JP7052794B2 - Positive electrode material for magnesium secondary batteries and magnesium secondary batteries - Google Patents

Description

The present disclosure relates to a magnesium secondary battery and a positive electrode material for a magnesium secondary battery.

As a next-generation secondary battery, the development of a magnesium-sulfur secondary battery is being enthusiastically promoted. By the way, as one of the causes of cycle deterioration of magnesium secondary batteries, sulfur is dissolved and / or eluted, that is, as sulfur (zero-valent molecule) or _Sn- ⁽ anionic molecule or atom). Elution is possible.

In lithium-sulfur secondary batteries, C. Bucur, et. Al., "A layer-by-layer supramolecular structure for a sulfur cathode", Energy is used as a technology to prevent elution of sulfur constituting the positive electrode member. The technology disclosed in Environ. Sci., 2016,9, 992-998 (Non-Patent Document 1) is known.

C. Bucur, et. Al., "A layer-by-layer supramolecular structure for a sulfur cathode", Energy Environ. Sci., 2016,9, 992-998

However, a technique for effectively preventing or suppressing the elution of sulfur constituting the positive electrode member of a magnesium secondary battery is not known as far as the present inventors have investigated.

Therefore, an object of the present disclosure is a positive electrode material for a magnesium secondary battery capable of effectively preventing or suppressing elution of sulfur constituting a positive electrode member of the magnesium secondary battery, and a magnesium secondary using such a positive electrode material. The next battery is to be provided.

The positive electrode material for the magnesium secondary battery of the present disclosure for achieving the above object is
Porous carbon materials, composite materials composed of sulfur or sulfur compounds, and
Coating material layer containing anionic polymer material and cationic polymer material,
Have.

The magnesium secondary battery of the present disclosure for achieving the above object is
A positive electrode member with at least a positive electrode active material layer,
Separator arranged facing the positive electrode member,
A negative electrode member containing magnesium or a magnesium compound disposed facing the separator, and
Electrolyte containing magnesium salt,
Equipped with
The positive electrode active material layer is
Porous carbon materials, composite materials composed of sulfur or sulfur compounds, and
It is composed of a positive electrode material composed of a coating material layer containing an anionic polymer material and a cationic polymer material.

The positive electrode material for the magnesium secondary battery of the present disclosure and the positive electrode material constituting the positive electrode member of the magnesium secondary battery of the present disclosure (hereinafter, these positive electrode materials are collectively referred to as "positive electrode material of the present disclosure". (Sometimes referred to as) is composed of a porous carbon material, a composite material composed of sulfur or a sulfur compound, and a coating material layer containing an anionic polymer material and a cationic polymer material. The coating material layer can prevent or suppress the elution of sulfur as a polysulfide anion even though magnesium ions (Mg ⁺² ) can easily pass through, resulting in high energy density and cycle characteristics. It is possible to realize an excellent magnesium secondary battery. It should be noted that the effects described in the present specification are merely exemplary and not limited, and may have additional effects.

FIG. 1 is a schematic (conceptual) cross-sectional view of a positive electrode material for a magnesium secondary battery of Example 1. FIG. 2 is a graph showing the measurement results of the zeta potential in the manufacturing process of the positive electrode material of Example 1 and Comparative Example 1. FIG. 3 is an SEM photograph of the positive electrode material of Example 1. FIG. 4 is a photograph showing the measurement results of carbon (C) atoms in the EDS measurement of the positive electrode material of Example 1. FIG. 5 is a photograph showing the measurement results of magnesium (Mg) atoms in the EDS measurement of the positive electrode material of Example 1. FIG. 6 is a photograph showing the measurement results of sulfur (S) atoms in the EDS measurement of the positive electrode material of Example 1. FIG. 7 is a graph showing the IR measurement results of the positive electrode material of Example 1. FIG. 8 is a schematic exploded view of the magnesium secondary battery of Example 1. FIG. 9 is a graph showing a charge / discharge curve of the magnesium secondary battery of Example 1. FIG. 10 is a schematic cross-sectional view of the electrochemical device (capacitor) of the second embodiment. FIG. 11 is a conceptual diagram of the electrochemical device (air battery) of the second embodiment. FIG. 12 is a conceptual diagram of the electrochemical device (fuel cell) of the second embodiment. FIG. 13 is a schematic cross-sectional view of the magnesium secondary battery (cylindrical magnesium secondary battery) according to the third embodiment. FIG. 14 is a schematic cross-sectional view of the magnesium secondary battery (flat plate type laminated film type magnesium secondary battery) in Example 3. FIG. 15 is a block diagram showing a circuit configuration example in Example 3 when the magnesium secondary battery of the present disclosure described in Example 1 is applied to a battery pack. 16A, 16B and 16C show a block diagram showing the configuration of the application example (electric vehicle) of the present disclosure in the third embodiment and the configuration of the application example (power storage system) of the present disclosure in the third embodiment, respectively. It is a block diagram and the block diagram which shows the structure of the application example (power tool) of this disclosure in Example 3. FIG. FIG. 17 is a conceptual diagram of the electrochemical device (battery) of the present disclosure. FIG. 18 is a diagram showing the production schemes of the positive electrode materials of Example 1 and Comparative Example 1. FIG. 19 is a diagram showing the production schemes of the positive electrode materials of Example 1 and Comparative Example 1, following FIG. FIG. 20 is a diagram showing the production schemes of the positive electrode materials of Example 1 and Comparative Example 1, following FIG. 19. FIG. 21 is a diagram showing the production schemes of the positive electrode materials of Example 1 and Comparative Example 1, following FIG. 20.

Hereinafter, the present disclosure will be described based on examples with reference to the drawings, but the present disclosure is not limited to the examples, and various numerical values and materials in the examples are examples. The explanation will be given in the following order.
1. 1. 2. Description of the present disclosure regarding the magnesium secondary battery, the positive electrode material for the magnesium secondary battery, and the whole. Example 1 (positive electrode material for the magnesium secondary battery and the magnesium secondary battery of the present disclosure)
3. 3. Example 2 (Modification of Example 1)
4. Example 3 (Application example of the magnesium secondary battery of Example 1)
5. others

<Explanation of the present disclosure of the magnesium secondary battery and the positive electrode material for the magnesium secondary battery, and general information>
In the positive electrode material and the like of the present disclosure, in the composite material, the porous carbon material may be dispersed inside the particles of sulfur or a sulfur compound. In this case, in the composite material, the particles of sulfur or a sulfur compound can be in a form of invading the inside of the pores of the porous carbon material. Alternatively, in the positive electrode material and the like of the present disclosure, the composite material may have a form in which the porous carbon material is dispersed inside the particles of layered sulfur or sulfur compound.

In the positive electrode material and the like of the present disclosure including the above-mentioned preferable form, the cationic polymer material can be in a form having at least one kind of the following cationic functional groups.

但し、Ｒ₁，Ｒ₂，Ｒ₃，Ｒ₄，Ｒ₅及びＲ₆は、それぞれ、独立に、水素、ハロゲン、アルキル基、アミノ基、ニトロ基、シアノ基、ヒドロシル基、サルフェート基、スルホネート基及びカルボニル基から成る群から選択される。

However, R ₁ , R ₂ , R ₃ , R ₄ , R ₅ and R ₆ are independently hydrogen, halogen, alkyl group, amino group, nitro group, cyano group, hydrosil group, sulfate group and sulfonate group, respectively. And selected from the group consisting of carbonyl groups.

Alternatively, in the positive electrode material and the like of the present disclosure including the above-mentioned preferable form, the cationic polymer material can be in the form of polydiallyldimethylammonium chloride (PDADMAC).

Further, in the positive electrode material and the like of the present disclosure including the above-mentioned preferable form, the anionic polymer material can be in a form having the following anionic functional groups.

但し、Ｒは、パーフルオロアルキル基、アルキル基、フェニル基及びエーテルから成る群から選択される。

However, R is selected from the group consisting of a perfluoroalkyl group, an alkyl group, a phenyl group and an ether.

Alternatively, in the positive electrode material and the like of the present disclosure including the above-mentioned preferable form, the anionic polymer material may be in the form of a perfluorocarbon material. In this case, the anionic polymer material can be in the form of a copolymer of tetrafluoroethylene and perfluoro (2-fluorosulfonylethoxy) propyl vinyl ester.
This material is commercially available as Nafion (registered trademark).

Alternatively, in the positive electrode material and the like of the present disclosure, the anionic polymer material is preferably an anionic polymer material capable of selectively passing magnesium ions (Mg ^{+ 2} ). In other words, the anionic polymer material is preferably an anionic polymer material having magnesium ion (Mg ^{+ 2} ) conductivity. Further, the anionic polymer material is preferably a material having a functional group having a high degree of dissociation (that is, easily dissociating magnesium). When coating the composite material with the anionic polymer material, sulfonic acid or the like may be doped. The cationic polymer material is preferably a cationic polymer material capable of electrically adsorbing polysulfide ions (S _n ⁻ ). Further, it is desirable that the cationic polymer material is a material having a high cationic density and a small number of negatively polarized atoms such as oxygen.

Further, in the positive electrode material and the like of the present disclosure including the preferable form or configuration described above, the carbon particles may be attached to the surface of the coating material layer.

In the positive electrode materials and the like of the present disclosure including the preferred forms or configurations described above, the porous carbon material and / or carbon particles may be composed of any porous carbon material. Examples of such a porous carbon material and carbon particles include a porous carbon material obtained from a plant-derived raw material such as coconut husk, activated charcoal made from petroleum pitch, and rice husk (see JP-A-2008-273816). Examples thereof include carbon materials such as graphite, carbon black or Ketjen black, non-graphitizable carbon materials (hard carbon), easily graphitized carbon (soft carbon), and / or graphitized carbon materials. The porous carbon material imparts conductivity to the composite material, and the carbon particles adhering to the surface of the coating material layer impart conductivity to the positive electrode material.

Further, examples of the sulfur coating the porous carbon material include _S8 sulfur, insoluble sulfur, colloidal sulfur and polysulfide, and examples of the sulfur compound include organic sulfur compounds (disulfide compounds, trisulfide compounds and the like). Can be done. Sulfur or a sulfur compound not only comes into contact with the surface of the porous carbon material, but also penetrates into the pores of the porous carbon material. That is, the particles of the porous carbon material are dispersed inside the particles of the sulfur or the sulfur compound, and the sulfur or the sulfur compound also penetrates into the pores of the porous carbon material. Alternatively, the sulfur or the sulfur compound is layered, and the particles of the porous carbon material are dispersed inside the layered sulfur or the sulfur compound, and the sulfur or the sulfur compound is the pores of the porous carbon material. It has also invaded the inside. The positive electrode active material layer is composed of an aggregate of particles of sulfur or a sulfur compound, or is also composed of a layered sulfur or a sulfur compound.

The positive electrode member may be composed of a positive electrode active material layer, or may be formed on a positive electrode current collector and a positive electrode current collector (on one side or both sides of the positive electrode current collector). It may be composed of a material layer.

The electrolytic solution can be in the form of a solvent and a magnesium salt dissolved in the solvent. Sulfone can be mentioned as a solvent constituting the electrolytic solution. In addition, as the solvent constituting the electrolytic solution, ether, broadly, an aprotic solvent can also be mentioned.

That is, the electrolytic solution in the magnesium secondary battery of the present disclosure can be in the form of containing, for example, a sulfone and a magnesium salt dissolved in the sulfone. For convenience, such a form is referred to as "the electrolytic solution according to the first form of the present disclosure".

