JP6368097B2 - Zinc negative electrode and battery - Google Patents

Description

The present invention relates to a zinc negative electrode and a battery. More specifically, the present invention relates to a zinc negative electrode that includes an active material layer containing a zinc species and that can form a battery with excellent performance and safety and high performance, and a battery using the zinc negative electrode.

The negative electrode is a negative electrode of a battery composed of a negative electrode active material. Among them, a zinc negative electrode using zinc as a negative electrode active material has been studied for a long time with the spread of batteries. Examples of batteries using zinc as a negative electrode include primary batteries, secondary batteries (storage batteries), air batteries, and the like. For example, air / zinc batteries using oxygen in the air as the positive electrode active material, nickel-containing compounds as the positive electrode active material Research and development of nickel / zinc batteries using manganese, manganese / zinc batteries and zinc ion batteries using manganese-containing compounds as the positive electrode active material, and silver / zinc batteries using silver oxide as the positive electrode active material, especially air / zinc Primary batteries, manganese / zinc primary batteries, and silver / zinc primary batteries have been put into practical use and are widely used in the world. On the other hand, in recent years, the importance of battery development and improvement has increased in many industries from portable devices to automobiles, etc., and a new battery system that is superior mainly in terms of battery performance and its conversion to secondary batteries. Is currently being developed and improved in various ways.

Conventionally, batteries that can be used for zinc as a negative electrode, which has been researched and developed, permeate at least the conductor and ions involved in the battery reaction, but not the negative electrode active material deposited on the negative electrode during charging. A negative electrode for a secondary battery having a negative electrode active material holder having a difficult insulator or semiconductor, wherein the negative electrode active material holder has voids with a porosity of 10% or more. (For example, refer to Patent Document 1). An electrochemical device having a laminate in which a positive electrode, an electrolyte layer, and a negative electrode are laminated in this order, wherein at least one of the positive electrode or the negative electrode is a current collector and the current collector. There is disclosed an electrochemical device comprising an active material layer containing acicular active material particles bonded to a surface and filled with a solid electrolyte in the active material layer (for example, , See Patent Document 2).

Furthermore, although there is no mention about the zinc electrode, in the electrode including the electrode active material on the current collector, the electrode is an electrode in which the surfaces of the electrode active material in a state of being connected to each other are coated with a polymer, There is disclosed an electrode characterized in that a polymer exists in an independent phase while maintaining a pore structure formed between electrode active material particles in a state of being connected to each other ( For example, see Patent Document 3.)

Japanese Patent Application Laid-Open No. 08-171901 JP 2010-80376 A Special table 2007-510267 gazette

As described above, various types of batteries using zinc as a negative electrode have been studied. However, as new batteries using other elements as negative electrodes have been developed, they have ceased to be the mainstream of battery development. However, the present inventors, when using zinc for the negative electrode in this way, the zinc negative electrode is inexpensive and a water-containing electrolyte can be used. In that case, in addition to high safety, the energy density is also high. From such a viewpoint, attention was paid to the possibility of being able to be suitably used in various applications. And when examining the performance aspect of the battery using zinc as the negative electrode, in order to satisfy the performance required for the battery used in recent years, the shape and shape change of the active material first becomes a problem. For example, the solid electrolyte may be introduced onto and / or into the active material layer. In the conventional solid electrolyte, there is a problem peculiar to the solid electrolyte. (1) Solid electrolyte Due to the expansion and contraction of the solid electrolyte during production and charge / discharge, the electrode active material layer cracks, etc., causing poor contact between the active material, solid electrolyte, and current collector, resulting in deterioration of the electrode. (2) The contact between the active material, the solid electrolyte, and the current collector deteriorates due to the change in the density of the active material during charging / discharging, and the electrode deteriorates and does not function (3 ) Solid electrolyte Problems such as that on conductivity is insufficient found that are still left.

The present invention has also been made in view of the above situation, and a solid electrolyte having a small degree of expansion / contraction when producing and operating a battery and having a high ion conductivity is provided on and / or within the layer. The present invention provides a zinc negative electrode capable of sufficiently suppressing the shape and shape change of the active material and forming a battery with sufficiently improved battery performance, and a battery using the zinc negative electrode. With the goal.

The present inventors have made various studies on a zinc negative electrode, and in order to sufficiently suppress changes in the shape and form of the active material, a solid electrolyte having a small degree of expansion / contraction when a battery is produced / operated is used as an active material layer. Focusing on the above and / or introduction into the layer, various studies were made on zinc negative electrodes capable of having excellent electrode performance while using a solid electrolyte.

Here, the present inventors have heretofore proposed that a zinc negative electrode in which a solid electrolyte is introduced into and / or into the active material layer is expanded or contracted during formation of the solid electrolyte or during charge / discharge operation. As a result, the connection between the active material and the conductive additive, and some or all of the connection between the active material and the conductive additive are interrupted. It has been found that the electron conduction path between the active materials disappears and the redox reaction of the active material is not smoothly performed. It has also been found that problems such as cracks occur in the electrode active material layer. Furthermore, it has been found that in a zinc negative electrode in which a solid electrolyte is introduced on and / or into an active material layer, the ion conductivity between the surface of the active material and the solid electrolyte is not sufficiently excellent. It was. As described above, the present inventors have found that the zinc negative electrode in which the conventional solid electrolyte is introduced into and / or into the active material layer has the above-mentioned specific problems, and the electrode performance has deteriorated. It was. Therefore, the inventors of the present invention provide a zinc negative electrode that retains both the electron conduction path and the ion conduction path, suppresses deterioration of electrode performance, and does not cause defects such as cracks in the electrode active material layer. Various studies were conducted. And the present inventors include that the solid electrolyte contains at least one compound selected from the group consisting of polyvalent ions, inorganic compounds, and nitrogen-containing organic compounds, and the polyvalent ions and / or inorganic compounds Contains at least one element selected from Li, Na, K, Rb, Cs, Group 2 to Group 14, P, Sb, Bi, Group 16 and Group 17 of the periodic table Therefore, the expansion / contraction of the solid electrolyte can be suppressed, the volume change of the solid electrolyte can be eliminated or reduced, and problems such as holding the electron conduction path and cracking in the electrode active material layer can occur. Found that it can not be. Furthermore, the ion conduction path is maintained and the ion conductivity is sufficiently excellent by at least one compound selected from the group consisting of such polyvalent ions, inorganic compounds and nitrogen-containing organic compounds. I found out that I can do it. The inventors of the present invention have conceived that a zinc negative electrode having such a feature can suppress degradation of electrode performance and can solve the above-mentioned problems. In addition, the zinc negative electrode which has such a characteristic can be used more suitably as a negative electrode of a battery. In addition, a battery using such a zinc negative electrode is a highly safe battery because a water-containing electrolyte can be used.

In addition, the battery disclosed in the above-described patent document includes, on the active material layer, a solid electrolyte containing at least one compound selected from the group consisting of a specific polyvalent ion, an inorganic compound, and a nitrogen-containing organic compound. And / or introduction into the layer was not disclosed. The battery disclosed in the above-mentioned patent document does not sufficiently suppress the change in the shape of the negative electrode active material of the zinc negative electrode and has excellent electrode performance. There was room for ingenuity.

That is, the present invention is a zinc negative electrode including a current collector and an active material layer containing a zinc species, and the zinc negative electrode is solid on and / or in the active material layer. The electrolyte contains an electrolyte, and the solid electrolyte includes at least one compound selected from the group consisting of polyvalent ions, inorganic compounds, and nitrogen-containing organic compounds, and the polyvalent ions and / or inorganic compounds are A zinc negative electrode containing at least one element selected from Li, Na, K, Rb, Cs, Group 2 to Group 14, P, Sb, Bi, Group 16 and Group 17. In addition, in this specification, a zinc negative electrode means the zinc electrode used as a negative electrode.

Moreover, this invention is also the said zinc negative electrode whose said solid electrolyte is an electrolyte containing a polymer.
Furthermore, the present invention is also the zinc negative electrode in which at least one compound selected from the group consisting of the multivalent ions, inorganic compounds, and nitrogen-containing organic compounds has anion conductivity.
The present invention is also the zinc negative electrode, wherein the inorganic compound is at least one compound selected from the group consisting of oxides, hydroxides, layered double hydroxides, clay compounds, and sulfuric acid compounds. In the present specification, the hydroxide refers to a hydroxide other than the layered double hydroxide.

Moreover, this invention is also a battery comprised using the zinc negative electrode of this invention, a positive electrode, a separator, and electrolyte.
The present invention is described in detail below.
In addition, the form which combined two or more each preferable form of this invention described below is also a preferable form of this invention.

In the zinc negative electrode of the present invention, usually, zinc oxide and a conductive additive are connected, and these and a current collector are connected, and between the zinc oxide and the conductive auxiliary or between these and the current collector. Can sufficiently hold an electron conduction path through which electrons can be conducted. In addition, when the solid electrolyte contains specific polyvalent ions and / or inorganic compounds and nitrogen-containing organic compounds, the ion conductivity through the ion conduction path between the surface of the active material and the solid electrolyte is excellent. Become.

Next, the solid electrolyte in the zinc negative electrode of the present invention will be described.
The zinc negative electrode of the present invention contains a solid electrolyte on and / or in the active material layer, thereby suppressing morphological changes such as shape change and dendrite of the electrode active material, dissolution, corrosion, and passive formation. In addition, it is possible to obtain an effect capable of exhibiting battery performance such as high cycle characteristics, rate characteristics, and coulomb efficiency. The solid electrolyte may have pores on the surface or inside thereof, or may have no pores, but preferably has no pores as much as possible.

The solid electrolyte includes at least one compound selected from the group consisting of multivalent ions, inorganic compounds, and nitrogen-containing organic compounds. These compounds are presumed to function as solid electrolytes due to interactions with electrolytes, electrolytes, active materials, polymers, etc., and interactions between the above compounds. 1 type may be used for a multivalent ion, an inorganic compound, and a nitrogen-containing organic compound, respectively, and 2 or more types may be used.

