battery 106]
(1) 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, and 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, and the broken line in the figure represents the result of the third cycle.

(2) Charging / Discharging Test of Magnesium Battery 106 A charging / discharging test was carried out in the same manner as in Experimental Example 4 (1) except that the magnesium battery 106 obtained in Comparative Example 6 was used instead of the magnesium battery 4. 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, and 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, and the broken line in the figure represents the result of the third cycle.

(3) Comparison of Changes in Discharge Capacity Based on the results obtained in the charge / discharge tests of (1) and (2), the changes in discharge capacity for each cycle in 1 to 10 cycles are shown in FIG.
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 represents the result of the magnesium battery 4 of Experimental Example 4 (1), and the dotted line in the figure represents the result of the magnesium battery 106 of Experimental Example 4 (2).
From FIG. 12, it was found that the magnesium battery 4 using the positive electrode 4 and the electrolytic solution 1 in combination maintains a higher discharge capacity than the magnesium battery 106 using the positive electrode 4 and the comparative electrolytic solution 1 in combination. That is, 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.

[Experimental Example 5: Charge / Discharge Test of Magnesium Battery 101 and Magnesium Battery 107]
(1) Charging / Discharging Test of Magnesium Battery 101 Using the magnesium battery 101 obtained in Comparative Example 1, a cutoff potential of 0.5 to 1.9 V (vs. negative electrode) was used 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 Mo ₆ S ₈ , and 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, and the broken line in the figure represents the result of the third cycle.

(2) Charge / Discharge Test of Magnesium Battery 107 A charge / discharge test was carried out in the same manner as in Experimental Example 1 (1) except that the magnesium battery 107 obtained in Comparative Example 7 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 Mo ₆ S ₈ , and 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, and the broken line in the figure represents the result of the third cycle.

From FIGS. 13 and 14, when the comparative positive electrode 1 was used, the magnesium battery 101 using the electrolytic solution 1 and the magnesium battery 107 using the comparative electrolytic solution 1 showed similar low discharge capacities. That is, in the comparative positive electrode 1 containing no silver or silver compound of the present invention, even if it is used in combination with the electrolytic solution 1 which is the electrolytic solution according to the present invention, the excellent effect as in the present invention cannot be achieved, and the comparative electrolysis cannot be achieved. It was found that only the same level of battery performance as when used in combination with Liquid 1 can be obtained.
Further, from FIGS. 1, 4, 7, 10, and 13, all of the magnesium batteries 1 to 4 using the positive electrodes 1 to 4 in combination with the electrolytic solution 1 have a voltage of about 2.0 V with respect to magnesium. It was found that it was operating and operated at a voltage higher than about 1.1 V of the magnesium battery 101 using the comparative positive electrode 1 and the electrolytic solution 1 in combination. That is, 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.

[Experimental Example 6: Charging / Discharging Test of Magnesium Battery 102]
(1) Charge / discharge test of magnesium battery 102 A charge / discharge test was carried out in the same manner as in Experimental Example 1 (1) except that the magnesium battery 102 obtained in Comparative 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 AgCl, and 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, and the broken line in the figure represents the result of the third cycle.

(2) Comparison of Transition of Discharge Capacity Based on the results obtained in the charge / discharge tests of Experimental Examples 1 to 4 and 6, 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), and 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), and the dotted line in the figure shows the result of the magnesium battery 102 of Experimental Example 6 (1). , Represent each.
From FIG. 16, all of the magnesium batteries 1 to 4 used in combination with the positive electrodes 1 to 4 and the electrolytic solution 1 have a higher initial discharge capacity than the magnesium batteries 102 used in combination with the comparative positive electrode 2 and the electrolytic solution 1. And it was found to maintain a high discharge capacity. That is, 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.

Claims (4)

1. A magnesium battery equipped 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. Yes, magnesium batteries:
   

   

   [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. ₂ groups, halogeno group, alkyl group, alkoxy group, vinyl group, phenyl group or phenoxy group, or unsubstituted, aryl group having 6 to 18 carbon atoms; or ₂ -B (OMgCl) groups as substituents , -B (OMgBr) ₂ group, with a halogeno group, an alkyl group, an alkoxy group, vinyl group, phenyl group or phenoxy group, or unsubstituted, a heterocyclic group of monocyclic or bicyclic. ];
   

   

   [In general formula (II), 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. ];
   

   

   {In general formula (III), m ₁ represents 0 or 2,
   When m ₁ = 0, m ₂ represents 2, and when m ₁ = 2, m ₂ represents 0 or 1.
   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. An aryloxy group having 6 to 10 carbon atoms, which has a group or is not substituted; or represents a group represented by the following general formula (III-1):
   

   

   [In general formula (III-1), 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. Alternatively, it represents an aryloxy group having 6 to 10 carbon atoms, which has an alkoxy group or is unsubstituted. ];
   Two 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. ]. };
   

   

   [In general formula (IV), 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. An aryl group having 6 to 14 carbon atoms; or a biphenyl group having a -SO ₃ MgCl group or a -SO ₃ MgBr group as a substituent, or an unsubstituted biphenyl group. ];
   

   

   [In the general formula (A), 4 pieces of R ⁷ each independently represent an alkyl group, a perfluoroalkyl group having 1 to 6 carbon atoms, a phenyl group or a perfluorophenyl group having 1 to 6 carbon atoms. ].
2. The magnesium battery according to claim 1, wherein the positive electrode contains at least one silver compound selected from Ag O, Ag ₂ O, Ag S or Ag ₂ S.
3. The magnesium battery according to claim 1, wherein the positive electrode contains Ag O, Ag ₂ O, or a combination thereof.
4. The magnesium battery according to claim 1, wherein the electrolytic solution is a mixture of a compound represented by the following general formula (I), a Lewis acid, and a solvent.
   

   

   [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. ₂ groups, halogeno group, alkyl group, alkoxy group, vinyl group, phenyl group or phenoxy group, or unsubstituted, aryl group having 6 to 18 carbon atoms; or ₂ -B (OMgCl) groups as substituents , -B (OMgBr) ₂ group, with a halogeno group, an alkyl group, an alkoxy group, vinyl group, phenyl group or phenoxy group, or unsubstituted, a heterocyclic group of monocyclic or bicyclic. ].

Images