The magnesium salt may be in the form of MgX _n (where n is 1 or 2 and X is a monovalent or divalent anion). In this case, X can be in the form of a halogen-containing molecule, -SO ₄ , -NO ₃ , or a hexaalkyldisiazide group. Specifically, the halogen-containing molecule (halide) can be in the form of MgX ₂ (X = F, Cl, Br, I). More specifically, magnesium fluoride (MgF ₂ ), magnesium chloride (MgCl ₂ ), magnesium bromide (MgBr ₂ ), and / or magnesium iodide (MgI ₂ ) can be mentioned. Alternatively, the magnesium salt is a mixed system of MgCl ₂ and Mg (TFSI) ₂ [magnesium bistrifluoromethanesulfonylimide], magnesium perchlorate (Mg (ClO ₄ ) ₂ ), magnesium nitrate (Mg (NO ₃ ) ₂ ). , Magnesium sulfate (0054 ₄ ), Magnesium acetate (Mg (CH ₃ COO) ₂ ), Magnesium trifluoroacetate (Mg (CF ₃ COO) ₂ ), Magnesium tetrafluoroborate (Mg (BF ₄ ) ₂ ), Tetraphenyl Magnesium borate (Mg (B (C ₆ H ₅ ) ₄ ) ₂ ), magnesium hexafluorophosphate (Mg (PF ₆ ) ₂ ), magnesium hexafluorophosphate (Mg (AsF ₆ ) ₂ ), perfluoroalkyl sulfone Magnesium acid ((Mg (R _f1 SO ₃ ) ₂ ), where R _f1 is a perfluoroalkyl group), magnesium perfluoroalkylsulfonylimide acid (Mg ((R _f2 SO ₂ ) ₂ N) ₂ , but R _f2 Is a form of at least one magnesium salt selected from the group consisting of perfluoroalkyl group) and hexaalkyldisiazidomagnesium ((Mg (HRDS) ₂ ), where R is an alkyl group). can. The magnesium salts listed above from magnesium fluoride to (Mg (HRDS) ₂ ) are referred to as "magnesium salt-A" for convenience. In the magnesium salt-A, the molar ratio of the sulfone to the magnesium salt is, for example, preferably 4 or more and 35 or less, more preferably 6 or more and 16 or less, and further preferably 7 or more and 9 or less. Preferred, but not limited to, these.

Alternatively, as the magnesium salt in the electrolytic solution according to the first aspect of the present disclosure, magnesium hydride (Mg (BH ₄ ) ₂ ) can be mentioned. As described above, if the magnesium salt used is composed of boron hydride (Mg (BH ₄ ) ₂ ) and does not contain a halogen atom, it is necessary to prepare various members constituting the magnesium secondary battery from a material having high corrosion resistance. Is gone. In addition, such an electrolytic solution can be produced by dissolving magnesium hydride in a sulfone. The magnesium salt composed of magnesium hydride (Mg (BH ₄ ) ₂ ) is referred to as "magnesium salt-B" for convenience. Such an electrolytic solution in the present disclosure is a magnesium ion-containing non-aqueous electrolytic solution in which magnesium salt-B is dissolved in a solvent composed of sulfone. The molar ratio of sulfone to magnesium salt-B in the electrolytic solution is, for example, 50 or more and 150 or less, typically 60 or more and 120 or less, and preferably 65 or more and 75 or less. It is not limited to this.

The sulfone in the electrolytic solution according to the first aspect of the present disclosure is typically represented by R ₁ R ₂ SO ₂ (in the formula, R ₁ and R ₂ each independently represent an alkyl group). It is an alkyl sulfone or an alkyl sulfone derivative. Here, the types (number of carbon atoms and combinations) of R ₁ and R ₂ are not particularly limited and are selected as necessary. The carbon number of each of R ₁ and R ₂ is preferably 4 or less. Further, the sum of the number of carbon atoms of R ₁ and the number of carbon atoms of R ₂ is preferably 4 or more and 7 or less, but is not limited thereto. R ₁ and R ₂ are independent of each other, for example, methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, i-butyl group, s-butyl group, and / or t. -Butyl group, etc. Specific examples of the alkyl sulfone include dimethyl sulfone (DMS), methyl ethyl sulfone (MES), methyl-n-propyl sulfone (MnPS), methyl-i-propyl sulfone (MiPS), and methyl-n-butyl sulfone (MnBS). ), Methyl-i-butyl sulfone (MiBS), Methyl-s-butyl sulfone (MsBS), Methyl-t-butyl sulfone (MtBS), Ethylmethyl sulfone (EMS), diethyl sulfone (DES), Ethyl-n-propyl Sulfone (EnPS), ethyl-i-propyl sulfone (EiPS), ethyl-n-butyl sulfone (EnBS), ethyl-i-butyl sulfone (EiBS), ethyl-s-butyl sulfone (EsBS), ethyl-t-butyl Sulfone (EtBS), di-n-propyl sulfone (DnPS), di-i-propyl sulfone (DiPS), n-propyl-n-butyl sulfone (nPnBS), n-butyl ethyl sulfone (nBES), i-butyl ethyl At least one type of alkyl sulfone selected from the group consisting of sulfone (iBES), s-butylethyl sulfone (sBES) and di-n-butyl sulfone (DnBS) can be mentioned. Further, as the alkyl sulfone derivative, ethyl phenyl sulfone (EPhS) can be mentioned. And, among these sulfones, at least one selected from the group consisting of EnPS, EiPS, EsBS and DnPS is preferable.

Alternatively, the electrolytic solution in the present disclosure may be in the form of containing an ether (generally, an aprotic solvent) and a magnesium salt dissolved in an ether (aprotic solvent). For convenience, such a form is referred to as "the electrolytic solution according to the second form of the present disclosure".

The ether can be in the form of a cyclic ether and / or a linear ether. Specifically, examples of the cyclic ether include at least one cyclic ether selected from the group consisting of tetrahydrofuran (THF), dioxolane, dioxane, epoxides and furans. Examples of the linear ether include dialkyl glycol ether. Further, the dialkyl glycol ether includes a group consisting of ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, triethylene glycol dimethyl ether, tetraethylene glycol dimethyl ether, pentaethylene glycol dimethyl ether, hexaethylene glycol dimethyl ether, polyethylene glycol dimethyl ether and triethylene glycol butyl methyl ether. At least one selected dialkyl glycol ether can be mentioned, but is not limited thereto.

In this case, the magnesium salt is Mg (AlCl ₃ R ¹ ) ₂ or Mg (AlCl ₂ R ² R ³ ) ₂ (however, R ¹ , R ² and R ³ are independently alkyl groups. It can be in the form of (a). The types (number of carbon atoms and combinations) of R ¹ , R ² and R ³ are not particularly limited and are selected as necessary. The carbon number of each of R ¹ , R ² and R ³ is preferably 4 or less, but is not limited thereto. The sum of the number of carbon atoms of R ² and the number of carbon atoms of R ³ is preferably 4 or more and 7 or less, but is not limited thereto. As each of R ¹ , R ² and R ³ , for example, methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, i-butyl group, s-butyl group and / or t-butyl. The group can be mentioned.

Alternatively, the electrolytic solution in the present disclosure has a solvent composed of a sulfone and a non-polar solvent, and a magnesium salt-A dissolved in the solvent.

The non-polar solvent is selected as necessary, but is preferably a non-aqueous solvent having a relative permittivity and a number of donors of 20 or less. More specifically, as the non-protic solvent, for example, at least one non-protic solvent selected from the group consisting of aromatic hydrocarbons, ethers, ketones, esters and chain carbonates can be mentioned. Examples of aromatic hydrocarbons include toluene, benzene, o-xylene, m-xylene, p-xylene and / or 1-methylnaphthalene. Examples of the ether include diethyl ether and / or tetrahydrofuran. Examples of the ketone include 4-methyl-2-pentanone and the like. Examples of the ester include methyl acetate and / or ethyl acetate. Examples of the chain carbonate ester include dimethyl carbonate, diethyl carbonate and / or ethyl methyl carbonate.

The sulfone and magnesium salt-A are as described above. Further, if necessary, the above-mentioned additives may be added to the electrolytic solution. The molar ratio of the sulfone to the magnesium salt-A is, for example, more preferably 4 or more and 20 or less, more preferably 6 or more and 16 or less, and further preferably 7 or more and 9 or less. However, it is not limited to these.

Alternatively, other solvents such as ethylene carbonate, propylene carbonate, dimethyl carbonate, diethyl carbonate, ethylmethyl carbonate, methylpropyl carbonate, acetonitrile, dimethoxyethane, diethoxyethane, vinylene carbonate, γ-butyrolactone and / or tetrahydrofuran can be used. Of these, one type may be used alone, or two or more types may be used in combination.

Alternatively, the solvent is preferably composed of linear ether. Specific examples of the linear ether include ethylene glycol dimethyl ether (dimethoxyethane), diethylene glycol dimethyl ether, triethylene glycol dimethyl ether, tetraethylene glycol dimethyl ether, pentaethylene glycol dimethyl ether, hexaethylene glycol dimethyl ether, polyethylene glycol dimethyl ether and / or triethylene glycol butylmethyl. Ether can be mentioned, but among them, ethylene glycol dimethyl ether (dimethoxyethane, DME) is preferably used.

The electrolyte layer may also be composed of the electrolytic solution in the present disclosure and a polymer compound composed of a retainer that holds the electrolytic solution. The polymer compound may be one that is swollen by an electrolytic solution. In this case, the polymer compound swollen by the electrolytic solution may be in the form of a gel. Examples of the polymer compound include polyacrylic nitrile, polyvinylidene fluoride, a copolymer of vinylidene fluoride and hexafluoropropylene, polytetrafluoroethylene, polyhexafluoropropylene, polyethylene oxide, polypropylene oxide, polyphosphazene, and polysiloxane. Examples thereof include polyvinylidene acetate, polyvinyl alcohol, methyl methacrylate, polyacrylic acid, polymethacrylic acid, styrene-butadiene rubber, nitrile-butadiene rubber, polystyrene and / or polycarbonate. In particular, from the viewpoint of electrochemical stability, polyacrylonitrile, polyvinylidene fluoride, polyhexafluoropropylene and / or polyethylene oxide are preferable. The electrolyte layer can also be a solid electrolyte layer.

In the magnesium secondary battery of the present disclosure including the preferred embodiment described above, it is more preferable that the magnesium salt is composed of magnesium chloride and the electrolytic solution contains ethyl-n-propyl sulfone (EnPS).

In the magnesium secondary battery of the present disclosure, the positive electrode current collector is, for example, a metal foil such as nickel, stainless steel, copper and / or molybdenum, an alloy foil, a metal plate, an alloy plate, a metal mesh, an alloy mesh or carbon fiber. It is made of carbon material such as carbon sheet and carbon sheet. However, as described above, the positive electrode member may not be provided with a positive electrode current collector and may have a structure consisting only of a positive electrode active material layer (layered positive electrode active material). The positive electrode active material layer may contain at least one of a conductive auxiliary agent and a binder, if necessary.