The solid electrolyte preferably contains an inorganic compound.
The inorganic compound contains at least one element selected from Li, Na, K, Rb, Cs, Group 2 to Group 14, P, Sb, Bi, Group 16 and Group 17 of the periodic table. For example, alkali metal, alkaline earth metal, Sc, Y, lanthanoid, Ti, Zr, Hf, V, Nb, Ta, Cr, Mo, W, Mn, Re, Fe, Ru , Co, Rh, Ir, Ni, Pd, Pt, Cu, Ag, Au, Zn, Cd, B, Al, Ga, In, Tl, Si, Ge, Sn, Pb, P, Sb, Bi, S, Se , Te, F, Cl, Br, I oxides containing at least one element selected from the group consisting of: complex oxides; alloys; layered double hydroxides such as hydrotalcite; hydroxides; clay compounds; solid solutions Zeolite; halide; carboxylation Carbonic acid compound; Hydrogen carbonate compound; Nitric acid compound; Sulfuric acid compound; Sulphonic acid compound; Sulfonate compound; Phosphoric acid compound such as hydroxyapatite; Phosphorous compound; Hypophosphorous acid compound; Boric acid compound; Examples thereof include aluminate compounds; sulfides; onium compounds; salts and the like. Preferably, an oxide containing at least one element selected from the group of the above elements; a composite oxide; an alloy; a layered double hydroxide such as hydrotalcite; a hydroxide; a clay compound; a solid solution; a zeolite; Carbonic acid compounds; sulfuric acid compounds; phosphoric acid compounds such as hydroxyapatite; boric acid compounds; silicic acid compounds;

Especially, it is preferable that the said inorganic compound is what has anion conductivity. More preferably, for example, it is at least one compound selected from the group consisting of oxides, hydroxides, layered double hydroxides, clay compounds and sulfuric acid compounds. More preferably, aluminum oxide (hydrate), bismuth oxide (hydrate), indium oxide (hydrate), calcium oxide (hydrate), yttrium oxide (hydrate), magnesium oxide (hydrate) ), Strontium oxide (hydrate), barium oxide (hydrate), lanthanum oxide (hydrate), titanium oxide (hydrate), gallium oxide (hydrate), cerium oxide (hydrate), At least one compound selected from the group consisting of niobium oxide (hydrate), tin oxide (hydrate), zirconium oxide (hydrate), cerium hydroxide, zirconium hydroxide, hydrotalcite and ettringite is there. Particularly preferably, aluminum oxide (hydrate), bismuth oxide (hydrate), indium oxide (hydrate), calcium oxide (hydrate), strontium oxide (hydrate), barium oxide (hydrate) ), Yttrium oxide (hydrate), magnesium oxide (hydrate), lanthanum oxide (hydrate), titanium oxide (hydrate), gallium oxide (hydrate), cerium oxide (hydrate), Niobium oxide (hydrate), tin oxide (hydrate), zirconium oxide (hydrate), and hydrotalcite.

The cerium oxide may be, for example, one doped with a metal oxide such as samarium oxide, gadolinium oxide, or bismuth oxide, or a solid solution with a metal oxide such as zirconium oxide. It may have an oxygen defect.
The hydrotalcite is the following formula:
[M ¹ _1-x M ² _x (OH) ₂ ] (A ⁿ⁻ ) _{x / n} · mH ₂ O
(M ¹ = Mg, Fe, Zn, Ca, Li, Ni, Co, Cu, etc .; M ² = Al, Fe, Mn, etc .; A = CO ₃ ^2−, etc., m is a positive number of 0 or more, and n is 2. Or 3, x is a compound represented by about 0.20 ≦ x ≦ 0.40), and dehydrated compounds and anions in the layers were decomposed by baking at 150 ° C. to 900 ° C. A compound, a compound obtained by exchanging anions in the interlayer with hydroxide ions, a natural mineral such as Mg ₆ Al ₂ (OH) ₁₆ CO ₃ .mH ₂ O, or the like may be used as the inorganic compound. When the solid electrolyte using hydrotalcite does not contain a polymer or oligomer, a polyvalent ion other than hydrotalcite and / or an inorganic compound is allowed to coexist, or a hydrotalcite with x = 0.33 is used. More preferably it is used. This compound is a compound dehydrated by firing at 150 ° C. to 900 ° C., a compound obtained by decomposing an anion in the interlayer, a compound obtained by exchanging the anion in the interlayer with a hydroxide ion, or a natural mineral. Mg ₆ Al ₂ (OH) ₁₆ CO ₃ .mH ₂ O or the like may be used as the inorganic compound. The hydrotalcite may be coordinated with a compound having a functional group such as a hydroxyl group, an amino group, a carboxyl group, or a silanol group. You may have organic substance in an interlayer.
The hydroxyapatite is a compound typified by Ca ₁₀ (PO ₄ ) ₆ (OH) ₂ , a compound in which the amount of Ca is reduced depending on the conditions during preparation, and hydroxyapatite into which an element other than Ca is introduced. A compound or the like may be used as the inorganic compound.

The inorganic compound may be generated in a solid electrolyte using a compound having the element as a precursor. The inorganic compound may be in any of a dissolved state, a dispersed state of a colloid, an insoluble state, etc. when it is introduced into an electrolytic solution raw material, an electrolytic solution, a solid electrolyte (gel electrolyte), etc. Those that are partially charged with a positive or negative charge are preferred, and the charged state of the particles can be inferred by measuring the zeta potential. As will be described later, these inorganic compounds mainly include a covalent bond, a coordinate bond, an ionic bond, a hydrogen bond, a bond between the inorganic compound and a functional group of the polymer, when the solid electrolyte contains a polymer. It is considered that the solid electrolyte is formed by interaction through noncovalent bonds such as π bond, van der Waals bond, and agostic interaction. Further, even when the solid electrolyte does not contain a polymer, it is possible to constitute the solid electrolyte. In this case, it is only necessary that the inorganic compound is present in the electrolytic solution, and it is assumed that the ions in the electrolytic solution and the inorganic compound are preferably acted and linked. At this time, the polyvalent ions may be contained, and the elements contained in the polyvalent ions and the elements contained in the inorganic compound may be the same or different, but at least one different one Is more preferable. When a layered compound such as hydrotalcite is used, a polymer, an organic molecule, or the like may be formed and arranged in the layer. The inorganic compound is used in a state where a part of its surface is not charged with a positive or negative charge (corresponding to an isoelectric point) when it is introduced into an electrolyte solution raw material, an electrolyte solution, a solid electrolyte, or the like. In this case, the solid electrolyte is formed by using not only electrical interaction but coordination bond or the like as a preferable driving force.

The element of the multivalent ion is at least one selected from Li, Na, K, Rb, Cs, Group 2 to Group 14, P, Sb, Bi, Group 16 and Group 17 of the periodic table. Any element may be used, but Mg, Ca, Sr, Ba, Sc, Y, La, Ce, Yb, Ti, Zr, Nb, Nd, Cr, Mo, W, Mn, Co, B are more preferable. Al, Ga, In, Tl, Si, Ge, Sn, P, Sb, Bi.
The polyvalent ions include oxides containing elements of the polyvalent ions; complex oxides; layered double hydroxides such as hydrotalcite; hydroxides; clay compounds; solid solutions; alloys; halides; Carbonic acid compound; Hydrogen carbonate compound; Nitric acid compound; Sulfuric acid compound; Sulfonic acid compound; Phosphoric acid compound; Phosphorous compound; Hypophosphorous acid compound, Boric acid compound; Silicic acid compound; Is an anion or a cation generated by introducing the above into an electrolyte solution raw material, an electrolyte solution, a solid electrolyte, or the like. The anion or cation may be generated by dissolving a part or all of the compound containing the element of the polyvalent ion in an electrolyte raw material, an electrolytic solution, a solid electrolyte, or the like. When the compound to be contained is insoluble, the anion and cation may be generated on a part of the surface and the like when introduced into an electrolyte solution raw material, an electrolyte solution, a solid electrolyte or the like. The multivalent ions may be generated in a solid electrolyte using a compound having the element as a precursor. When the solid electrolyte is a solid electrolyte containing a polymer, the polyvalent ion may be derived from the polymer.
As will be described later, when the solid electrolyte is a solid electrolyte containing a polymer, the polyvalent ion is mainly a covalent bond with a functional group of the polymer, a coordinate bond, an ionic bond, a hydrogen bond, It interacts by noncovalent bonds such as π bond, van der Waals bond, agostic interaction, etc., and becomes a solid electrolyte.
Moreover, it is possible to constitute a solid electrolyte even when the solid electrolyte is a solid electrolyte containing no polymer. In this case, it is only necessary that the polyvalent ion and the inorganic compound described later coexist in the electrolytic solution, and it is presumed that the polyvalent ion can bind the inorganic compound more suitably together with the ion in the electrolyte. . At this time, the element contained in the multivalent ion and the element contained in the inorganic compound may be the same or different, but at least one is more preferable.
In the case where a polyvalent ion and an inorganic compound are used in combination, the mass ratio between the polyvalent ion and the inorganic compound is preferably 50,000 / 1 to 1/100000.
Examples of the nitrogen-containing organic compound include alkylene diamine such as ethylene diamine, substituted alkylene diamine such as ethylene diamine in which a hydrogen atom on nitrogen is substituted with an alkyl group and / or an aromatic ring-containing group, polyethylene imine, bipyridine, imidazole, pyrazole, and triazole. -Heterocyclic compounds represented by tetrazole, pyrazine, phenanthroline, phenazine and the like, and organic compounds containing azo group, nitro group, nitroso group, quaternary ammonium base and the like.

The total amount of at least one compound selected from the group consisting of the polyvalent ions, inorganic compounds and nitrogen-containing organic compounds is preferably 0.01% by mass or more in 100% by mass of the solid electrolyte. More preferably, it is 0.1 mass% or more, More preferably, it is 0.5 mass% or more. Moreover, it is preferable that the total amount of the said compound is 99.9 mass% or less. More preferably, it is 98 mass% or less, More preferably, it is 95 mass% or less.

When the water-containing electrolyte described later is used as the electrolyte used when preparing the solid electrolyte, the compound that generates the polyvalent ions, the inorganic compound, and the nitrogen-containing organic compound have high ion conductivity. Contributes to the absorption and permeability of the gas generated during charge and discharge, as well as side reactions that can occur thermodynamically, such as side reactions in which water decomposition proceeds and hydrogen and oxygen are generated, and the form of active material It also serves to suppress changes, dissolution, and corrosion, and to significantly improve charge / discharge characteristics and coulomb efficiency. This is thought to be due to the favorable interaction of the polyvalent ions, inorganic compounds, and nitrogen-containing organic compounds with the negative electrode surface and the suppression of zinc-containing compound diffusion.