The negative electrode member contains magnesium or a magnesium compound. Specifically, the negative electrode member is made of magnesium (a simple substance of magnesium metal), a magnesium alloy, or a magnesium compound. Alternatively, the structure may be such that the negative electrode active material layer is formed on the surface of the negative electrode current collector constituting the negative electrode member, and in this case, the negative electrode active material layer is composed of a layer having magnesium ion conductivity. Specifically, as a material constituting the negative electrode active material layer, a magnesium (Mg) -based material can be mentioned, and further, carbon (C), oxygen (O), sulfur (S) and halogen are contained at least. You may. Such a negative electrode active material layer preferably has a single peak derived from magnesium in the range of 40 eV or more and 60 eV or less. As the halogen, for example, at least one selected from the group consisting of fluorine (F), chlorine (Cl), bromine (Br) and iodine (I) can be mentioned. In this case, it is more preferable to have a single peak derived from magnesium in the range of 40 eV or more and 60 eV or less, extending from the surface of the negative electrode active material layer to a depth of 2 × 10 ^-7 m. This is because the negative electrode active material layer extends from the surface to the inside and exhibits good electrochemical activity. Further, for the same reason, it is preferable that the oxidation state of magnesium is substantially constant over 2 × 10 ^-7 m in the depth direction from the surface of the negative electrode active material layer. Here, the back surface of the negative electrode active material layer means the surface of both sides of the negative electrode active material layer that constitutes the interface between the negative electrode current collector and the negative electrode active material layer, and is the surface of the negative electrode active material layer. , Means the surface opposite to the back surface of the negative electrode active material layer. Whether or not the negative electrode active material layer contains the above elements can be confirmed based on the XPS (X-ray Photoelectron Spectroscopy) method. Further, the fact that the negative electrode active material layer has the above peak and the oxidation state of magnesium can be similarly confirmed based on the XPS method. The negative electrode active material layer may contain at least one of a conductive auxiliary agent and a binder, if necessary. The negative electrode member is made of, for example, a plate-like material or a foil-like material, but the present invention is not limited to this, and it is also possible to form (form) using powder. As described above, the negative electrode member may include a negative electrode current collector.
Examples of the material constituting the negative electrode current collector include metal foils such as copper, nickel, stainless steel, molybdenum, magnesium and / or magnesium compounds, alloy foils, metal plates, and alloy plates.

Examples of the conductive auxiliary agent contained in the positive electrode active material layer or the negative electrode active material layer include carbon materials such as graphite, carbon fiber, carbon black, and carbon nanotubes, and one type or two or more of these can be mixed. Can be used. As the carbon fiber, for example, vapor growth carbon fiber (VGCF) or the like can be used. As the carbon black, for example, acetylene black and / or Ketjen black can be used. As the carbon nanotubes, for example, multi-wall carbon nanotubes (MWCNTs) such as single-wall carbon nanotubes (SWCNTs) and / or double-wall carbon nanotubes (DWCNTs) can be used. As long as the material has good conductivity, a material other than the carbon material can be used, and for example, a metal material such as Ni powder, a conductive polymer material, or the like can be used. As the binder contained in the positive electrode active material layer or the negative electrode active material layer, for example, a fluororesin such as polyvinylidene fluoride (PVdF) and / or polytetrafluoroethylene (PTFE), a polyvinyl alcohol (PVA) -based resin, and / Or a polymer resin such as a styrene-butadiene copolymerized rubber (SBR) resin can be used. Further, a conductive polymer may be used as the binder. As the conductive polymer, for example, substituted or unsubstituted polyaniline, polypyrrole, polythiophene, and / or a (co) polymer composed of one or two selected from these can be used.

The positive electrode member and the negative electrode member are separated by an inorganic separator or an organic separator through which magnesium ions pass while preventing a short circuit due to contact between the two electrodes. Examples of the inorganic separator include glass filters and / or glass fibers. Examples of the organic separator include a porous membrane made of a synthetic resin made of polytetrafluoroethylene, polypropylene and / or polyethylene, and a structure in which two or more of these porous membranes are laminated can also be used. .. Above all, the porous film made of polyolefin is preferable because it has an excellent short-circuit prevention effect and can improve the safety of the battery by the shutdown effect.

In the magnesium secondary battery having the configuration described above, as shown in FIG. 17, the conceptual diagram of the electrochemical device (battery) is that magnesium ions (Mg ^{+ 2} ) charge the electrolytic solution 18 from the positive electrode member 16 during charging. By moving to the negative electrode member 17 through the electric energy, the electric energy is converted into chemical energy and stored. At the time of discharge, electric energy is generated by returning magnesium ions from the negative electrode member 17 to the positive electrode member 16 through the electrolytic solution 18.

The magnesium secondary battery of the present disclosure includes, for example, a notebook personal computer, a PDA (portable information terminal), a mobile phone, a smartphone, a master unit or a slave unit of a cordless telephone, a video movie, a digital still camera, an electronic book, an electronic dictionary, and the like. Portable music player, radio, headphones, game console, navigation system, memory card, heart pacemaker, hearing aid, power tool, electric shaver, refrigerator, air conditioner, television receiver, stereo, water heater, microwave, dishwasher, Power supply for driving washing machines, dryers, lighting equipment, toys, medical equipment, IoT equipment, IoT terminals, robots, road conditioners, traffic lights, railroad vehicles, golf carts, electric carts, electric vehicles (including hybrid vehicles), etc. It can be used as an auxiliary power source. Further, it can be mounted on a power storage power source for a building such as a house or a power generation facility, or can be used to supply power to these. In an electric vehicle, a conversion device that converts electric power into driving force by supplying electric power is generally a motor. The control device (control unit) that processes information related to vehicle control includes a control device that displays the remaining battery level based on information on the remaining amount of the magnesium secondary battery. Further, a magnesium secondary battery can also be used in a power storage device in a so-called smart grid. Such a power storage device can not only supply power but also store power by receiving power from another power source. As other power sources, for example, thermal power generation, nuclear power generation, hydroelectric power generation, solar cells, wind power generation, geothermal power generation, fuel cells (including biofuel cells) and the like can be used.

The present disclosure includes the above-mentioned various preferable forms and configurations in a secondary battery in a battery pack having a secondary battery, a control means (control unit) for controlling the secondary battery, and an exterior including the secondary battery. A magnesium secondary battery can be applied. In this battery pack, the control means controls, for example, charge / discharge, overdischarge, or overcharge of the secondary battery.

The magnesium secondary battery of the present disclosure including the above-mentioned various preferred forms and configurations can be applied to a secondary battery in an electronic device that receives power from the secondary battery.

A secondary in an electric vehicle having a conversion device that receives electric power from a secondary battery and converts it into the driving force of the vehicle, and a control device (control unit) that performs information processing on vehicle control based on information on the secondary battery. The magnesium secondary battery of the present disclosure including the above-mentioned various preferable forms and configurations can be applied to the battery. In this electric vehicle, the converter typically receives power from a magnesium secondary battery to drive the motor and generate driving force. Regenerative energy can also be used to drive the motor. Further, the control device (control unit) performs information processing related to vehicle control based on, for example, the remaining battery level of the magnesium secondary battery. The electric vehicle includes, for example, an electric vehicle, an electric motorcycle, an electric bicycle, a railroad vehicle, and a so-called hybrid vehicle.

The present disclosure comprises the above various preferred forms and configurations of a secondary battery in a power system configured to receive power from a secondary battery and / or supply power from a power source to the secondary battery. Magnesium secondary batteries can be applied. This electric power system may be any electric power system as long as it uses approximately electric power, and includes a simple electric power device. This power system includes, for example, a smart grid, a household energy management system (HEMS), a vehicle, and the like, and can also store electricity.

A magnesium secondary battery of the present disclosure comprising the various preferred embodiments and configurations described above, wherein the secondary battery in a power storage power source having a secondary battery and configured to be connected to an electronic device to which power is supplied. Can be applied. The power storage power source can be used for basically any power system or device regardless of the use, but can be used for, for example, a smart grid.

The positive electrode material for a magnesium secondary battery of the present disclosure can be applied not only to a magnesium secondary battery but also to an electrochemical device such as various sensors. The capacitor includes a positive electrode, a negative electrode, and a separator sandwiched between the positive electrode and the negative electrode and impregnated with an electrolytic solution.

Example 1 relates to a magnesium secondary battery and a positive electrode material for a magnesium secondary battery (hereinafter, simply referred to as “positive electrode material”) of the present disclosure. The positive electrode material 10 of the first embodiment showing a schematic (conceptual) cross-sectional view in FIG. 1 is
A porous carbon material 13, a composite material (composite member) 11 composed of sulfur or a sulfur compound (specifically, for example, sulfur S ₈₁₂ ), and
Coating Material Layer 14, Containing Anionic Polymer Material and Cationic Polymer Material,
Have. Further, the carbon particles 15 are attached to the surface of the coating material layer 14.

In the composite material 11, the porous carbon material 13 is dispersed inside the particles of the sulfur or the sulfur compound, and further, in the composite material 11, the particles of the sulfur or the sulfur compound are contained in the porous carbon material 11. It has penetrated into the pores. Alternatively, in the composite material, the porous carbon material 13 is dispersed inside the particles of layered sulfur or sulfur compound. Alternatively, these states are mixed.

More specifically, the particles of the porous carbon material 13 are dispersed inside the particles of the sulfur 12, and the sulfur 12 also penetrates into the pores of the porous carbon material 13. Alternatively, the sulfur is layered, particles of the porous carbon material are dispersed inside the layered sulfur, and the sulfur also penetrates into the pores of the porous carbon material (shown). figure). In FIG. 1, the particles of the porous carbon material 13 are shown to be uniformly dispersed inside the particles of sulfur 12, but in reality, they may be randomly dispersed. Further, although the shape of the sulfur 12 particles is shown in a spherical shape, various shapes can be actually taken. Further, although the coating material layer 14 is shown to uniformly cover the sulfur 12 particles, in reality, the coating material layer 14 may uniformly cover the sulfur 12 particles. .. Further, although the carbon particles 15 are shown to be uniformly adhered to the surface of the coating material layer 14, in reality, they may be randomly adhered.

Here, the porous carbon material 13 and the carbon particles 15 are made of Ketjen black. The anionic polymer material is composed of a perfluorocarbon material, specifically, a copolymer (naphthion) of tetrafluoroethylene and perfluoro (2-fluorosulfonylethoxy) propyl vinyl ester. Furthermore, the cationic polymer material consists of polydiallyl dimethylammonium chloride (PDADMAC).

Alternatively, the cationic polymer material may be configured to have at least one of the following cationic functional groups, and the anionic polymer material may be configured to have the following anionic functional groups. can. Alternatively, the anionic polymer material is an anionic polymer material capable of selectively passing magnesium ions (Mg ⁺² ), that is, an anionic high anionic polymer material having magnesium ion (Mg ⁺² ) conductivity. It is preferable to use a molecular material, and the cationic polymer material is preferably a cationic polymer material capable of electrically adsorbing polysulfide ions (S _n ⁻ ).

但し、Ｒ₁，Ｒ₂，Ｒ₃，Ｒ₄，Ｒ₅及びＲ₆は、それぞれ、独立に、水素、ハロゲン、アルキル基、アミノ基、ニトロ基、シアノ基、ヒドロシル基、サルフェート基、スルホネート基及びカルボニル基から成る群から選択される。

However, R ₁ , R ₂ , R ₃ , R ₄ , R ₅ and R ₆ are independently hydrogen, halogen, alkyl group, amino group, nitro group, cyano group, hydrosil group, sulfate group and sulfonate group, respectively. And selected from the group consisting of carbonyl groups.

但し、Ｒは、パーフルオロアルキル基、アルキル基、フェニル基及びエーテルから成る群から選択される。

However, R is selected from the group consisting of a perfluoroalkyl group, an alkyl group, a phenyl group and an ether.

Further, as shown in FIG. 8 as a schematic exploded view of the magnesium secondary battery of Example 1, the magnesium secondary battery 20 of Example 1 is
A positive electrode member 23 including at least a positive electrode active material layer 23B (specifically, in Example 1, a positive electrode member 23 including a positive electrode current collector 23A and a positive electrode active material layer 23B).
The separator 24, which is disposed so as to face the positive electrode member 23 (more specifically, the positive electrode active material layer 23B).
A negative electrode member 25 containing magnesium or a magnesium compound disposed facing the separator 24, and
Electrolyte containing magnesium salt,
It is a magnesium secondary battery equipped with. The positive electrode active material layer 23A is made of the positive electrode material 10 of Example 1 described above (specifically, an aggregate of the positive electrode materials 10 or layered sulfur).

The electrolytic solution consists of a solvent and a magnesium salt dissolved in the solvent. Sulfone can be mentioned as the solvent constituting the electrolytic solution, and ether, and broadly, an aprotic solvent can also be mentioned. In Example 1, specifically, the electrolytic solution contains a sulfone and a magnesium salt dissolved in the sulfone. Here, the magnesium salt is composed of magnesium chloride (MgCl ₂ ), and the sulfone constituting the electrolytic solution contains ethyl-n-propyl sulfone (EnPS).

A positive electrode material was manufactured based on the method described below.

<Preparation of functionalized porous carbon material> (See FIG. 18 showing the production scheme of the positive electrode material) 1.25 grams in a mixture of 292 ml of 60% nitrate and 208 ml of distilled water. Ketjen Black (ECP600JD manufactured by Lion Co., Ltd.) was introduced. Next, this mixture was heated and stirred at 70 ° C. for 3 days in a 1-liter eggplant-shaped flask, and then centrifuged (12000 rpm, 1 minute) to remove the supernatant. Then, it was washed 5 times with 500 ml of distilled water to obtain a functionalized porous carbon material.

<Preparation of composite material> (See FIG. 19 showing the production scheme of the positive electrode material).
17.5 ml of poly (3,4-ethylenedioxythiophene) / polystyrene sulfonic acid [PEDOT / PSS] is added to a solution of 25 g of sodium thiosulfate in 750 ml of distilled water, and Stirrer is used. And stirred to obtain a mixed solution (referred to as "mixed solution-A"). PEDOT / PSS is added to impart conductivity to the composite material. Then, using a 2 liter beaker, 78.5 grams of oxalic acid was added to 1.22 liters of distilled water to dissolve it, and the above functionalized porous carbon material solution (3 mg / 1 liter of distilled water) was added. After dispersing 30 ml of the mixture, the mixed solution-A was quickly added, and the mixture was vigorously stirred with a stirrer for 3 hours at room temperature, then subjected to ultrasonic treatment for 5 minutes, and then distilled (3000 rpm, 5 minutes) was performed to remove the supernatant. Then, by washing with 2 liters of distilled water five times, a composite material in which the porous carbon material was coated with sulfur S ₈ could be obtained. The yield was 5.07 grams.

<First coating of composite material with cationic polymer material> (See FIG. 20 showing the production scheme of the positive electrode material).
3 ml of PDADMAC was added to a solution of 3.45 grams of lithium nitrate in 500 ml of distilled water (referred to as "Aqueous Solution-A"), and the mixture was stirred with a stirrer for 5 minutes. Then 5.07 grams of composite material was added and stirred with stirrer for 1 hour. Then, centrifugation (3000 rpm, 5 minutes) was performed to remove the supernatant.
Then, after redispersion with 500 ml of aqueous solution-A, centrifugation was performed, the supernatant was removed, and the washing treatment was performed twice. The obtained substance is called "PDADMAC-1".

<Second coating of composite material with anionic polymer material> (See FIG. 20 showing the production scheme of the positive electrode material).
A 3 ml Nafion solution was added to a solution (referred to as "aqueous solution-B") in which 3.45 g of lithium nitrate was dissolved in 500 ml of a mixed solution of distilled water and ethanol (volume ratio 1: 1). Next, PDADMAC-1 described above was dispersed in this mixture, stirred with a stirrer for 1 hour, and then centrifuged (3000 rpm, 5 minutes) to remove the supernatant. Then, aqueous solution-B was added, shaken well, redispersed, and then centrifuged to remove the supernatant. Then, after redispersing with 500 ml of the aqueous solution-B, centrifugation was performed, the supernatant was removed, and the washing treatment was performed twice. The obtained substance is called "Nafion-1".

<Third coating of composite material with cationic polymer material>
Using Nafion-1 instead of the composite material, the same step as the first coating step with the cationic polymer material of the composite material was carried out to obtain PDADMAC-2.

<Fourth coating of composite material with anionic polymer material>
Using PDADMAC-2, the same step as the first coating step with the anionic polymer material of the composite material was carried out to obtain Nafion-2.

<Preparation of positive electrode material of Example 1>
Half of the obtained Nafion-2 was added to 500 ml of a 0.05 mol-MgCl ₂ aqueous solution, shaken well, dispersed, and then centrifuged to remove the supernatant. Then, after further redispersing in 500 mm of a 0.05 mol-MgCl ₂ aqueous solution, centrifugation was performed, the supernatant was removed, and a washing treatment was performed twice. In this way, the positive electrode material of Example 1 was obtained. In the process of this treatment, lithium (Li) in the coating material layer was replaced with magnesium (Mg).

<Adhesion of carbon particles to the positive electrode material of Example 1> (See FIG. 21 showing a production scheme of the positive electrode material).
To the solution in which the positive electrode material of Example 1 was dispersed in 150 ml of distilled water, 100 ml of the above functionalized porous carbon material solution (3 mg / 1 liter of distilled water) was added. Then, the mixture was stirred with a stirrer for 4 hours and then centrifuged (3000 rpm, 5 minutes) to remove the supernatant. Then, the washing treatment was performed twice with 250 ml of distilled water, and the mixture was dried at 80 ° C. for 12 hours to obtain the final positive electrode material of Example 1.

<Preparation of positive electrode material of Comparative Example 1>
Half of the obtained Nafion-2 was added to 500 ml of aqueous solution-A, shaken well, dispersed, and then centrifuged to remove the supernatant. Then, after further redispersing in 500 ml of the aqueous solution-A, centrifugation was performed, the supernatant was removed, and the washing treatment was performed twice. In this way, the positive electrode material of Comparative Example 1 was obtained.

<Adhesion of carbon particles to the positive electrode material of Comparative Example 1> (See FIG. 21 showing a production scheme of the positive electrode material).
To the solution in which the positive electrode material of Comparative Example 1 was dispersed in 150 ml of distilled water, 100 ml of the above functionalized porous carbon material solution (3 mg / 1 liter of distilled water) was added. Then, the mixture was stirred with a stirrer for 4 hours and then centrifuged (3000 rpm, 5 minutes) to remove the supernatant. Then, the washing treatment was performed twice with 250 ml of distilled water, and the mixture was dried at 80 ° C. for 12 hours to obtain the final positive electrode material of Comparative Example 1.

The positive electrode material of Comparative Example 1 thus obtained is substantially the material disclosed in Non-Patent Document 1 described above.

In order to confirm the coating state and the laminated structure of the particles in the manufacturing process of the positive electrode material, the zeta potential was measured for the particles in the manufacturing process. The zeta potential measurement conditions are as follows.

Measuring device: Zetasizer Nano ZS manufactured by MALVERN
Measurement conditions: Distilled water is used as the dispersion solvent.
(Parameters used: solvent refractive index 1.330, viscosity 0.8872)
Measurement temperature: 25 ° C
Measurement cell: Disposable singing cell
Measurement procedure: Measurement is performed 3 times in a row, and the average value is calculated.
Sample pretreatment: Measure the dispersion after ultrasonic dispersion treatment for 1 minute.

FIG. 2 shows the measurement results of the zeta potential in the manufacturing process of the positive electrode material of Example 1 and Comparative Example 1. The zeta potentials of the positive electrode materials of Example 1 and Comparative Example 1 are
First coating step with a cationic polymer material of the composite material (indicated by "B" in FIG. 2)
Third coating step with a cationic polymer material of the composite material (indicated by "D" in FIG. 2)
Preparation step of positive electrode material of Example 1 and Comparative Example 1 (indicated by "F" and "G" in FIG. 2)
While showing a positive value in
Composite material preparation step (indicated by "A" in FIG. 2)
Second coating step with anionic polymer material of composite material (indicated by "C" in FIG. 2)
Fourth coating step with anionic polymer material of composite material (indicated by "E" in FIG. 2)
The finally obtained positive electrode materials of Example 1 and Comparative Example 1 (indicated by "H" and "J" in FIG. 2).
Showed a negative value in. That is, it was confirmed that the potential state of the surface of the material in each treatment step was a desired state. The thickness of the coating material layer is not particularly limited, but it is desirable that the thickness is such that the zeta potential changes depending on the coating.

SEM-EDS measurement was performed on the positive electrode material of Example 1 to confirm the presence of carbon (C), magnesium (Mg) and sulfur (S). The SEM-EDS measurement results are shown in FIGS. 3, 4, 5 and 6. 3 is an SEM photograph, FIG. 4 is a measurement result of a carbon (C) atom in the EDS measurement, FIG. 5 is a measurement result of a magnesium (Mg) atom in the EDS measurement, and FIG. 6 is a measurement result in the EDS measurement. It is a measurement result of a sulfur (S) atom. From FIGS. 4, 5 and 6, the presence of carbon (C) atom, magnesium (Mg) atom and sulfur (S) atom was clearly recognized. The SEM-EDS measurement conditions are as follows. As a pre-observation treatment, the sample was placed on a silicon semiconductor substrate or carbon tape, a platinum thin film was deposited, and then observation, measurement and analysis were performed.

SEM: Scanning electron microscope SU3500 manufactured by Hitachi High-Technologies Corporation
EDX: Energy dispersive X-ray analyzer manufactured by HORIBA, Ltd. EMAXEvolution EX-370 X-MAX20
SEM observation conditions ・ Vacuum degree: Low vacuum mode (30Pa)
・ WD: 5 mm to 6 mm
・ Acceleration voltage: 15kV
・ Spot intensity: 50
-Observation mode: BSE-3D
EDX measurement conditions ・ Vacuum degree: Low vacuum mode (30Pa)
・ WD: 10 mm
・ Acceleration voltage: 15kV
・ Spot intensity: 60

Further, as shown in FIG. 7, it was possible to confirm that Nafion and PDADMAC were present in the positive electrode material of Example 1 based on the IR measurement.

On the other hand, an electrolytic solution (MgCl ₂ -EnPS) was prepared as follows.

Reagents were weighed and mixed in the glove box (argon gas atmosphere / dew point −80 ° C to −90 ° C). While stirring 100 ml of dehydrated methanol with a stirrer, 3.81 grams of anhydrous magnesium chloride (II) (MgCl ₂ ) was added. MgCl ₂ (anhydride) manufactured by Sigma-Aldrich was used. It was confirmed by measuring the temperature outside the reaction vessel with a contact thermometer that some heat was generated when MgCl ₂ was dissolved in methanol. This exotherm is due to the heat of reaction when methanol is coordinated to Mg, and it is considered that it has a structure in which methanol is coordinated to Mg in methanol. In addition, there was some cloudiness even after the dissolution of MgCl ₂ . It is considered that this is due to the reaction between the water remaining in the methanol and Mg to generate Mg (OH) ₂ . Since the white turbidity was very slight, the operation was continued without filtering.

After dissolving MgCl ₂ , 43.6 g of ethyl normal propyl sulfone (EnPS) for battery dehydration manufactured by Tomiyama Pure Chemical Industries, Ltd. was added while stirring with a stirrer. Next, the solution was taken out of the glove box while being kept free of air, and the mixture was heated and stirred at 120 ° C. for 2 hours while reducing the pressure using a rotary pump to remove methanol. When the amount of methanol decreased, a white precipitate was formed, but when heating under reduced pressure was continued, the formed precipitate dissolved. It is considered that this change in solubility is due to the exchange of the ligand of Mg from methanol to EnPS. The removal of methanol was confirmed by ¹ H NMR measurement.

Since the sample after removing the methanol had white turbidity when MgCl ₂ was dissolved in methanol, it was filtered in a glove box (pore diameter 0.45 μm: manufactured by Whatman). The obtained electrolytic solution had Mg: Cl: EnPS = 1: 2: 8 (molar ratio) and a Mg concentration of 0.99 mol / liter.