The solid electrolyte may be a solid electrolyte consisting of at least one compound selected from the group consisting of polyvalent ions, inorganic compounds and nitrogen-containing organic compounds, and an electrolytic solution alone, and further a solid electrolyte containing a polymer or an oligomer. There may be. When the solid electrolyte further contains an oligomer or polymer, the oligomer or polymer can interact with at least one compound selected from the group consisting of polyvalent ions, inorganic compounds, and nitrogen-containing organic compounds. Due to the use of these solid electrolytes, it is possible to effectively and physically limit the diffusion of ions in the electrode and / or on the surface thereof, so that the shape change or dissolution of the electrode active material, such as shape change or dendrite, It is assumed that corrosion can be suppressed. In addition, by using such a solid electrolyte, it is possible to obtain the effect of suppressing the formation of passivation and self-discharge during charging or storage in the charged state. The effect of suppressing the formation of passives and self-discharge is also presumed to be obtained by the action of the solid electrolyte as described above. Furthermore, a storage battery formed using such a solid electrolyte can exhibit high cycle characteristics, rate characteristics, and coulomb efficiency while maintaining high electrical conductivity. Therefore, although the said solid electrolyte can be used for any electrochemical devices, such as a primary battery, a secondary battery (storage battery), a capacitor, and a hybrid capacitor, it is preferable to be used for a storage battery.
In the following, the term “polymer” includes oligomers.

It is one of the preferred embodiments of the present invention that the solid electrolyte contains a polymer. When a polymer is used for the solid electrolyte, the polymer preferably exhibits a covalent bond, a coordinate bond, a non-covalent bond such as an ionic bond, a hydrogen bond, a π bond, and a van der Waals bond. More preferably, the polymer is a polymer that interacts with a functional group of the polymer and a polyvalent ion and / or an inorganic compound. Conventionally, the polymer coupling sites are often decomposed under acidic or basic conditions and / or under an electrical load caused by the electrolytic solution. It dissolves and the deterioration of the solid electrolyte gradually proceeds. However, a structure that interacts with at least one compound selected from the group consisting of multivalent ions, inorganic compounds, and nitrogen-containing organic compounds, and the functional group of the polymer serves as a connection point by the compound, thereby expressing suitable battery characteristics. It is believed that a compound having As a result, deterioration of the solid electrolyte can be sufficiently suppressed, and as a result, shape change, dissolution, corrosion, and passivation formation such as shape change and dendrite of the electrode active material can be suppressed, and stored in the charged state or in the charged state. It is possible to continuously suppress the self-discharge at the time, and to suppress the expansion / contraction of the solid electrolyte as much as possible during the formation of the solid electrolyte or during the charge / discharge operation. Both of the ion conduction paths can be maintained well, and high battery performance can be maintained for a longer time.

Polymers used for the solid electrolyte include aromatic group-containing polymers represented by polystyrene and the like; ether group-containing polymers represented by alkylene glycol and the like; polyvinyl alcohol, poly (α-hydroxymethyl acrylate), polyvinyl Hydroxyl group-containing polymers typified by alcohol and poly (α-hydroxymethyl acrylate); amide group-containing polymers typified by polyamide, nylon, polyacrylamide, polyvinylpyrrolidone, N-substituted polyacrylamide, etc .; Representative imide group-containing polymers; carboxyl group-containing polymers typified by poly (meth) acrylic acid, polymaleic acid, polyitaconic acid, polymethyleneglutaric acid, etc .; poly (meth) acrylates, polymaleates, polyitaconates , Carboxylic acid group-containing polymers represented by polymethylene glutarate; halogen-containing polymers such as polyvinyl chloride, polyvinylidene fluoride, and polytetrafluoroethylene; polymers bonded by opening of epoxy groups such as epoxy resins; AR ¹ R ² R ³ B (A represents N or P. B represents an anion such as a halogen anion or OH ^−. R ¹ , R ² and R ³ are the same or Differently, it represents an alkyl group having 1 to 7 carbon atoms, a hydroxyalkyl group, an alkyl carboxyl group, or an aromatic ring group, and R ¹ , R ² , and R ³ may combine to form a ring structure. Quaternary ammonium salts and quaternary phosphonium salt-containing polymers represented by polymers to which the represented groups are bonded; used for cation / anion exchange membranes, etc. Ion exchange polymer; natural rubber; artificial rubber represented by styrene butadiene rubber (SBR), etc .; cellulose, cellulose acetate, hydroxyalkyl cellulose (for example, hydroxyethyl cellulose), carboxymethyl cellulose, chitin, chitosan, alginic acid (salt), etc. An amino group-containing polymer represented by polyethyleneimine; a carbamate group site-containing polymer; a carbamide group site-containing polymer; an epoxy group site-containing polymer; a heterocyclic ring and / or an ionized heterocyclic site-containing polymer; Examples thereof include conductive polymers; polymer alloys; heteroatom-containing polymers; low molecular weight surfactants. Polymer is radical polymerization, radical (alternate) copolymerization, anion polymerization, anion (alternate) copolymerization, cationic polymerization, cationic (alternate) copolymerization, graft polymerization, graft (alternate) copolymerization from monomers corresponding to the structural unit. , Living polymerization, living (alternate) copolymerization, dispersion polymerization, emulsion polymerization, suspension polymerization, ring-opening polymerization, cyclization polymerization, polymerization by light, ultraviolet ray or electron beam irradiation, metathesis polymerization, electrolytic polymerization, etc. . A monomer that is a raw material of the polymer may be used at the time of electrode preparation, and polymerized at the time of charge / discharge. When these polymers have a functional group, they may be present in the main chain and / or side chain, and may exist as a binding site with a crosslinking agent. These polymers may be used alone or in combination of two or more. The polymer includes an ester bond, an amide bond, an ionic bond, a van der Waals bond, and an organic crosslinking agent compound other than at least one compound selected from the group consisting of the polyvalent ions, inorganic compounds, and nitrogen-containing organic compounds. Agostic interaction, hydrogen bond, acetal bond, ketal bond, ether bond, peroxide bond, carbon-carbon bond, carbon-nitrogen bond, carbon-oxygen bond, carbon-sulfur bond, carbamate bond, thiocarbamate bond, carbamide bond, thio It may be crosslinked via a carbamide bond, an oxazoline moiety-containing bond, a triazine bond, or the like.

The polymer preferably has a weight average molecular weight of 200 to 7000000. When the weight average molecular weight of the polymer is in such a range, a solid electrolyte can be sufficiently formed. More preferably, it is 400-6500000 as a weight average molecular weight, More preferably, it is 500-55,000. The strength of the solid electrolyte to be generated can be controlled by selecting the molecular weight of the polymer and using multiple polymers with different molecular weights and types. Suppresses passive formation, suppresses self-discharge during charging and storage in the charged state, and maintains high ionic conductivity while maintaining high cycle characteristics, rate characteristics, and Coulomb efficiency. Can be expressed. In addition, hydrogen and oxygen generated by a side reaction in the positive electrode and the negative electrode can be transported well to the counter electrode, and these can be eliminated. The polymer may be in a fiberized state by heat or pressure. The fiberization of the polymer can also adjust the strength of the active material site and the solid electrolyte site, in other words, the interaction involving the polymer.
The weight average molecular weight can be measured by gel permeation chromatography (GPC) or a UV detector.

The blending ratio of the polymer in the solid electrolyte and at least one compound selected from the group consisting of polyvalent ions, inorganic compounds and nitrogen-containing organic compounds is as follows: polymer, polyvalent ions, inorganic compounds and nitrogen-containing organics It is preferable that a mass ratio with the compound corresponding to at least one of the compounds is 5000000/1 to 1/100000. With such a blending ratio, deterioration of the solid electrolyte is suppressed, shape change such as shape change and dendrite, dissolution, corrosion and passivation formation are suppressed, and self-discharge during storage in the charged state or charged state is prevented. Effective suppression can be performed sufficiently continuously, and high battery performance can be maintained for a longer time. More preferably, it is 2000000/1-1/10000, More preferably, it is 1000000/1-1/1000. More preferably, it is 1000000/1 to 1/100. Even more preferably, it is 100/3 to 75/100. Most preferably, it is 100 / 50-75 / 100.

As the inorganic compound, the electrolytic solution, and the polymer used for producing the solid electrolyte, those subjected to deoxygenation treatment are preferably used. Moreover, it is preferable to mix at least one compound selected from the group consisting of multivalent ions, inorganic compounds, and nitrogen-containing organic compounds, an electrolytic solution, and a polymer in an inert atmosphere. When mixing is performed in an inert atmosphere using a raw material that has been subjected to deoxygenation treatment, the resulting solid electrolyte has good electrical characteristics. More preferably, the amount of dissolved oxygen in the solid electrolyte is as close as possible to 0 mg / L. By reducing the dissolved oxygen concentration, it becomes possible to reduce the dissolution of the zinc electrode active material into the electrolyte as much as possible, suppressing the shape change, dissolution, and corrosion reaction of the zinc electrode active material, and improving the life of the electrode. It will be. In addition, in the case of a strong alkaline aqueous solution-containing electrolyte, when carbon dioxide is mixed in, a large amount of carbonate is generated, which may lower the conductivity and adversely affect the battery performance. It is preferable to remove at the same time.

The solid electrolyte has an interaction with at least one compound selected from the group consisting of polyvalent ions, inorganic compounds and nitrogen-containing organic compounds, and a storage battery using such a solid electrolyte is an electrode. High cycle characteristics while maintaining high ionic conductivity while suppressing morphological change such as shape change and dendrite of active material, suppressing dissolution, corrosion and passive formation, suppressing self-discharge during charging and storage in charged state , Rate characteristics and coulomb efficiency can be expressed. Further, by suppressing the expansion / contraction of the solid electrolyte as much as possible during the formation of the solid electrolyte or during the charge / discharge operation, both the electron conduction path and the ion conduction path can be satisfactorily maintained. Moreover, this solid electrolyte can be used suitably also for a primary battery, can suppress the form change of an electrode active material, and can express a high rate characteristic, maintaining high ion conductivity.
As described above, since the solid electrolyte can enhance various characteristics of the storage battery, it is one of the preferred embodiments of the present invention that the battery of the present invention is a storage battery.

The solid electrolyte contained in and / or within the active material layer of the zinc negative electrode of the present invention may all be the solid electrolyte of the present invention, or partly contains the solid electrolyte of the present invention. It may be. The battery in which all the solid electrolytes are the solid electrolytes of the present invention includes those in which the electrolyte contains an electrolytic solution and becomes a solid electrolyte. The solid electrolyte of the present invention includes at least one compound selected from the group consisting of polyvalent ions, inorganic compounds and nitrogen-containing organic compounds, and when the polyvalent ions and / or inorganic compounds are included, The multivalent ions and / or inorganic compounds are selected from Li, Na, K, Rb, Cs, Group 2 to Group 14, P, Sb, Bi, Group 16 and Group 17 of the periodic table. A substance containing at least one element.