The state in which the magnesium secondary battery (coin battery 20, CR2016 type) of Example 1 is disassembled is shown in the schematic diagram of FIG. 8, in which the gasket 22 is placed on the coin battery can 21 and the positive electrode member 23 (nickel wire mesh (mesh) ), Positive electrode active material layer 23B) made of the positive electrode material of Example 1, separator 24, Mg plate having a diameter of 15 mm and a thickness of 0.20 mm (manufactured by Rikazai Co., Ltd., purity 99.9%). After laminating the negative electrode member 25 made of the negative electrode member 25, the spacer 26 made of a stainless steel plate having a thickness of 0.5 mm, and the coin battery lid 27 in this order, the coin battery can 21 was crimped and sealed. The spacer 26 was spot welded to the coin battery lid 27 in advance. The separator (glass filter GC50 manufactured by Advantech Co., Ltd.) 24 contains the above electrolytic solution.

Next, the voltage range is set to 0.7 to 2.5 volts, the current density is set to a constant current of 0.1 mA, charging is stopped when the current reaches 2.5 volts during charging, and 0.7 when discharged. When it reached the bolt, the discharge was stopped. The charge / discharge curve thus obtained is shown in FIG. 9. In FIG. 9, "A" is a charge curve and "B" is a discharge curve.

As described above, the positive electrode material for the magnesium secondary battery of Example 1 or the positive electrode material constituting the positive electrode member of the magnesium secondary battery of Example 1 is a porous carbon material coated with sulfur or a sulfur compound. The composite material has a structure in which a coating material layer composed of an anionic polymer material and a cationic polymer material is covered, and the coating material layer can easily pass magnesium ions (Mg ^{+ 2} ). Nevertheless, it can prevent or suppress the elution of sulfur as a polysulfide anion.

Specifically, the anionic polymer material (specifically, Nafion) has a function of selectively permeating magnesium ions (Mg ^{+ 2} ), and the ionic conductivity is increased by making the film thinner. be able to. Further, the cationic polymer material (specifically, PDADMAC) has a function of electrically adsorbing a polysulfide anion (S _n ⁻ ). Moreover, by coating the composite material with the coating material layer, it is possible to reduce the exposure of the particles of the composite material due to the volume change of the positive electrode material. Further, the presence of the porous carbon material can impart electrical conductivity to the positive electrode material and can physically adsorb the polysulfide anion.

As a result of the above, it has become possible to realize a magnesium secondary battery having high energy density and excellent cycle characteristics.

Example 2 is a modification of Example 1. The electrochemical device of the second embodiment is composed of a capacitor as shown in FIG. 10 in a schematic cross-sectional view, and a positive electrode 31 and a negative electrode 32 are arranged to face each other via a separator 33. Reference numbers 35 and 36 indicate current collectors, and reference numbers 37 indicate gaskets. Further, the positive electrode 31 is made of the positive electrode member of Example 1. The negative electrode 32 contains magnesium or a magnesium compound.

Alternatively, the electrochemical device of Example 2 comprises an air battery, as the conceptual diagram is shown in FIG. The air cell has, for example, an oxygen selective permeable film 47 that is difficult to permeate water vapor and selectively permeates oxygen, an air electrode side current collector 44 made of a conductive porous material, and the air electrode side current collector 44. A porous diffusion layer 46 made of a conductive material arranged between the and a porous positive electrode 41, a porous positive electrode 41 containing a conductive material and a catalyst material, a separator and an electrolytic solution (or an electrolytic solution) that do not easily pass through water vapor. It is composed of a solid electrolyte (including solid electrolyte) 43, a negative electrode member 42 that emits magnesium ions, a current collector 45 on the negative electrode side, and an exterior body 48 that houses each of these layers. The porous positive electrode 41 is made of the positive electrode member of Example 1.

Oxygen 52 in the air (atmosphere) 51 is selectively permeated by the oxygen selective permeation membrane 47, passes through the air electrode side current collector 44 made of a porous material, is diffused by the diffusion layer 46, and is diffused by the diffusion layer 46, and is diffused by the porous positive electrode 41. Is supplied to. The progress of oxygen that has permeated the oxygen selective permeation membrane 47 is partially blocked by the air electrode side current collector 44, but the oxygen that has passed through the air electrode side current collector 44 is diffused and spread by the diffusion layer 46. The porous positive electrode 41 can be efficiently spread over the entire surface, and the supply of oxygen to the entire surface of the porous positive electrode 41 is not hindered by the air electrode side current collector 44. Further, since the permeation of water vapor is suppressed by the oxygen-selective permeation membrane 47, deterioration due to the influence of moisture in the air is small, and oxygen is efficiently supplied to the entire porous positive electrode 41, so that the battery output is increased. It becomes possible to use it stably for a long period of time.

Alternatively, the electrochemical device of Example 2 comprises a fuel cell, as the conceptual diagram is shown in FIG. The fuel cell includes, for example, a positive electrode member 61, an electrolytic solution 62 for a positive electrode, an electrolytic solution transport pump 63 for a positive electrode, a fuel flow path 64, an electrolytic solution storage container 65 for a positive electrode, a negative electrode member 71, an electrolytic solution 72 for a negative electrode, and a negative electrode. It is composed of an electrolytic solution transport pump 73, a fuel flow path 74, an electrolytic solution storage container 75 for a negative electrode, and an ion exchange membrane 66. The positive electrode electrolyte 62 continuously or intermittently flows (circulates) in the fuel flow path 64 via the positive electrode electrolyte storage container 65 and the positive electrode electrolyte transport pump 63, and the fuel flow. The negative electrode electrolytic solution 72 continuously or intermittently flows (circulates) in the path 74 via the negative electrode electrolyte storage container 75 and the negative electrode electrolyte transport pump 73, and the positive electrode member 61 and the positive electrode member 61. Power is generated between the negative electrode member 71 and the negative electrode member 71. As the positive electrode electrolytic solution 62, a positive electrode active material added to the electrolytic solution of Example 1 can be used, and as the negative electrode electrolytic solution 72, a negative electrode active material added to the electrolytic solution of Example 1 is used. be able to. The positive electrode member 61 is made of the positive electrode member of Example 1.

In Example 3, the electrochemical device (specifically, a magnesium secondary battery) of the present disclosure and an application example thereof will be described.

The magnesium secondary battery of the present disclosure described in the first embodiment is a machine, an apparatus, an instrument, an apparatus, a system (s) which can use the secondary battery as a power source for driving / operation or a power storage source for power storage. It can be applied to an aggregate of devices or the like without particular limitation. The magnesium secondary battery used as a power source (specifically, a magnesium-sulfur secondary battery) may be a main power source (a power source used preferentially) or an auxiliary power source (instead of the main power source). , Or a power source that is used by switching from the main power source). When a magnesium secondary battery is used as an auxiliary power source, the main power source is not limited to the magnesium secondary battery.

Specific uses of the magnesium secondary battery (specifically, magnesium-sulfur secondary battery) of the present disclosure include video cameras, camcoders, digital still cameras, mobile phones, personal computers, television receivers, and various types. Display devices, cordless phones, headphone stereos, music players, portable radios, electronic papers such as electronic books and newspapers, various electronic devices such as portable information terminals including PDA, electrical devices (including portable electronic devices); toys; Portable living appliances such as electric shavers; Lighting appliances such as interior lights; Medical electronic devices such as pacemakers and hearing aids; Storage devices such as memory cards; Battery packs used for personal computers as removable power sources; Electric drills And electric tools such as electric saws; power storage systems such as household battery systems and home energy servers (household power storage devices) that store power in case of emergency, power supply systems; power storage units and backup power supplies; Electric vehicles such as electric vehicles, electric bikes, electric bicycles, and Segways (registered trademarks); driving of electric power conversion devices (specifically, for example, power motors) of aircraft and ships can be exemplified. It is not limited to these uses.

Above all, it is effective that the magnesium secondary battery of the present disclosure is applied to a battery pack, an electric vehicle, an energy storage system, an electric power supply system, an electric tool, an electronic device, an electric device and the like.
The battery pack is a power source using the magnesium secondary battery of the present disclosure, and is a so-called assembled battery or the like. The electric vehicle is a vehicle that operates (runs) using the magnesium secondary battery of the present disclosure as a drive power source, and may be a vehicle (hybrid vehicle or the like) that also includes a drive source other than the secondary battery. The power storage system (power supply system) is a system using the magnesium secondary battery of the present disclosure as a power storage source. For example, in a household power storage system (power supply system), since power is stored in the magnesium secondary battery of the present disclosure, which is a power storage source, household electric products and the like can be used by using the power. Will be. The power tool is a tool in which a movable part (for example, a drill or the like) can be moved by using the magnesium secondary battery of the present disclosure as a power source for driving. Electronic devices and electrical devices are devices that exhibit various functions using the magnesium secondary battery of the present disclosure as a power source (power supply source) for operation.

Hereinafter, a cylindrical magnesium secondary battery and a flat plate type laminated film type magnesium secondary battery will be described.

FIG. 13 shows a schematic cross-sectional view of the cylindrical magnesium secondary battery 100. In the magnesium secondary battery 100, the electrode structure 121 and a pair of insulating plates 112 and 113 are housed inside the electrode structure storage member 111 having a substantially hollow columnar shape. The electrode structure 121 can be manufactured, for example, by laminating the positive electrode member 122 and the negative electrode member 124 via the separator 126 to obtain an electrode structure, and then winding the electrode structure. The positive electrode member 122 is made of the positive electrode member of Example 1. The electrode structure storage member (battery can) 111 has a hollow structure in which one end is closed and the other end is open, and is made of iron (Fe), aluminum (Al), or the like. The surface of the electrode structure accommodating member 111 may be plated with nickel (Ni) or the like. The pair of insulating plates 112 and 113 sandwich the electrode structure 121 and are arranged so as to extend perpendicularly to the winding peripheral surface of the electrode structure 121. A battery lid 114, a safety valve mechanism 115, and a heat-sensitive resistance element (PTC element, Positive Temperature Coefficient element) 116 are crimped to the open end of the electrode structure storage member 111 via a gasket 117, whereby the electrode is formed. The structure storage member 111 is hermetically sealed. The battery lid 114 is made of, for example, the same material as the electrode structure accommodating member 111. The safety valve mechanism 115 and the heat-sensitive resistance element 116 are provided inside the battery lid 114, and the safety valve mechanism 115 is electrically connected to the battery lid 114 via the heat-sensitive resistance element 116. In the safety valve mechanism 115, the disc plate 115A reverses when the internal pressure exceeds a certain level due to an internal short circuit, heating from the outside, or the like. As a result, the electrical connection between the battery lid 114 and the electrode structure 121 is cut off. In order to prevent abnormal heat generation due to a large current, the resistance of the heat-sensitive resistance element 116 increases as the temperature rises. The gasket 117 is made of, for example, an insulating material. Asphalt or the like may be applied to the surface of the gasket 117.

A center pin 118 is inserted at the winding center of the electrode structure 121. However, the center pin 118 does not have to be inserted at the center of the winding. A positive electrode lead portion 123 made of a conductive material such as aluminum is connected to the positive electrode member 122. Specifically, the positive electrode lead portion 123 is attached to the positive electrode current collector. A negative electrode lead portion 125 made of a conductive material such as copper is connected to the negative electrode member 124. Specifically, the negative electrode lead portion 125 is attached to the negative electrode current collector. The negative electrode lead portion 125 is welded to the electrode structure storage member 111 and is electrically connected to the electrode structure storage member 111. The positive electrode lead portion 123 is welded to the safety valve mechanism 115 and is electrically connected to the battery lid 114. In the example shown in FIG. 13, the negative electrode lead portion 125 has one location (the outermost peripheral portion of the wound electrode structure), but two locations (the outermost peripheral portion and the outermost portion of the wound electrode structure). It may be provided on the inner circumference).