A battery in which a part of the electrolyte is the solid electrolyte of the present invention is one in which the electrolyte is composed of the solid electrolyte of the present invention, a solid electrolyte other than the solid electrolyte, and the like. For example, a mode in which a zinc-containing compound is used as a negative electrode and the electrolyte is composed of the solid electrolyte of the present invention and a solid electrolyte that does not contain any of the specific polyvalent cations and / or inorganic compounds and nitrogen-containing organic compounds described above. Point to. In addition, when the zinc negative electrode contains a solid electrolyte on the active material layer, the solid electrolyte may have a shape change such as a shape change or dendrite of the electrode active material, dissolution, corrosion, suppression of passive formation, in a charged state or It is possible to suppress self-discharge during storage in a charged state, and to suppress the expansion / contraction of the solid electrolyte as much as possible during formation of the solid electrolyte or during charge / discharge operation. It is preferable that the solid electrolyte of the present invention is essential. In this case, at least a part of the electrolyte in contact with the active material layer may be formed by using the solid electrolyte of the present invention as essential, but all of the electrolyte in contact with the active material layer is formed by using the solid electrolyte of the present invention as essential. It is preferred that The solid electrolyte is prepared by prepolymerizing or kneading at least one compound selected from the group consisting of polyvalent ions, inorganic compounds and nitrogen-containing organic compounds, a polymer and an electrolytic solution. You may use for a battery, and after putting the raw material of solid electrolytes including a monomer in a battery, it may superpose | polymerize in a battery and this may be produced. In addition, a solid electrolyte (gel electrolyte) prepared in advance with a thickness of 20 nm or more and 5 mm or less on the current collector or the active material layer is applied, pressed, bonded, piezoelectric, rolled, stretched, melted, etc. Alternatively, after applying a solid electrolyte raw material, an electrolyte coating may be formed on the electrode surface by polymerization.
Further, when the zinc negative electrode contains a solid electrolyte in the active material layer, for example, as described above, a solid electrolyte that has been coated, pressed, bonded, piezoelectric, rolled, stretched, melted, etc. on the active material layer is heated. -It can be introduced into the active material layer by using a pressure, a solvent, or the like. In this case, the solid electrolyte is preferably substantially introduced into the entire active material layer, but may be introduced into only a part of the active material layer. For example, by using heat of 0 ° C. to 400 ° C., using a pressure of normal pressure to 20 t, using a solvent such as water, methanol, ethanol, propanol, butanol, hexanol, N-methylpyrrolidone, or a combination thereof. The solid electrolyte can be preferably introduced into the active material layer. In addition, when introducing a solid electrolyte into an active material layer, a solid electrolyte may be used on the zinc negative electrode as described above, but an electrolytic solution (liquid) may be used. In addition, a zinc negative electrode mixture is prepared using a process in which a solid electrolyte or a solid electrolyte raw material is mixed with a zinc negative electrode mixture raw material, and then collected by coating, pressure bonding, adhesion, piezoelectric, rolling, stretching, melting, etc. An active material layer containing a solid electrolyte may be formed on the body. In this case, it is preferable to produce only the active material layer containing the solid electrolyte using only the zinc negative electrode mixture in which the solid electrolyte or the solid electrolyte raw material is mixed with the zinc negative electrode mixture raw material, but the solid electrolyte or the solid electrolyte raw material The active material layer containing the solid electrolyte is prepared using the zinc negative electrode mixture mixed with the zinc negative electrode mixture raw material, and the solid electrolyte is prepared using the zinc negative electrode mixture containing no solid electrolyte or solid electrolyte raw material. An active material layer not included may be prepared, and both active material layers may be stacked. In this way, an active material layer containing a solid electrolyte therein may be produced.

When the solid electrolyte is composed of the solid electrolyte of the present invention and another solid electrolyte other than the solid electrolyte, the ratio of the solid electrolyte of the present invention to 100% by mass of the total amount of the solid electrolyte is 0. It is preferable that it is 0.001 mass% or more and less than 100 mass%. More preferably, it is 0.01 mass% or more. More preferably, it is 0.02 mass% or more.

As the electrolytic solution used when preparing the solid electrolyte and the electrolytic solution, those usually used as the electrolytic solution of the battery can be used, and are not particularly limited, and an organic solvent-based electrolytic solution and a water-containing electrolytic solution are used. Can be used.

The electrolyte is not particularly limited as long as it is usually used as a battery electrolyte, and examples thereof include water-containing electrolytes and organic solvent-based electrolytes, and water-containing electrolytes are preferred. The water-containing electrolytic solution refers to an electrolytic solution using only water as an electrolytic solution raw material (aqueous electrolytic solution) or an electrolytic solution using a solution obtained by adding an organic solvent to water as an electrolytic solution raw material. Examples of the aqueous electrolyte include potassium hydroxide aqueous solution, sodium hydroxide aqueous solution, lithium hydroxide aqueous solution, zinc sulfate aqueous solution, zinc nitrate aqueous solution, zinc phosphate aqueous solution, and zinc acetate aqueous solution. Thus, although it does not restrict | limit especially as an electrolyte, When using aqueous electrolyte solution, the compound which generate | occur | produces the hydroxide ion which bears ion conduction in a system is preferable. In particular, an aqueous potassium hydroxide solution is preferable from the viewpoint of ion conductivity. The aqueous electrolyte solution can be used alone or in combination of two or more.

Moreover, the said water containing electrolyte solution may contain the organic solvent used for an organic solvent type electrolyte solution. Examples of the organic solvent include ethylene carbonate, propylene carbonate, dimethyl carbonate, diethyl carbonate, γ-butyrolactone, dimethoxymethane, diethoxymethane, dimethoxyethane, tetrahydrofuran, methyltetrahydrofuran, diethoxyethane, dimethyl sulfoxide, sulfolane, acetonitrile, Examples include benzonitrile, ionic liquid, fluorine-containing carbonates, fluorine-containing ethers, polyethylene glycols, fluorine-containing polyethylene glycols and the like. The organic solvent electrolyte can be used alone or in combination of two or more.
In the case of a water-containing electrolyte containing an organic solvent-based electrolyte, the content of the water-based electrolyte is preferably 10-99.9% by mass with respect to a total of 100% by mass of the water-based electrolyte and the organic solvent-based electrolyte. More preferably, it is 20-99.9 mass%.

The concentration of the electrolytic solution is preferably 0.01 to 50 mol / L of an electrolyte (for example, potassium hydroxide). By using an electrolytic solution having such a concentration, good battery performance can be exhibited. More preferably, it is 1-20 mol / L, More preferably, it is 3-18 mol / L. In addition, when the following water-containing electrolyte is used for a primary battery or a secondary battery using a water-containing electrolyte having a zinc-containing compound as a negative electrode, zinc oxide, zinc hydroxide, phosphorous is further added to the electrolyte. It is preferable to add at least one zinc compound selected from zinc acid, zinc pyrophosphate, zinc borate, zinc silicate, zinc aluminate, zinc metal, tetrahydroxy zinc ion salt, and zinc sulfide. As a result, changes in the shape of the electrode active material such as shape change and dendrite accompanying the dissolution of the zinc electrode active material during charge and discharge, formation of growth and passivation, and self-retention during charging and storage in the charged state Discharge can be further suppressed. The zinc compound in the electrolytic solution is preferably from 0.0001 mol / L to a saturated concentration.

The electrolytic solution may contain as an additive at least one compound selected from the group consisting of the polyvalent ions, inorganic compounds, and nitrogen-containing organic compounds. When an aqueous electrolyte is used, side reactions during charge and discharge, where hydrogen decomposition occurs as the water decomposition reaction proceeds, which can usually occur thermodynamically, morphological change of zinc electrode active material, passive formation, The dissolution and corrosion reaction, and the self-discharge during the charge state or during storage in the charge state are suppressed, and the charge / discharge characteristics and coulomb efficiency are greatly improved. This is because the additive interacts favorably with the surface of zinc oxide and zinc-containing compounds in the electrolyte, etc. to prevent side reactions, morphological changes of zinc active materials, passive formation, dissolution, corrosion reactions and self-discharge. It is thought to suppress.
As an additive, for example, in the case of an aqueous electrolyte using potassium hydroxide as an electrolyte, lithium hydroxide, sodium hydroxide, rubidium hydroxide, cesium hydroxide, magnesium hydroxide, barium hydroxide, calcium hydroxide, Strontium hydroxide, lithium oxide, magnesium oxide, barium oxide, calcium oxide, strontium oxide, strontium acetate, magnesium acetate, barium acetate, calcium acetate, lithium carbonate, potassium carbonate, sodium carbonate, magnesium carbonate, calcium carbonate, barium carbonate, fluorine Lithium fluoride, sodium fluoride, potassium fluoride, rubidium fluoride, cesium fluoride, beryllium fluoride, magnesium fluoride, calcium fluoride, strontium fluoride, barium fluoride, potassium acetate, boric acid, meta Potassium oxalate, potassium borate, potassium hydrogen borate, calcium borate, borofluoric acid, phosphoric acid, potassium phosphate, potassium pyrophosphate, potassium phosphite, potassium oxalate, potassium silicate, potassium aluminate, potassium sulfide , Potassium sulfate, potassium thiosulfate, titanium oxide, zirconium oxide, aluminum oxide, lanthanoid oxide, niobium oxide, chromium oxide, copper oxide, gallium oxide, thallium oxide, antimony oxide, bismuth oxide, lead oxide, tellurium oxide, tin oxide, Indium oxide, trialkyl phosphate, quaternary ammonium salt-containing compound, quaternary phosphonium salt-containing compound, carboxylate group-containing compound, polyethylene glycol chain-containing compound, chelating agent, methanol, ethanol, butanol, carboxylic acid, carboxylic acid Salt Phonic acid, sulfonate, sulfonamide, sulfone, sulfoxide, polymer, gel compound, carboxylate group and / or sulfonate group and / or sulfinate group and / or quaternary ammonium salt, and / Or quaternary phosphonium salts and / or polyethylene glycol chains and / or low molecular weight organic compounds having halogen groups such as fluorine, surfactants, elements belonging to Groups 1 to 17 of the periodic table Examples thereof include polymers and gel compounds containing a compound containing at least one element selected from the group consisting of:
A compound having at least one element selected from the group consisting of elements belonging to Group 1 to Group 17 of the periodic table may be added to the electrolytic solution. One type or two or more types of additives can be used.

Examples of the solid electrolyte other than the solid electrolyte of the present invention include, for example, a solid electrolyte capable of conducting cations such as lithium even in the absence of a liquid such as an electrolytic solution, and the polyvalent ions and / or Examples thereof include a solid electrolyte that does not contain an inorganic compound and is crosslinked with another compound (crosslinking agent).

When the zinc negative electrode of the present invention contains a solid electrolyte on the active material layer, a zinc negative electrode mixture, which will be described later, is applied to the current collector by coating, pressure bonding, adhesion, piezoelectricity, rolling, stretching, melting, etc. After preparing the layer, the above-described solid electrolyte may be formed on the active material layer. Further, when the zinc negative electrode of the present invention contains a solid electrolyte in the active material layer, the solid electrolyte coated, pressure-bonded, bonded, piezoelectric, rolled, stretched, melted, etc. on the active material layer is subjected to heat, pressure, What is necessary is just to introduce | transduce in an active material layer by use of a solvent etc. Also, a zinc negative electrode mixture, which will be described later, is prepared using a process in which a solid electrolyte or a solid electrolyte raw material is mixed with a zinc negative electrode mixture raw material, and thereafter coating, pressure bonding, adhesion, piezoelectric, rolling, stretching, melting, etc. Thus, an active material layer containing a solid electrolyte may be formed on the current collector. Thereby, an active material layer containing the solid electrolyte therein is produced.
When the solid electrolyte contains a polymer, prepare a solid electrolyte raw material containing the monomer as the raw material, and after coating, crimping, bonding, piezoelectric, rolling, stretching, melting, etc. on the active material layer, Alternatively, a zinc negative electrode mixture, which will be described later, is prepared using a process of mixing the above raw materials together with the zinc negative electrode mixture raw material, and then, on the current collector by coating, pressure bonding, adhesion, piezoelectric, rolling, stretching, melting, etc. After producing the active material layer, a solid electrolyte can be contained on and / or in the active material layer through a polymerization step. As polymerization methods, radical (co) polymerization, anion (co) polymerization, cation (co) polymerization, graft (co) polymerization, living (co) polymerization, dispersion (co) polymerization, emulsion (co) polymerization, suspension ( Co) polymerization, ring-opening (co) polymerization, cyclization (co) polymerization, polymerization by irradiation with light / ultraviolet rays / electron beams, metathesis (co) polymerization, electrolytic (co) polymerization and the like can be used.
The mass ratio between the solid electrolyte and the zinc species (zinc-containing compound) in the active material layer is preferably 10,000 / 1 to 1/10000. More preferably, it is 1000/1 to 1/10000, and still more preferably 500/1 to 1/10000.

The zinc species in the active material layer containing the zinc species refers to a zinc-containing compound. The zinc-containing compound is not particularly limited as long as it can be used as a negative electrode active material. For example, zinc oxide (1 type / 2 types / 3 types), conductive zinc oxide, zinc metal, zinc powder, Zinc fiber, zinc hydroxide, zinc sulfide, tetrahydroxyzinc alkali metal salt, tetrahydroxyzinc alkaline earth metal salt, zinc halogen compound, zinc carboxylate compound, zinc alloy, zinc solid solution, zinc borate, zinc phosphate, Selected from the group consisting of elements belonging to Groups 1 to 17 of the periodic table represented by zinc hydrogen phosphate, zinc silicate, zinc aluminate, carbonic acid compound, hydrogen carbonate compound, nitric acid compound, sulfuric acid compound, etc. Examples include zinc (alloy) compounds, organic zinc compounds, and zinc compound salts having at least one element. Among these, zinc oxide (1 type / 2 types / 3 types), conductive zinc oxide, zinc metal, zinc dust, zinc fiber, zinc hydroxide, tetrahydroxy zinc alkali metal salt, tetrahydroxy zinc alkaline earth metal salt Zinc halogen compounds, zinc carboxylate compounds, zinc alloys, zinc solid solutions, zinc borate, zinc phosphate, zinc silicate, zinc aluminate, and zinc carbonate are more preferred. The zinc metal and zinc alloy may be zinc metal used for (alkali) dry batteries and air batteries, and zinc alloy used for (alkali) dry batteries and air batteries, respectively. The zinc-containing compound can be used alone or in combination of two or more.

The active material layer containing the zinc species can be prepared by coating, pressure bonding, bonding, piezoelectric, rolling, stretching, melting, etc. a zinc negative electrode mixture containing a zinc-containing compound on a current collector.
As a compounding quantity in the zinc negative electrode mixture of the said zinc containing compound, it is preferable that it is 50-99.9 mass% with respect to 100 mass% of whole quantity of a zinc negative electrode mixture. When the amount of the zinc-containing compound is in such a range, better battery performance is exhibited when a zinc negative electrode formed from a zinc negative electrode mixture is used as the negative electrode of the battery. More preferably, it is 55-99.5 mass%, More preferably, it is 60-99 mass%.

Examples of the shape of the zinc-containing compound particles include fine powder, powder, granule, fine granule, scaly, fiber, granule, polyhedron, rod, rectangular, cylindrical, curved surface, and the like. .

The specific surface area of the zinc-containing compound is preferably 0.01 m ² / g or more. More preferably, it is 0.1 m < ² > / g or more as a specific surface area, More preferably, it is 0.2 m < ² > / g or more. Moreover, it is preferable that this specific surface area is 200 m < ² > / g or less.
The specific surface area can be measured by a specific surface area measuring device or the like. The particles having a specific surface area as described above can be produced, for example, by making the particles into nanoparticles or by making the particle surface uneven by selecting the preparation conditions for particle production. is there.

The zinc-containing compound preferably includes particles satisfying the following average particle diameter and / or aspect ratio. Moreover, it is more preferable that the zinc-containing compound satisfies the following average particle diameter and / or aspect ratio.
The average particle size of the zinc-containing compound is preferably 1 nm to 500 μm, more preferably 5 nm to 100 μm, still more preferably 10 nm to 20 μm, and particularly preferably 100 nm to 10 μm.
When the zinc-containing compound is measured with a particle size distribution measuring device after adding zinc oxide particles to ion-exchanged water and ultrasonically dispersing for 5 minutes, the average particle size is preferably 100 nm to 100 μm. More preferably, it is 200 nm-50 micrometers, More preferably, it is 300 nm-10 micrometers. The mode diameter is preferably 50 nm to 20 μm. More preferably, it is 70 nm-10 micrometers, More preferably, it is 100 nm-5 micrometers. The median diameter is preferably 100 nm to 10 μm. More preferably, it is 150 nm-7 micrometers, More preferably, it is 500 nm-5 micrometers.
The aspect ratio (vertical / horizontal) of the zinc-containing compound is, for example, when the zinc-containing compound can be measured in a rectangular shape, a columnar shape, a spherical shape, a curved surface-containing shape, a polyhedral shape, a scale shape, a rod shape, etc. Preferably it is 1.1-100,000, More preferably, it is 1.2-50000, More preferably, it is 1.5-10000. When particles that satisfy the above average particle size and aspect ratio are not included, cycle characteristics decrease due to shape change or passive formation of the negative electrode active material, and self-discharge occurs during charging or storage in the charged state. There is a possibility of becoming easy.
The average particle size can be measured with a particle size distribution analyzer after adding zinc-containing compound particles to ion-exchanged water and ultrasonically dispersing the particles for 5 minutes. The aspect ratio (vertical / horizontal) is, for example, from the shape of particles observed by a scanning electron microscope (SEM), in the case of a rectangular shape, the longest side is vertical and the second longest side is horizontal. Is obtained by dividing the length by the horizontal length. In the case of a cylinder, sphere, curved surface, polyhedron, etc., when a certain part is placed on the bottom so that the aspect ratio is maximized, it is projected from the direction that maximizes the aspect ratio. Measure the length of a point that is farthest from a point in a two-dimensional shape that can be made, with the longest side as the vertical, the longest side of the straight line passing through the vertical center point as the horizontal, and the vertical length as the horizontal. It can be obtained by dividing by the length of.

It is preferable that the said zinc negative electrode mixture contains a conductive support agent with a zinc containing compound.
Examples of the conductive assistant include conductive carbon, conductive ceramics, zinc / zinc powder / zinc alloy / (alkali) (storage) batteries and zinc used in air batteries (hereinafter collectively referred to as metallic zinc). Further, metals such as copper, brass, nickel, silver, bismuth, indium, lead, and tin can be used.
Examples of the conductive carbon include graphite, natural graphite, artificial graphite, glassy carbon, amorphous carbon, graphitizable carbon, non-graphitizable carbon, carbon nanofoam, activated carbon, graphene, nanographene, graphene nanoribbon, fullerene, carbon black, graphite Carbon black, ketjen black, vapor grown carbon fiber, pitch-based carbon fiber, mesocarbon microbeads, metal coated carbon, carbon coated metal, fibrous carbon, boron containing carbon, nitrogen containing carbon, multilayer / single Single-walled carbon nanotubes, carbon nanohorns, vulcan, acetylene black, carbon treated by introducing oxygen-containing functional groups, SiC-coated carbon, surface by dispersion / emulsion / suspension / microsuspension polymerization, etc. Management and carbon, microcapsules carbon.
Examples of the conductive ceramic include a compound containing at least one selected from Bi, Co, Nb and Y fired with zinc oxide.
Among the conductive aids, graphite, natural graphite, artificial graphite, graphitizable carbon, non-graphitizable carbon, graphene, carbon black, graphitized carbon black, ketjen black, vapor-grown carbon fiber, pitch-based carbon fiber, Mesocarbon microbeads, fibrous carbon, multi-walled / single-walled carbon nanotubes, Vulcan, acetylene black, carbon treated with hydrophilicity by introducing oxygen-containing functional groups, metallic zinc, copper, brass, nickel, silver, bismuth, indium, Metals such as lead and tin are preferred. In addition, the metal zinc may be used for an actual battery such as an alkaline (storage) battery or an air battery, or may have a surface treated with other elements or carbon, or may be alloyed. May be. It may be a solid solution. The said conductive support agent can be used by 1 type, or 2 or more types.

Metallic zinc can also act as an active material.
Metallic zinc is added as a negative electrode mixture in the negative electrode preparation stage. In the process of using the battery, zinc metal generated from zinc oxide, zinc hydroxide or the like, which is a zinc-containing compound, also functions as a conductive additive. In this case, the zinc-containing compound substantially functions as a negative electrode active material and a conductive additive in the process of using the battery.
In the case of using a water-containing electrolyte when producing a storage battery using this conductive auxiliary agent, there may be a case where a side reaction of water proceeds in the process of using the battery, and this side reaction is suppressed. In order to do this, a specific element may be introduced into the conductive additive. Specific elements include Al, B, Ba, Bi, Br, C, Ca, Cd, Ce, Cl, Cu, Eu, F, Ga, Hg, In, La, Mg, Mn, N, Nb, Nd, Ni, P, Pb, Sb, Sc, Si, Sm, Sn, Sr, Ti, Tl, Y, Zr, etc. are mentioned. When conductive carbon is used as one of the conductive assistants, specific elements include Al, B, Ba, Bi, C, Ca, Cd, Ce, Cu, F, In, La, Mg, Mn N, Nb, Nd, Ni, P, Pb, Sb, Sc, Si, Sn, Tl, Y, Zr are preferable.
Here, introducing a specific element into a conductive additive means that the conductive auxiliary is a compound having these elements as constituent elements.