The electrode structure 121 is formed on a positive electrode member 122 having a positive electrode active material layer formed on a positive electrode current collector (specifically, on both sides of the positive electrode current collector) and on a negative electrode current collector (specifically, on both sides of the positive electrode current collector). The negative electrode member 124 on which the negative electrode active material layer is formed (on both sides of the negative electrode current collector) is laminated via the separator 126. The positive electrode active material layer is not formed in the region of the positive electrode current collector to which the positive electrode lead portion 123 is attached, and the negative electrode active material layer is not formed in the region of the negative electrode current collector to which the negative electrode lead portion 125 is attached.

The specifications of the magnesium secondary battery 100 are illustrated in Table 1 below, but the specifications are not limited thereto.

<Table 1>
Positive electrode current collector 20 μm thick nickel foil positive electrode active material layer 50 μm thick per side
Positive electrode lead part Nickel foil negative electrode current collector with a thickness of 100 μm Copper foil negative electrode active material layer with a thickness of 20 μm Thickness 50 μm per side
Negative electrode lead part Nickel (Ni) foil with a thickness of 100 μm

The magnesium secondary battery 100 can be manufactured, for example, based on the following procedure.

That is, first, the positive electrode active material layer is formed on both sides of the positive electrode current collector, and the negative electrode active material layer is formed on both sides of the negative electrode current collector.

After that, the positive electrode lead portion 123 is attached to the positive electrode current collector by using a welding method or the like. Further, the negative electrode lead portion 125 is attached to the negative electrode current collector by using a welding method or the like. Next, the positive electrode member 122 and the negative electrode member 124 are laminated and wound via a separator 126 made of a microporous polyethylene film having a thickness of 20 μm (more specifically, the positive electrode member 122 / separator 126 / negative electrode member). After winding the electrode structure (laminated structure) of the member 124 / separator 126 to produce the electrode structure 121, a protective tape (not shown) is attached to the outermost peripheral portion. After that, the center pin 118 is inserted into the center of the electrode structure 121. Next, the electrode structure 121 is housed inside the electrode structure storage member (battery can) 111 while sandwiching the electrode structure 121 between the pair of insulating plates 112 and 113. In this case, the tip of the positive electrode lead portion 123 is attached to the safety valve mechanism 115 and the tip of the negative electrode lead portion 125 is attached to the electrode structure storage member 111 by using a welding method or the like. Then, the electrolytic solution of Example 1 is injected based on the reduced pressure method to impregnate the separator 126 with the electrolytic solution. Next, the battery lid 114, the safety valve mechanism 115, and the heat-sensitive resistance element 116 are crimped to the open end of the electrode structure storage member 111 via the gasket 117.

Next, a flat plate type laminated film type magnesium secondary battery will be described. FIG. 14 shows a schematic exploded perspective view of the magnesium secondary battery. In this magnesium secondary battery, the electrode structure 221 basically the same as described above is housed inside the exterior member 200 made of a laminated film. The electrode structure 221 can be manufactured by laminating a positive electrode member and a negative electrode member via a separator and an electrolyte layer, and then winding the laminated structure. A positive electrode lead portion 223 is attached to the positive electrode member, and a negative electrode lead portion 225 is attached to the negative electrode member. The outermost peripheral portion of the electrode structure 221 is protected by a protective tape. The positive electrode lead portion 223 and the negative electrode lead portion 225 project in the same direction from the inside to the outside of the exterior member 200. The positive electrode lead portion 223 is formed of a conductive material such as aluminum. The negative electrode lead portion 225 is formed of a conductive material such as copper, nickel, or stainless steel.

The exterior member 200 is a single film that can be folded in the direction of the arrow R shown in FIG. 14, and a portion of the exterior member 200 is provided with a recess (emboss) for accommodating the electrode structure 221. There is. The exterior member 200 is, for example, a laminated film in which a fused layer, a metal layer, and a surface protective layer are laminated in this order. In the manufacturing process of the magnesium secondary battery, the exterior member 200 is folded so that the fused layers face each other via the electrode structure 221, and then the outer peripheral edges of the fused layers are fused to each other. However, the exterior member 200 may be one in which two laminated films are bonded together via an adhesive or the like. The fused layer is made of, for example, a film such as polyethylene or polypropylene. The metal layer is made of, for example, aluminum foil or the like. The surface protective layer is made of, for example, nylon, polyethylene terephthalate, or the like. Above all, the exterior member 200 is preferably an aluminum laminated film in which a polyethylene film, an aluminum foil, and a nylon film are laminated in this order. However, the exterior member 200 may be a laminated film having another laminated structure, a polymer film such as polypropylene, or a metal film. Specifically, a moisture-resistant aluminum laminated film (total thickness) in which a nylon film (thickness 30 μm), an aluminum foil (thickness 40 μm), and an unstretched polypropylene film (thickness 30 μm) are laminated in this order from the outside. It consists of 100 μm).

In order to prevent the intrusion of outside air, a close contact film 201 is inserted between the exterior member 200 and the positive electrode lead portion 223, and between the exterior member 200 and the negative electrode lead portion 225.
The adhesion film 201 is made of a material having adhesion to the positive electrode lead portion 223 and the negative electrode lead portion 225, for example, a polyolefin resin or the like, more specifically, a polyolefin resin such as polyethylene, polypropylene, modified polyethylene or modified polypropylene. ..

Next, some application examples of the magnesium secondary battery of the present disclosure will be specifically described. The configuration of each application example described below is only an example, and the configuration can be changed as appropriate.

The battery pack is a simple battery pack (so-called soft pack) using one magnesium secondary battery of the present disclosure, and is mounted on, for example, an electronic device represented by a smartphone. Alternatively, it comprises an assembled battery composed of six magnesium secondary batteries of the present disclosure connected so as to be in two parallels and three series. The connection type of the magnesium secondary battery may be serial, parallel, or a mixed type of both.

FIG. 15 shows a block diagram showing an example of a circuit configuration when the magnesium secondary battery of the present disclosure is applied to a battery pack. The battery pack includes a cell (assembled battery) 1001, an exterior member, a switch unit 1021, a current detection resistor 1014, a temperature detection element 1016, and a control unit 1010. The switch unit 1021 includes a charge control switch 1022 and a discharge control switch 1024. Further, the battery pack includes a positive electrode terminal 1031 and a negative electrode terminal 1032, and at the time of charging, the positive electrode terminal 1031 and the negative electrode terminal 1032 are connected to the positive electrode terminal and the negative electrode terminal of the charger, respectively, to perform charging. When using an electronic device, the positive electrode terminal 1031 and the negative electrode terminal 1032 are connected to the positive electrode terminal and the negative electrode terminal of the electronic device, respectively, and discharge is performed.

The cell 1001 is configured by connecting a plurality of magnesium secondary batteries 1002 of the present disclosure in series and / or in parallel. Note that FIG. 15 shows a case where six magnesium secondary batteries 1002 are connected in two parallels and three series (2P3S), but in addition, it seems to be p parallel q series (where p and q are integers). In addition, any connection method may be used.

The switch unit 1021 includes a charge control switch 1022 and a diode 1023, and a discharge control switch 1024 and a diode 1025, and is controlled by the control unit 1010. The diode 1023 has a polarity opposite to the charge current flowing from the positive electrode terminal 1031 toward the cell 1001 and a forward polarity to the discharge current flowing from the negative electrode terminal 1032 toward the cell 1001. The diode 1025 has polarities in the forward direction with respect to the charge current and in the reverse direction with respect to the discharge current. In the example, the switch portion is provided on the plus (+) side, but it may be provided on the minus (−) side. The charge control switch 1022 is closed when the battery voltage reaches the overcharge detection voltage, and is controlled by the control unit 1010 so that the charge current does not flow in the current path of the cell 1001. After the charge control switch 1022 is closed, only discharge is possible via the diode 1023. Further, it is controlled by the control unit 1010 so as to be closed when a large current flows during charging and to cut off the charging current flowing in the current path of the cell 1001. The discharge control switch 1024 is closed when the battery voltage reaches the over-discharge detection voltage, and is controlled by the control unit 1010 so that the discharge current does not flow in the current path of the cell 1001. After the discharge control switch 1024 is closed, only charging is possible via the diode 1025. Further, it is controlled by the control unit 1010 so as to be closed when a large current flows during discharging and to cut off the discharging current flowing in the current path of the cell 1001.

The temperature detection element 1016 is composed of, for example, a thermistor and is provided in the vicinity of the cell 1001. The temperature measurement unit 1015 measures the temperature of the cell 1001 using the temperature detection element 1016 and sends the measurement result to the control unit 1010. The voltage measuring unit 1012 measures the voltage of the cell 1001 and the voltage of each magnesium secondary battery 1002 constituting the cell 1001, converts the measurement result into A / D, and sends it to the control unit 1010. The current measuring unit 1013 measures the current using the current detection resistor 1014, and sends the measurement result to the control unit 1010.

The switch control unit 1020 controls the charge control switch 1022 and the discharge control switch 1024 of the switch unit 1021 based on the voltage and current sent from the voltage measurement unit 1012 and the current measurement unit 1013. The switch control unit 1020 controls the switch unit 1021 when the voltage of any of the magnesium secondary batteries 1002 becomes equal to or lower than the overcharge detection voltage or the overdischarge detection voltage, or when a large current suddenly flows. By sending a signal, overcharging, overdischarging, and overcurrent charging / discharging are prevented. The charge control switch 1022 and the discharge control switch 1024 can be configured from a semiconductor switch such as a MOSFET.
In this case, the diode 1023, 1025 is configured by the parasitic diode of the MOSFET. When a p-channel FET is used as the MOSFET, the switch control unit 1020 supplies the control signal DO and the control signal CO to the respective gate units of the charge control switch 1022 and the discharge control switch 1024. The charge control switch 1022 and the discharge control switch 1024 are conducted by a gate potential lower than the source potential by a predetermined value or more. That is, in normal charging and discharging operations, the control signal CO and the control signal DO are set to a low level, and the charge control switch 1022 and the discharge control switch 1024 are set to a conductive state. Then, for example, in the case of overcharging or overdischarging, the control signal CO and the control signal DO are set to a high level, and the charge control switch 1022 and the discharge control switch 1024 are closed.

The memory 1011 is composed of, for example, an EPROM (Erasable Programmable Read Only Memory) which is a non-volatile memory. The memory 1011 stores in advance the numerical value calculated by the control unit 1010, the internal resistance value of the magnesium secondary battery in the initial state of each magnesium secondary battery 1002 measured at the stage of the manufacturing process, and the like. , Can be rewritten as appropriate. Further, by storing the fully charged capacity of the magnesium secondary battery 1002, for example, the remaining capacity can be calculated together with the control unit 1010.

The temperature measuring unit 1015 measures the temperature using the temperature detecting element 1016, performs charge / discharge control at the time of abnormal heat generation, and corrects in the calculation of the remaining capacity.

Next, FIG. 16A shows a block diagram showing the configuration of an electric vehicle such as a hybrid vehicle which is an example of an electric vehicle. The electric vehicle may include, for example, a control unit 2001, various sensors 2002, a power supply 2003, an engine 2010, a generator 2011, an inverter 2012, 2013, a drive motor 2014, and a differential device 2015 inside a metal housing 2000. It is equipped with a transmission 2016 and a clutch 2017. In addition, the electric vehicle includes, for example, a front wheel drive shaft 2021, a front wheel 2022, a rear wheel drive shaft 2023, and a rear wheel 2024 connected to a differential device 2015 and a transmission 2016.