As a compounding quantity of the said conductive support agent, it is preferable that it is 0.0001-100 mass% with respect to 100 mass% of zinc containing compounds in a zinc negative electrode mixture. When the blending amount of the conductive auxiliary is in such a range, better battery performance is exhibited when the zinc negative electrode formed from the zinc negative electrode mixture is used as the negative electrode of the battery. More preferably, it is 0.0005-60 mass%, More preferably, it is 0.001-40 mass%.
In addition, when using metal zinc as a conductive support agent at the time of preparing a negative electrode mixture, the metal zinc is not a zinc-containing compound but is calculated as a conductive support agent. In addition, zinc metal produced in the process of battery use from zinc oxide or zinc hydroxide, which are zinc-containing compounds, will also function as a conductive aid in the system. Since it is not zero-valent zinc metal at the time of preparation, it is not considered here as a conductive additive. That is, the preferable compounding quantity of the said conductive support agent is a preferable quantity of the conductive support agent mix | blended at the time of preparation of a zinc negative electrode mixture or a zinc negative electrode.

The average particle size of the conductive aid is preferably 1 nm to 500 μm, more preferably 5 nm to 200 μm, still more preferably 10 nm to 100 μm, and most preferably 10 nm to 60 μm.

The specific surface area of the conductive aid is preferably 0.1 m ² / g or more, and more preferably 1 m ² / g or more. Further, it is preferably 1500 m ² / g or less, more preferably 1200 m ² / g or less, still more preferably 900 m ² / g or less, still more preferably 250 m ² / g or less, Particularly preferably, it is 50 m ² / g or less.
By setting the specific surface area of the conductive additive to the above value, there are effects such as the ability to suppress the shape change of the zinc-containing compound which is the active material and the formation of the passive state in the process of using the battery.
The average particle diameter and specific surface area can be measured by the same method as described above.

The zinc negative electrode mixture used for preparing the active material layer is selected from the group consisting of elements belonging to Group 1 to Group 17 of the periodic table, if necessary, together with the zinc-containing compound and the conductive assistant. It can be prepared by mixing at least one selected from the group consisting of a compound having at least one element, an organic compound, and an organic compound salt. Various compounds can be used as the compound having at least one element selected from the group consisting of elements belonging to Group 1 to Group 17 of the periodic table. For example, nitrogen-containing compounds such as ammonium salts and thioureas Is also preferable. For example, a zinc-containing compound and a compound having at least one element selected from the group consisting of elements belonging to Group 1 to Group 17 of the periodic table are optionally added with a conductive additive, and a dry process. Alternatively, a zinc negative electrode mixture may be prepared by mixing by a wet method. A zinc-containing compound and a compound having at least one element selected from the group consisting of elements belonging to Group 1 to Group 17 of the periodic table may be alloyed. It is also possible to introduce an element having a reduction potential more noble than zinc into the zinc-containing compound by a charge / discharge process. A spray laser or the like may be used, and a mechanochemical method, a sol-gel method, a coprecipitation method, or the like may also be used.

The zinc negative electrode mixture may further contain an additive to the above-described active material layer and / or a solid electrolyte in the layer, or an additive to the electrolytic solution. Thereby, the effect similar to the effect which the additive in the electrolyte solution exhibits can be exhibited.

The zinc negative electrode of the present invention is preferably one in which an active material layer is formed using the zinc negative electrode mixture.

Examples of the method for preparing the active material layer of the zinc negative electrode include the following methods.
A zinc negative electrode mixture-containing slurry or paste mixture is obtained by using the same polymer as the binder or a thickener in the zinc negative electrode mixture obtained by the preparation method described above. Next, the obtained slurry or paste mixture is coated, pressure-bonded, bonded, piezoelectric, rolled, stretched / melted, etc. on the current collector so that the film thickness is as constant as possible. As described above, when the zinc negative electrode of the present invention contains a solid electrolyte on the active material layer, the zinc negative electrode mixture is applied onto the current collector, pressure bonded, bonded, piezoelectric, rolled, stretched, After preparing an active material layer by melting or the like, a solid electrolyte can be formed on the active material layer. Further, as described above, when the zinc negative electrode of the present invention contains a solid electrolyte in the active material layer, a solid electrolyte that has been coated, pressed, bonded, piezoelectric, rolled, stretched, melted, etc. on the active material layer is used. It may be introduced into the active material layer by using heat, pressure, solvent, or the like. In addition, a zinc negative electrode mixture is prepared using a process of mixing a solid electrolyte or a solid electrolyte raw material together with a zinc negative electrode mixture raw material, and then collected by coating, pressure bonding, adhesion, piezoelectric, rolling, stretching, melting, etc. An active material layer containing a solid electrolyte in the electric body may be produced. Thereby, an active material layer containing the solid electrolyte therein is produced.

The current collectors are (electrolytic) copper foil, copper mesh (expanded metal), foamed copper, punched copper, copper alloys such as brass, brass foil, brass mesh (expanded metal), foamed brass, punched brass, nickel foil , Corrosion resistant nickel, nickel mesh (expanded metal), punching nickel, metallic zinc, corrosion resistant metallic zinc, zinc foil, zinc mesh (expanded metal), (punched) steel sheet, non-woven fabric with conductivity; Ni, Zn, Sn, Pb · Copper foil with added Hg, Bi, In, Tl, brass, etc. · Copper mesh (expanded metal) · Copper alloy such as foamed copper, punched copper, brass · Brass foil · Brass mesh (expanded metal) · Foam Brass, punching brass, nickel foil, corrosion-resistant nickel, nickel mesh (expanded metal), Plating with Ni / Zn / Sn / Pb / Hg / Bi / In / Tl / Brass, etc. Niching nickel, metal zinc, corrosion resistant metal zinc, zinc foil, zinc mesh (expanded metal), (punched) steel plate, non-woven fabric (Electrolysis) Copper foil, copper mesh (expanded metal), foamed copper, punched copper, copper alloys such as brass, brass foil, brass mesh (expanded metal), foamed brass, punched brass, nickel foil, corrosion-resistant nickel, nickel mesh ( Expanded metal), punched nickel, metal zinc, corrosion-resistant metal zinc, zinc foil, zinc mesh (expanded metal), (punched) steel sheet, non-woven fabric, silver; used as a current collector and container for alkaline (storage) batteries and zinc-air batteries And the like.

The slurry or paste mixture may be applied to one side of the current collector, pressure-bonded, bonded, piezoelectric, rolled, stretched, melted, etc., or coated, pressure-bonded, bonded, piezoelectrically rolled, rolled, stretched on both sides and the entire surface. -It may be melted. It is dried at 0 to 400 ° C. during coating / crimping / adhesion / piezoelectric / rolling / stretching / melting and / or after coating / crimping / adhesion / piezoelectricity / rolling / stretching / melting. More preferably, it is 15-380 degreeC as drying temperature. Drying may be performed by vacuum drying or reduced pressure drying. The drying time is preferably 5 minutes to 48 hours. You may repeat the process of coating and drying. Moreover, it is preferable to press with a roll press machine etc. by the pressure of normal pressure-20t with a roll press machine before and behind drying of the said slurry or paste mixture. The pressure for pressing is more preferably a pressure of normal pressure to 15 t. You may apply the temperature of 10-500 degreeC at the time of a press. The pressing process may be performed once or a plurality of times. When performing pressing, the adhesion between the active materials, the active material and the binder, the active material and the current collector is improved, and the active material amount, the thickness of the active material layer, the strength, the flexibility, etc. It is also possible to adjust.

The zinc negative electrode (zinc mixture electrode) thus obtained suppresses the decomposition of water in the zinc negative electrode, particularly when used as a negative electrode for a secondary battery. Deformation such as dendrite, deterioration due to passive formation, and generation of hydrogen in the process of use as a negative electrode of a battery can be suppressed to the maximum.
The film thickness of the zinc negative electrode is preferably 1 nm to 10000 μm from the viewpoint of the battery configuration and the suppression of peeling of the active material from the current collector. More preferably, it is 10 nm-1500 micrometers, More preferably, it is 20 nm-1000 micrometers, Most preferably, it is 100 nm-800 micrometers.

Since the battery using the zinc electrode of the present invention can use a water-containing electrolyte as the electrolyte, a highly safe battery can be obtained.
In addition to the zinc negative electrode, the battery of the present invention can include a positive electrode, an electrolyte sandwiched between the zinc negative electrode and the positive electrode, and the like. Thus, the battery comprised using the zinc negative electrode of this invention, a positive electrode, and electrolyte is also one of this invention.
Moreover, as an electrolyte solution, a water-containing electrolyte solution is preferable as described later. Accordingly, the present invention also includes a zinc negative electrode, a positive electrode, a separator, and a battery including the water-containing electrolyte that is sandwiched between the zinc negative electrode and the positive electrode. The battery of the present invention may include one of each of these components, or may include two or more.
The preferable configuration of the zinc negative electrode in the battery of the present invention is the same as the preferable configuration of the zinc negative electrode of the present invention described above.

The positive electrode can be formed using a material normally used as a positive electrode active material of a primary battery or a secondary battery, and is not particularly limited. For example, oxygen (when oxygen becomes a positive electrode active material, the positive electrode is Perovskite compounds capable of reducing oxygen and oxidizing water, cobalt-containing compounds, iron-containing compounds, copper-containing compounds, manganese-containing compounds, vanadium-containing compounds, nickel-containing compounds, iridium-containing compounds, platinum-containing compounds; palladium-containing compounds; Gold-containing compounds; silver compounds; air electrodes composed of carbon-containing compounds, etc.); nickel-containing compounds such as nickel oxyhydroxide, nickel hydroxide, cobalt-containing nickel hydroxide; manganese-containing compounds such as manganese dioxide; oxidation Silver; lithium-containing compounds such as lithium cobaltate; iron-containing compounds and the like.