The electric vehicle can travel, for example, by using either the engine 2010 or the motor 2014 as a drive source. The engine 2010 is a main power source, for example, a gasoline engine or the like. When the engine 2010 is used as a power source, the driving force (rotational force) of the engine 2010 is transmitted to the front wheels 2022 or the rear wheels 2020 via, for example, a differential device 2015, a transmission 2016, and a clutch 2017, which are driving units. The rotational force of the engine 2010 is also transmitted to the generator 2011, the generator 2011 uses the rotational force to generate AC power, and the AC power is converted to DC power via the inverter 2013 and stored in the power supply 2003. .. On the other hand, when the motor 2014, which is a conversion unit, is used as a power source, the electric power (DC power) supplied from the power supply 2003 is converted into AC power via the inverter 2012, and the AC power is used to drive the motor 2014. The driving force (rotational force) converted from the electric power by the motor 2014 is transmitted to the front wheels 2022 or the rear wheels 2024 via, for example, the differential device 2015, the transmission 2016, and the clutch 2017, which are the driving units.

When the electric vehicle decelerates through a braking mechanism (not shown), the resistance force at the time of deceleration is transmitted to the motor 2014 as a rotational force, and the motor 2014 may generate AC power by using the rotational force. The AC power is converted into DC power via the inverter 2012, and the DC regenerative power is stored in the power supply 2003.

The control unit 2001 controls the operation of the entire electric vehicle, and includes, for example, a CPU and the like. The power supply 2003 includes one or more magnesium secondary batteries (not shown) described in the first embodiment. The power supply 2003 may be configured to be connected to an external power source and to store electric power by receiving power supply from the external power source. Various sensors 2002 are used, for example, to control the rotation speed of the engine 2010 and to control the opening degree (throttle opening degree) of a throttle valve (not shown). Various sensors 2002 include, for example, a speed sensor, an acceleration sensor, an engine speed sensor, and the like.

Although the case where the electric vehicle is a hybrid vehicle has been described, the electric vehicle may be a vehicle (electric vehicle) that operates using only the power supply 2003 and the motor 2014 without using the engine 2010.

Next, a block diagram showing the configuration of the power storage system (power supply system) is shown in FIG. 16B. The power storage system includes, for example, a control unit 3001, a power supply 3002, a smart meter 3003, and a power hub 3004 inside a house 3000 such as a general house and a commercial building.

The power supply 3002 is connected to, for example, an electric device (electronic device) 3010 installed inside the house 3000, and can also be connected to an electric vehicle 3011 stopped outside the house 3000. Further, the power supply 3002 can be connected to, for example, the private power generator 3021 installed in the house 3000 via the power hub 3004, and can be connected to the external centralized power system 3022 via the smart meter 3003 and the power hub 3004. be. The electrical device (electronic device) 3010 includes, for example, one or more home appliances. Examples of home appliances include refrigerators, air conditioners, television receivers, water heaters, and the like. The private power generator 3021 is composed of, for example, a solar power generator, a wind power generator, or the like. Examples of the electric vehicle 3011 include an electric vehicle, a hybrid vehicle, an electric motorcycle, an electric bicycle, a Segway (registered trademark), and the like. Examples of the centralized power system 3022 include commercial power sources, power generation devices, power transmission networks, smart grids (next-generation power transmission networks), and for example, thermal power plants, nuclear power plants, hydroelectric power plants, and wind power plants. As the power generation device provided in the centralized power system 3022, various solar cells, fuel cells, wind power generation devices, micro-hydraulic power generation devices, geothermal power generation devices, and the like can be exemplified. It is not limited to these.

The control unit 3001 controls the operation of the entire power storage system (including the usage state of the power supply 3002), and includes, for example, a CPU and the like. The power supply 3002 includes one or more magnesium secondary batteries (not shown) described in the first embodiment. The smart meter 3003 is, for example, a network-compatible power meter installed in a house 3000 on the power demand side, and can communicate with the power supply side. The smart meter 3003 can, for example, control the balance between supply and demand in the house 3000 while communicating with the outside, thereby enabling efficient and stable energy supply.

In this power storage system, for example, power is stored in the power supply 3002 from the centralized power system 3022, which is an external power source, via the smart meter 3003 and the power hub 3004, and from the private power generator 3021, which is an independent power source, via the power hub 3004. Power is stored in the power supply 3002. The electric power stored in the power supply 3002 is supplied to the electric device (electronic device) 3010 and the electric vehicle 3011 in response to the instruction of the control unit 3001, so that the electric device (electronic device) 3010 can be operated and the electric device (electronic device) 3010 can be operated. The vehicle 3011 becomes rechargeable. That is, the power storage system is a system that enables the storage and supply of power in the house 3000 by using the power supply 3002.

The electric power stored in the power source 3002 can be arbitrarily used. Therefore, for example, electric power can be stored in the power supply 3002 from the centralized power system 3022 at midnight when the electricity charge is low, and the electric power stored in the power supply 3002 can be used during the daytime when the electricity charge is high.

The power storage system described above may be installed in each household (one household) or in each of a plurality of households (multiple households).

Next, a block diagram showing the configuration of the power tool is shown in FIG. 16C. The power tool is, for example, an electric drill, and has a control unit 4001 and a power supply 4002 inside a tool body 4000 made of a plastic material or the like. For example, a drill portion 4003, which is a movable portion, is rotatably attached to the tool body 4000. The control unit 4001 controls the operation of the entire power tool (including the usage state of the power supply 4002), and includes, for example, a CPU and the like. The power supply 4002 includes one or more magnesium secondary batteries (not shown) described in the first embodiment. The control unit 4001 supplies electric power from the power supply 4002 to the drill unit 4003 in response to an operation of an operation switch (not shown).

Although the present disclosure has been described above based on preferred examples, the present disclosure is not limited to these examples. The raw materials, manufacturing methods, manufacturing conditions, electronic devices and electrochemical devices, and the configurations and structures of the magnesium secondary batteries described in the examples are examples and are not limited thereto. , And can be changed as appropriate.

但し、Ｒ₁，Ｒ₂，Ｒ₃，Ｒ₄，Ｒ₅及びＲ₆は、それぞれ、独立に、水素、ハロゲン、アルキル基、アミノ基、ニトロ基、シアノ基、ヒドロシル基、サルフェート基、スルホネート基及びカルボニル基から成る群から選択される。
［Ａ０６］カチオン性高分子材料は、ポリジアリルジメチルアンモニウムクロライド（ＰＤＡＤＭＡＣ）から成る［Ａ０１］乃至［Ａ０４］のいずれか１項に記載のマグネシウム二次電池用の正極材料。
［Ａ０７］カチオン性高分子材料は、ポリスルフィドイオン（Ｓ_n ^-）を電気的に吸着することができるカチオン性高分子材料から成る［Ａ０１］乃至［Ａ０４］のいずれか１項に記載のマグネシウム二次電池用の正極材料。
［Ａ０８］アニオン性高分子材料は、下記のアニオン性官能基を有する［Ａ０１］乃至［Ａ０７］のいずれか１項に記載のマグネシウム二次電池用の正極材料。

但し、Ｒは、パーフルオロアルキル基、アルキル基、フェニル基及びエーテルから成る群から選択される。
［Ａ０９］アニオン性高分子材料は、パーフルオロカーボン材料から成る［Ａ０１］乃至［Ａ０７］のいずれか１項に記載のマグネシウム二次電池用の正極材料。
［Ａ１０］アニオン性高分子材料は、テトラフルオロエチレンと、パーフルオロ（２－フルオロスルフォニルエトキシ）プロピルビニルエステルとの共重合体から成る［Ａ０１］乃至［Ａ０７］いずれか１項に記載のマグネシウム二次電池用の正極材料。
［Ａ１１］アニオン性高分子材料は、マグネシウムイオンを選択的に通過させることができるアニオン性高分子材料から成る［Ａ０１］乃至「Ａ０７］のいずれか１項に記載のマグネシウム二次電池用の正極材料。
［Ａ１２］アニオン性高分子材料は、マグネシウムイオン伝導性を有するアニオン性高分子材料から成る［Ａ０１］乃至「Ａ０７］のいずれか１項に記載のマグネシウム二次電池用の正極材料。
［Ａ１３］被覆材料層表面に炭素粒子が付着している［Ａ０１］乃至［Ａ１２］いずれか１項に記載のマグネシウム二次電池用の正極材料。
［Ｂ０１］《マグネシウム二次電池》
少なくとも正極活物質層を備えた正極部材、
正極部材に対向して配設されたセパレータ、
セパレータに対向して配設されたマグネシウム又はマグネシウム化合物を含む負極部材、及び、
マグネシウム塩を含む電解液、
を備えており、
正極活物質層は、
多孔質炭素材料、及び、硫黄又は硫黄化合物によって構成された複合材料、並びに、
アニオン性高分子材料及びカチオン性高分子材料を含む被覆材料層、
から構成された正極材料から成るマグネシウム二次電池。
［Ｂ０２］複合材料においては、硫黄又は硫黄化合物の粒子の内部に多孔質炭素材料が分散している［Ｂ０１］に記載のマグネシウム二次電池。
［Ｂ０３］複合材料においては、硫黄又は硫黄化合物の粒子が、多孔質炭素材料の有する細孔の内部に侵入している［Ｂ０２］に記載のマグネシウム二次電池用の正極材料。
［Ｂ０４］複合材料においては、層状の硫黄又は硫黄化合物の粒子の内部に多孔質炭素材料が分散している［Ｂ０１］に記載のマグネシウム二次電池。
［Ｂ０５］カチオン性高分子材料は、下記のカチオン性官能基を少なくとも１種類、有する［Ｂ０１］乃至［Ｂ０４］のいずれか１項に記載のマグネシウム二次電池。

但し、Ｒ₁，Ｒ₂，Ｒ₃，Ｒ₄，Ｒ₅及びＲ₆は、それぞれ、独立に、水素、ハロゲン、アルキル基、アミノ基、ニトロ基、シアノ基、ヒドロシル基、サルフェート基、スルホネート基及びカルボニル基から成る群から選択される。
［Ｂ０６］カチオン性高分子材料は、ポリジアリルジメチルアンモニウムクロライド（ＰＤＡＤＭＡＣ）から成る［Ｂ０１］乃至［Ｂ０４］のいずれか１項に記載のマグネシウム二次電池。
［Ｂ０７］カチオン性高分子材料は、ポリスルフィドイオン（Ｓ_n ^-）を電気的に吸着することができるカチオン性高分子材料から成る［Ｂ０１］乃至［Ｂ０４］のいずれか１項に記載のマグネシウム二次電池。
［Ｂ０８］アニオン性高分子材料は、下記のアニオン性官能基を有する［Ｂ０１］乃至［Ｂ０７］のいずれか１項に記載のマグネシウム二次電池。

但し、Ｒは、パーフルオロアルキル基、アルキル基、フェニル基及びエーテルから成る群から選択される。
［Ｂ０９］アニオン性高分子材料は、パーフルオロカーボン材料から成る［Ｂ０１］乃至［Ｂ０７］のいずれか１項に記載のマグネシウム二次電池。
［Ｂ１０］アニオン性高分子材料は、テトラフルオロエチレンと、パーフルオロ（２－フルオロスルフォニルエトキシ）プロピルビニルエステルとの共重合体から成る［Ｂ０１］乃至［Ｂ０７］いずれか１項に記載のマグネシウム二次電池。
［Ｂ１１］アニオン性高分子材料は、マグネシウムイオンを選択的に通過させることができるアニオン性高分子材料から成る［Ｂ０１］乃至「Ａ０７］のいずれか１項に記載のマグネシウム二次電池。
［Ｂ１２］アニオン性高分子材料は、マグネシウムイオン伝導性を有するアニオン性高分子材料から成る［Ｂ０１］乃至「Ａ０７］のいずれか１項に記載のマグネシウム二次電池。
［Ｂ１３］被覆材料層表面に炭素粒子が付着している［Ｂ０１］乃至［Ｂ１２］いずれか１項に記載のマグネシウム二次電池。
［Ｂ１４］正極活物質層は、硫黄あるいは硫黄化合物の粒子の集合体から構成されている［Ｂ０１］に記載のマグネシウム二次電池。
［Ｂ１５］正極活物質層は、層状の硫黄あるいは硫黄化合物から構成されている［Ｂ０１］に記載のマグネシウム二次電池。The present disclosure may also have the following structure.
[A01] << Positive electrode material for magnesium secondary batteries >>
Porous carbon materials, composite materials composed of sulfur or sulfur compounds, and
Coating material layer containing anionic polymer material and cationic polymer material,
Positive electrode material for magnesium secondary batteries with.
[A02] The positive electrode material for a magnesium secondary battery according to [A01], wherein the porous carbon material is dispersed inside the particles of sulfur or a sulfur compound in the composite material.
[A03] The positive electrode material for a magnesium secondary battery according to [A02], wherein particles of sulfur or a sulfur compound have penetrated into the pores of the porous carbon material in the composite material.
[A04] The positive electrode material for a magnesium secondary battery according to [A01], wherein the porous carbon material is dispersed inside the particles of layered sulfur or a sulfur compound in the composite material.
[A05] The positive electrode material for a magnesium secondary battery according to any one of [A01] to [A04], wherein the cationic polymer material has at least one of the following cationic functional groups.