The electrolytic solution sandwiched between the zinc negative electrode and the positive electrode is not particularly limited as long as it is usually used as an electrolytic solution for a battery, and examples thereof include a water-containing electrolytic solution and an organic solvent-based electrolytic solution. A water-containing electrolyte is preferred. The water-containing electrolytic solution refers to an electrolytic solution using only water as an electrolytic solution raw material (aqueous electrolytic solution) or an electrolytic solution using a solution obtained by adding an organic solvent to water as an electrolytic solution raw material.
The preferable thing of the said aqueous electrolyte solution is the same as that of the preferable aqueous electrolyte solution used for the solid electrolyte on the active material layer mentioned above and / or in this layer. That is, the electrolytic solution may be used as a raw material for the solid electrolyte, or when the solid electrolyte is contained in the active material layer, only the electrolytic solution may be used between the positive electrode and the negative electrode.

The preferable range of the concentration of the electrolytic solution is the same as the preferable range of the concentration of the electrolytic solution of the solid electrolyte on the active material layer and / or in the layer.
Note that the electrolytic solution may or may not be circulated.

The electrolytic solution may contain an additive. In the case of using an aqueous electrolyte, side reactions in the process of using a battery in which hydrogen is generated by the progress of a water decomposition reaction, which usually occurs thermodynamically, the shape change of the zinc electrode active material, the Dynamic formation can be suppressed. It is considered that this is because the additive suitably interacts with the surface on the zinc oxide to suppress side reactions, morphological change of the zinc electrode active material, and passive formation.
The preferable additive is the same as the preferable additive on the above-described active material layer and / or the solid electrolyte in the layer.

The electrolyte sandwiched between the zinc negative electrode and the positive electrode may be a solid electrolyte (gel electrolyte). The preferable thing of this solid electrolyte is the same as that of the preferable solid electrolyte on the active material layer mentioned above and / or in this layer.

The battery of the present invention can further use a separator. The separator is a member that separates the positive electrode and the negative electrode and holds the electrolyte solution to ensure ionic conductivity between the positive electrode and the negative electrode. When a solid electrolyte (gel electrolyte) is used as the electrolyte, this also serves as a separator, but a separator other than the solid electrolyte may be used.

The said separator can use the general separator represented by description in the international publication 2013/027767. The separator may include a material similar to the above-described anion conductive material according to the first aspect of the present invention. The anion conductive material itself can also serve as a separator. As will be described later, when a solid electrolyte (gel electrolyte) is used as an electrolyte, it can also serve as a separator, but a separator other than the solid electrolyte may be used. Anion conductive material or solid electrolyte (gel electrolyte) is applied to the separator, glass filter, carbon paper, membrane filter, water repellent (porous) compound (hereinafter also referred to as structure), etc. , Adhesion, piezoelectricity, rolling, stretching, melting, etc. may be integrated. In this case, since the polymer is contained in the anion conductive material or the solid electrolyte, the strength and flexibility of the obtained material are increased, and the anion conductive material and the solid electrolyte from the structure are greatly slipped off. Will be reduced. The structure can increase the strength and flexibility of the material, and can also increase the function of wetting the positive and negative electrodes, the function of avoiding liquid drainage, and the like. The structure is preferably a sheet (film).
When used in an air battery, a fuel cell, or the like, an anion conductive material, a solid electrolyte, a structure in which an anion conductive material or a solid electrolyte is integrated may include a catalyst layer or a gas diffusion layer.
The separator can be used singly or in combination of two or more, and any number can be used as long as the resistance increases and the battery performance does not deteriorate. The separator may have pores, micropores, and a gas diffusion layer. When using a water-containing electrolyte, it is preferable to perform a hydrophilic treatment on the separator by introducing a surfactant or the like. A water-containing electrolytic solution and a solid electrolyte may be used in combination.

As a separator, the said specific polyvalent cation and / or an inorganic compound, a nitrogen-containing organic compound, surfactant, electrolyte solution, etc. may be included in the separator.

The form of the battery using the zinc electrode of the present invention as a negative electrode is as follows: primary battery; secondary battery (storage battery) capable of charge / discharge; use of mechanical charge (mechanical replacement of zinc negative electrode); zinc negative electrode of the present invention In addition, any form such as use of a third electrode (for example, an electrode for removing oxygen and hydrogen generated during charge / discharge) different from the positive electrode composed of the positive electrode active material as described later may be used. A secondary battery (storage battery) is preferable.

As described above, a battery having a zinc negative electrode prepared from the zinc negative electrode mixture is also one aspect of the present invention. The positive electrode is more preferably a nickel electrode, a manganese electrode, or an air electrode. Here, taking the nickel electrode as an example, the configuration of the nickel / zinc storage battery will be described below.
The nickel-zinc storage battery includes the zinc negative electrode, a nickel positive electrode, a separator that separates the positive electrode and the negative electrode, an electrolyte and an electrolytic solution, an assembly including them, and a holding container.
There is no restriction | limiting in particular as a nickel electrode, It is also possible to use the nickel electrode used for a nickel hydrogen battery, a nickel metal hydride battery (nickel metal hydride alloy battery), a nickel cadmium battery, etc. The inner walls of the assembly and the holding container are made of a material that does not deteriorate due to corrosion or reaction in the process of using the battery. It is also possible to use a container used for an alkaline battery or a zinc-air battery. The storage battery is a single type, single type, single type, single type, single type, single type, single type, R123A type, cylindrical type such as R-1 / 3N type, etc .; square type such as 9V type, 006P type, etc. A button type; a coin type; a laminate type; a laminated type; a type in which positive and negative plates formed into strips are alternately sandwiched between pleated separators, a sealed type, an open type, or a vent type Good. You may have the site | part which reserves the gas generated in the process of using a battery.

The battery manufacturing process of the present invention may be a wet process or a dry process. In the wet process, for example, the positive electrode current collector and the negative electrode current collector are respectively coated with a paste or slurry of a positive electrode material and a paste or slurry of a negative electrode material, and the coated electrode sheet is dried and compressed, and cutting and cleaning are performed. Thereafter, the cut electrodes and separators are stacked in layers to form a battery assembly. The dry process is a process using, for example, electrode component powder or a granular dry mixture instead of slurry or paste. (1) The negative electrode material is applied to a current collector, and (2) the positive electrode material is collected in a dry state. (3) A separator is placed between the sheets of (1) and (2) to form a layered structure to form a battery assembly, and (4) the battery assembly of (3) is wrapped or folded. The three-dimensional structure is formed through the same process. The electrode may be wrapped with or coated with a separator, an anion conductive material, a (gel) solid electrolyte, or the like. The positive electrode and the negative electrode may also serve as a container constituting the battery. As the step of attaching the terminal, spot welding, ultrasonic welding, laser welding, soldering, or any other conductive joining method suitable for the material of the terminal and the current collector is selected. During the battery manufacturing process or storage, the battery may be in a charged state or a discharged state.

When the battery of the present invention is a storage battery, the charge / discharge rate of the storage battery is preferably 0.01 C or more and 100 C or less. More preferably, they are 0.01C or more and 80C or less, More preferably, they are 0.01C or more and 60C or less, Especially preferably, they are 0.01C or more and 30C or less. It is preferable that the storage battery can be used in both a cold region and a tropical region on the earth, and it is preferable that the storage battery can be used at a temperature of −50 ° C. to 100 ° C.

The zinc negative electrode of the present invention has the above-described configuration. When a battery is formed using this, the solid electrolyte is placed on the active material layer and / or in the layer as compared with the conventional battery using the zinc negative electrode. Introduced to sufficiently suppress changes in the shape and shape of the active material, while suppressing the expansion and contraction of the solid electrolyte, holding the electron conduction path and causing defects such as cracks in the electrode active material layer The ion conductivity can be sufficiently improved, and the battery performance can be sufficiently improved.

1 is a graph showing the results of a charge / discharge test performed on the solid electrolyte according to Example 1. FIG. FIG. 2 is a photomicrograph of the zinc mixture electrode before the 200-cycle charge / discharge test in Example 5. FIG. 3 is a photomicrograph of the zinc mixture electrode after the 200-cycle charge / discharge test in Example 5. FIG. 4 is a photomicrograph of the zinc mixture electrode before the 200-cycle charge / discharge test in Example 7. FIG. 5 is a microscope in which a zinc mixture electrode after a 200-cycle charge / discharge test was photographed in Example 7. 6 is a photomicrograph of the zinc mixture electrode before the 200-cycle charge / discharge test in Example 9. FIG. FIG. 7 is a microscope in which a zinc mixture electrode after a 200-cycle charge / discharge test was photographed in Example 9. FIG. 8 is a photomicrograph of the zinc mixture electrode before the 200-cycle charge / discharge test in Example 11. FIG. 9 is a photomicrograph of the zinc mixture electrode after the 200-cycle charge / discharge test in Example 11. FIG. 10 is a photomicrograph of the zinc mixture electrode before the 200-cycle charge / discharge test in Example 15. FIG. 11 is a photomicrograph of the zinc mixture electrode after the 200-cycle charge / discharge test in Example 15. FIG. 12 is a photomicrograph of the zinc mixture electrode before the 200-cycle charge / discharge test in Example 21. FIG. 13 is a photomicrograph of the zinc mixture electrode after the 200-cycle charge / discharge test in Example 21. 14 is a photomicrograph of the zinc mixture electrode before the 200-cycle charge / discharge test in Example 22. FIG. FIG. 15 is a photomicrograph of the zinc mixture electrode after the 200-cycle charge / discharge test in Example 22. FIG. 16 is a photomicrograph of the zinc mixture electrode before the 200-cycle charge / discharge test in Example 24. FIG. 17 is a photomicrograph of the zinc mixture electrode after a 200-cycle charge / discharge test in Example 24.

The present invention will be described in more detail with reference to the following examples. However, the present invention is not limited to these examples. In the examples, the average particle size of the inorganic compound was measured using a particle size distribution measuring device.
1 is a graph showing the results of a charge / discharge test performed on the solid electrolyte according to Example 1. FIG. In FIG. 1, “1st-charge” and “100th-charge” represent the first and 100th charging curves, respectively. Also, “3rd-discharge”, “10th-discharge”, “20th-discharge”, “40th-discharge”, “80th-discharge”, “100th-discharge” are the third, tenth, twentieth, The 40th, 80th and 100th discharge curves are shown.