However, R ₁ , R ₂ , R ₃ , R ₄ , R ₅ and R ₆ are independently hydrogen, halogen, alkyl group, amino group, nitro group, cyano group, hydrosil group, sulfate group and sulfonate group, respectively. And selected from the group consisting of carbonyl groups.
[A06] The positive electrode material for a magnesium secondary battery according to any one of [A01] to [A04], wherein the cationic polymer material is made of polydiallyldimethylammonium chloride (PDADMAC).
[A07] The magnesium battery according to any one of [A01] to [A04], wherein the cationic polymer material comprises a cationic polymer material capable of electrically adsorbing polysulfide ions (S _n- ⁾ . Positive electrode material for next battery.
[A08] The positive electrode material for a magnesium secondary battery according to any one of [A01] to [A07], wherein the anionic polymer material has the following anionic functional groups.

However, R is selected from the group consisting of a perfluoroalkyl group, an alkyl group, a phenyl group and an ether.
[A09] The positive electrode material for a magnesium secondary battery according to any one of [A01] to [A07], wherein the anionic polymer material is made of a perfluorocarbon material.
[A10] The magnesium diarium according to any one of [A01] to [A07], wherein the anionic polymer material is composed of a copolymer of tetrafluoroethylene and perfluoro (2-fluorosulfonylethoxy) propyl vinyl ester. Positive electrode material for next battery.
[A11] The positive electrode for a magnesium secondary battery according to any one of [A01] to "A07], wherein the anionic polymer material is an anionic polymer material capable of selectively passing magnesium ions. material.
[A12] The positive electrode material for a magnesium secondary battery according to any one of [A01] to "A07], wherein the anionic polymer material is an anionic polymer material having magnesium ion conductivity.
[A13] The positive electrode material for a magnesium secondary battery according to any one of [A01] to [A12], wherein carbon particles are attached to the surface of the coating material layer.
[B01] << Magnesium secondary battery >>
A positive electrode member with at least a positive electrode active material layer,
Separator arranged facing the positive electrode member,
A negative electrode member containing magnesium or a magnesium compound disposed facing the separator, and
Electrolyte containing magnesium salt,
Equipped with
The positive electrode active material layer is
Porous carbon materials, composite materials composed of sulfur or sulfur compounds, and
Coating material layer containing anionic polymer material and cationic polymer material,
Magnesium secondary battery made of positive electrode material composed of.
[B02] The magnesium secondary battery according to [B01], wherein in the composite material, the porous carbon material is dispersed inside the particles of sulfur or a sulfur compound.
[B03] The positive electrode material for a magnesium secondary battery according to [B02], wherein particles of sulfur or a sulfur compound have penetrated into the pores of the porous carbon material in the composite material.
[B04] The magnesium secondary battery according to [B01], wherein in the composite material, the porous carbon material is dispersed inside the particles of layered sulfur or sulfur compound.
[B05] The magnesium secondary battery according to any one of [B01] to [B04], wherein the cationic polymer material has at least one of the following cationic functional groups.

However, R ₁ , R ₂ , R ₃ , R ₄ , R ₅ and R ₆ are independently hydrogen, halogen, alkyl group, amino group, nitro group, cyano group, hydrosil group, sulfate group and sulfonate group, respectively. And selected from the group consisting of carbonyl groups.
[B06] The magnesium secondary battery according to any one of [B01] to [B04], wherein the cationic polymer material is composed of polydiallyldimethylammonium chloride (PDADMAC).
[B07] The magnesium battery according to any one of [B01] to [B04], wherein the cationic polymer material comprises a cationic polymer material capable of electrically adsorbing polysulfide ions (S _n ⁻ ). Next battery.
[B08] The magnesium secondary battery according to any one of [B01] to [B07], wherein the anionic polymer material has the following anionic functional groups.

However, R is selected from the group consisting of a perfluoroalkyl group, an alkyl group, a phenyl group and an ether.
[B09] The magnesium secondary battery according to any one of [B01] to [B07], wherein the anionic polymer material is made of a perfluorocarbon material.
[B10] The magnesium diarium according to any one of [B01] to [B07], wherein the anionic polymer material is composed of a copolymer of tetrafluoroethylene and perfluoro (2-fluorosulfonylethoxy) propyl vinyl ester. Next battery.
[B11] The magnesium secondary battery according to any one of [B01] to "A07], wherein the anionic polymer material comprises an anionic polymer material capable of selectively passing magnesium ions.
[B12] The magnesium secondary battery according to any one of [B01] to "A07], wherein the anionic polymer material is an anionic polymer material having magnesium ion conductivity.
[B13] The magnesium secondary battery according to any one of [B01] to [B12], wherein carbon particles are attached to the surface of the coating material layer.
[B14] The magnesium secondary battery according to [B01], wherein the positive electrode active material layer is composed of an aggregate of sulfur or sulfur compound particles.
[B15] The magnesium secondary battery according to [B01], wherein the positive electrode active material layer is composed of a layered sulfur or a sulfur compound.

10 ... Positive electrode material, 11 ... Composite material (composite member), 12 ... Sulfur or sulfur compound, 13 ... Porous carbon material, 14 ... Coating material layer, 15 ... Carbon particles , 16 ... Positive electrode material, 17 ... Negative electrode member, 18 ... Electrolytic solution, 20 ... Magnesium secondary battery (coin battery), 21 ... Coin battery can, 22 ... Gasket, 23 ... Positive electrode member, 23A ... Positive electrode current collector, 23B ... Positive electrode active material layer, 24 ... Separator, 25 ... Negative electrode member, 26 ... Spacer, 27 ... Coin battery lid , 31 ... Positive electrode, 32 ... Negative electrode, 33 ... Separator, 35, 36 ... Current collector, 37 ... Gasket, 41 ... Porous positive electrode, 42 ... Negative electrode member, 43 ... Separator and electrolyte, 44 ... Air electrode side current collector, 45 ... Negative electrode side current collector, 46 ... Diffusion layer, 47 ... Oxygen-selective permeable film, 48 ... -Exterior body, 51 ... air (atmosphere), 52 ... oxygen, 61 ... positive electrode member, 62 ... positive electrode electrolyte, 63 ... positive electrode electrolyte transport pump, 64 ... Fuel flow path, 65 ... Positive electrode electrolyte storage container, 71 ... Negative electrode member, 72 ... Negative electrode electrolyte, 73 ... Negative electrode electrolyte transport pump, 74 ... Fuel flow path, 75 ... Electrode electrolyte storage container for negative electrode, 66 ... Ion exchange film, 100 ... Magnesium secondary battery, 111 ... Electrode structure storage member (battery can), 112, 113 ... Insulation plate , 114 ... Battery lid, 115 ... Safety valve mechanism, 115A ... Disc plate, 116 ... Heat-sensitive resistance element (PTC element), 117 ... Gasket, 118 ... Center pin, 121. .. Electrode structure, 122 ... Positive electrode member, 123 ... Positive electrode lead part, 124 ... Negative electrode member, 125 ... Negative electrode lead part, 126 ... Separator, 200 ... Exterior member, 201 ... Adhesive film, 221 ... Electrode structure, 223 ... Positive electrode lead part, 225 ... Negative electrode lead part, 1001 ... Cell (assembled battery), 1002 ... Magnesium secondary battery, 1010 ... Control unit, 1011 ... Memory, 1012 ... Voltage measurement unit, 1013 ... Current measurement unit, 1014 ... Current detection resistor, 1015 ... Temperature measurement unit, 1016 ... Temperature Detection element, 1020 ... Switch control unit, 1021 ... Switch unit, 1022 ... Charge control switch, 1024 ... Discharge control switch, 1023, 1025 ... Electrode , 1031 ... Positive terminal, 1032 ... Negative terminal, CO, DO ... Control signal, 2000 ... Housing, 2001 ... Control unit, 2002 ... Various sensors, 2003 ... Power supply , 2010 ... Engine, 2011 ... Generator, 2012 ... Inverter, 2014 ... Drive motor, 2015 ... Differential device, 2016 ... Transmission, 2017 ... Clutch , 2021 ... front wheel drive shaft, 2022 ... front wheel, 2023 ... rear wheel drive shaft, 2024 ... rear wheel 3000 ... house, 3001 ... control unit, 3002 ... power supply, 3003 ... Smart meter, 3004 ... Power hub, 3010 ... Electrical equipment (electronic equipment), 3011 ... Electric vehicle, 3021 ... Private generator, 3022 ... Centralized power system, 4000.・ ・ Tool body, 4001 ・ ・ ・ Control unit, 4002 ・ ・ ・ Power supply, 4003 ・ ・ ・ Drill part

Claims (6)

Porous carbon materials, composite materials composed of sulfur or sulfur compounds, and
Coating material layer containing anionic polymer material and cationic polymer material,
Have,
The anionic polymer material is composed of a copolymer of tetrafluoroethylene and perfluoro (2-fluorosulfonylethoxy) propyl vinyl ester.
The cationic polymer material is a positive electrode material for a magnesium secondary battery made of polydiallyldimethylammonium chloride (PDADMAC). The positive electrode material for a magnesium secondary battery according to claim 1, wherein in the composite material, the porous carbon material is dispersed inside the particles of sulfur or a sulfur compound. The positive electrode material for a magnesium secondary battery according to claim 2, wherein in the composite material, particles of sulfur or a sulfur compound have penetrated into the pores of the porous carbon material. The positive electrode material for a magnesium secondary battery according to claim 1, wherein in the composite material, the porous carbon material is dispersed inside the particles of layered sulfur or sulfur compound. The positive electrode material for a magnesium secondary battery according to any one of claims 1 to 4, wherein carbon particles are attached to the surface of the coating material layer. A positive electrode member with at least a positive electrode active material layer,
Separator arranged facing the positive electrode member,
A negative electrode member containing magnesium or a magnesium compound disposed facing the separator, and
Electrolyte containing magnesium salt,
Equipped with
The positive electrode active material layer is
Porous carbon materials, composite materials composed of sulfur or sulfur compounds, and
Coating material layer containing anionic polymer material and cationic polymer material,
Consists of a positive electrode material composed of
The anionic polymer material is composed of a copolymer of tetrafluoroethylene and perfluoro (2-fluorosulfonylethoxy) propyl vinyl ester.
The cationic polymer material is a magnesium secondary battery made of polydiallyldimethylammonium chloride (PDADMAC).

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