Example 1
Zinc oxide (27.6 g), acetylene black (0.90 g), cerium (IV) oxide (2.4 g), ethanol (99.5%) (92.7 g), water (92.7 g) in a ball mill. Added and ball mill mixed. Then, it dried at 100 degreeC under pressure reduction for 2 hours with the evaporator, and also dried at 110 degreeC under pressure reduction with the stationary type vacuum dryer overnight. The solid after drying was pulverized for 60 seconds at a rotation speed of 18000 rpm using a pulverizer (X-Treme MX1200XTM manufactured by WARING). The obtained solid (1.1 g), 12% polyvinylidene fluoride / N-methylpyrrolidone solution (2.0 g) and N-methylpyrrolidone (0.90 g) were added to a glass vial, and a stirrer bar was used. Stir overnight. The obtained slurry was coated on a copper foil using an automatic coating apparatus and dried at 80 ° C. for 12 hours. After pressing the copper foil coated with the zinc mixture with a press pressure of 3 t, this was punched out with a punching machine (diameter: 15.95 mm) to obtain a zinc mixture electrode, and a working electrode with an apparent area of 0.50 cm ² Used as is.

Next, acrylic acid (1.1 g) was slowly added to 8 mol / L potassium hydroxide + 20 g / L lithium hydroxide aqueous solution (10 g) in which zinc oxide was dissolved until saturation, followed by hydrotalcite [Mg _0.8 Al _0.2 (OH) ₂ ] (CO ₃ ²⁻ ) _0.1 · mH ₂ O (0.5 g) was added and stirred. A 4% ammonium persulfate aqueous solution (0.4 g) was added thereto, and the mixture was applied to the zinc mixture electrode and polymerized under nitrogen, whereby a hydrotalcite-containing acrylate was formed on the electrode active material and in the layer. The formation of the solid electrolyte (1) was confirmed by a scanning electron microscope (SEM) or a laser microscope.

Subsequently, 8 mol / L potassium hydroxide and 20 g / L lithium hydroxide aqueous solution (8.2 g) in which zinc oxide was dissolved until saturation were added to sodium polyacrylate (weight average molecular weight 1,500,000) (1.0 g) and hydrotalc. Hydrotalcite-containing acrylate solid electrolyte by adding and stirring the site [Mg _0.8 Al _0.2 (OH) ₂ ] (CO ₃ ²⁻ ) _0.1 · mH ₂ O (1.5 g) (2) was prepared.

Nickel electrode as the counter electrode (active material: cobalt-coated nickel hydroxide, capacity is set to 3 times or more of the zinc electrode), hydrotalcite-containing acrylate solid electrolyte prepared as the gel electrolyte (2) (thickness: 1 mm) ) And a coin cell was used to conduct a charge / discharge test at a current value of 0.89 mA (charge / discharge time: 1 hour / 1.9 V and 1.2 V cut-off each). The results are shown in FIG. From FIG. 1, it can be seen that Example 1 using the solid electrolyte according to the present invention can be stably charged and discharged with a high capacity. In addition, when the zinc mixture electrode after the 100-cycle charge / discharge test was observed with an SEM or a laser microscope, no deterioration such as cracking or active material shape change was observed in the electrode. It was visually confirmed that there was no change in the hydrotalcite-containing acrylate solid electrolyte (2).

(Example 2)
A zinc mixture electrode was prepared in the same manner as in Example 1 and used so as to be a working electrode having an apparent area of 0.50 cm ² . Next, a hydrotalcite-containing acrylate solid electrolyte (2) was prepared in the same manner as in Example 1, and this was applied to the zinc mixture electrode and allowed to stand for 24 hours. By this operation, it was confirmed by SEM or a laser microscope that the hydrotalcite-containing acrylate solid electrolyte (2) was formed on the electrode active material and part of the layer.

Nickel electrode as the counter electrode (active material: cobalt-coated nickel hydroxide, capacity is set to 3 times or more of the zinc electrode), hydrotalcite-containing acrylate solid electrolyte prepared as the gel electrolyte (2) (thickness: 1 mm) ) And a charge / discharge test was performed using a coin cell at a current value of 1.0 mA (charge / discharge time: 1 hour each). The discharge capacity at the 100th cycle was 504 mAh / g. In addition, when the zinc mixture electrode after the 100-cycle charge / discharge test was observed with an SEM or a laser microscope, no deterioration such as cracking or active material shape change was observed in the electrode. It was visually confirmed that there was no change in the hydrotalcite-containing acrylate solid electrolyte (2).

(Example 3)
Zinc oxide (0.86 g), zinc (0.26 g), hydrotalcite [Mg _0.67 Al _0.33 (OH) ₂ ] (CO ₃ ²⁻ ) _0.165 · mH ₂ O (0.1 g) A 60% polytetrafluoroethylene aqueous solution (0.2 g), a 2% sodium polyacrylate (weight average molecular weight 1,500,000) aqueous solution (0.1 g), and water were added thereto, and the mixture was stirred in an agate mortar. After pressing the obtained solid with a rolling mill, it is pressure-bonded to a copper mesh current collector with a roll press (active material layer thickness: about 300 μm on one side) to form a zinc mixture electrode, and a working electrode with an apparent area of 1 cm ² Used as is.
4 mol / L potassium hydroxide aqueous solution in which zinc oxide is dissolved as an electrolyte until saturation, non-woven fabric as separator, nickel electrode as counter electrode (active material: cobalt-coated nickel hydroxide, capacity set to 1.8 times that of zinc electrode) ) And a charge / discharge test was conducted using a triode cell at a current value of 10 mA / cm ² (charge / discharge time: 1 hour each). Charge / discharge of at least 50 cycles is possible, and when the zinc mixture electrode after the 50-cycle charge / discharge test is observed with an SEM or a laser microscope, the electrode shows no deterioration such as cracks and changes in the shape of the active material. There wasn't. At this time, it was also confirmed that the current collector copper was plated with zinc.

Example 4
A zinc mixture electrode was prepared in the same manner as in Example 3 except that the 2% sodium polyacrylate aqueous solution (0.1 g) was replaced with the 2% carboxymethylcellulose aqueous solution so that the working electrode had an apparent area of 1 cm ^2. Used.
4 mol / L potassium hydroxide aqueous solution in which zinc oxide is dissolved as an electrolyte until saturation, non-woven fabric as separator, nickel electrode as counter electrode (active material: cobalt-coated nickel hydroxide, capacity set to 1.8 times that of zinc electrode) ) And a charge / discharge test was conducted using a triode cell at a current value of 10 mA / cm ² (charge / discharge time: 1 hour each). Charge / discharge of at least 50 cycles is possible, and when the zinc mixture electrode after the 50-cycle charge / discharge test is observed with an SEM or a laser microscope, the electrode shows no deterioration such as cracks and changes in the shape of the active material. There wasn't. At this time, it was also confirmed that the current collector copper was plated with zinc.

(Comparative Example 1)
A zinc mixture electrode was prepared in the same manner as in Example 1 except that cerium oxide was not added, and was used so as to be a working electrode having an apparent area of 0.50 cm ² . Next, sodium polyacrylate (weight average molecular weight 1,500,000) (1.0 g) was added to 8 mol / L potassium hydroxide + 20 g / L lithium hydroxide aqueous solution (8.2 g) in which zinc oxide was dissolved until saturation. By stirring, an acrylate solid electrolyte (3) was prepared, which was applied to the zinc mixture electrode and allowed to stand for 24 hours. By this operation, it was confirmed by SEM or a laser microscope that an acrylate solid electrolyte (3) was formed on the electrode active material and part of the layer.

Nickel electrode (active material: cobalt-coated nickel hydroxide, capacity set to 3 times or more of zinc electrode) as counter electrode, and acrylate solid electrolyte (3) (thickness: 1 mm) prepared above as gel electrolyte. A charge / discharge test was performed using a coin cell at a current value of 0.90 mA (charge / discharge time: 1 hour each). However, charging and discharging became impossible at the 48th cycle. When the zinc mixture electrode after the 48-cycle charge / discharge test was observed with an SEM or a laser microscope, a change in the shape of the electrode active material was observed, and contact between particles such as the active material was also deteriorated. Moreover, it is confirmed visually that zinc-type dendrite has grown in the acrylate solid electrolyte (3) from the negative electrode to the positive electrode, and the cause of the inability to charge / discharge the coin cell is a short circuit. I also understood that.

(Comparative Example 2)
A zinc mixture electrode was prepared in the same manner as in Example 1 except that cerium oxide was not added, and used as a working electrode having an apparent area of 2 cm ² . Nickel electrode as counter electrode (active material: cobalt-coated nickel hydroxide, capacity is set to 3 times or more of zinc electrode), and electrolyte solution is 8 mol / L potassium hydroxide +20 g / L in which zinc oxide is dissolved until saturation A lithium hydroxide aqueous solution (8.2 g) was used, a non-woven fabric (2 sheets) and a hydrophilic microporous film (1 sheet) were sandwiched between a zinc electrode and a nickel electrode as a separator, and a current of 3.2 mA was used using a coin cell. The charge / discharge test was conducted using the values (charge / discharge time: 1 hour each). However, with the generation of oxygen from the nickel electrode and / or hydrogen from the zinc electrode, swelling is observed in the coin cell, which gradually reduces the discharge capacity, making charging and discharging impossible at the 19th cycle. It was.

(Example 5)
Hydrotalcite [Mg _0.8 Al _0.2 (OH) ₂ ] (CO ₃ ²⁻ ) _0.1 · mH ₂ O (2.0 g) was added with polytetrafluoroethylene (3 g) and water, and an agate mortar Stir with. The obtained solid was pressed with a rolling mill and then rolled with a roll press to produce a solid electrolyte.
Next, 60% polytetrafluoroethylene aqueous solution (0.033 g) and water were added to zinc oxide (0.61 g) and bismuth oxide (0.019 g), and the mixture was stirred in an agate mortar. After pressing the obtained solid with a rolling mill, this is pressure-bonded to a copper mesh current collector with a roll press machine, and then the solid electrolyte is pressure-bonded with a roll press machine to have a solid electrolyte on the active material The zinc mixture electrode was used so as to be a working electrode having an apparent area of 1 cm ² .
8 mol / L potassium hydroxide aqueous solution in which zinc oxide is dissolved as an electrolytic solution until saturation,
Non-woven fabric as separator, nickel electrode as counter electrode (active material: cobalt-coated nickel hydroxide, capacity is set to 0.7 times that of zinc electrode), and electrode charged 50% of the same electrode as positive electrode (counter electrode) as reference electrode Using a triode cell, a charge / discharge test (charge / discharge time: 1 hour each) was performed at a current value of 25 mA / cm ² , and a cycle life of at least 200 cycles was observed (Coulomb efficiency of the 200th charge / discharge) : 88.6%). Moreover, when the zinc mixture electrode after a 200-cycle charging / discharging test was observed by SEM, deterioration, such as a dendrite and a big active material form change, was not seen. Similar results were obtained when the current collector was changed from a copper mesh to a nickel-plated steel plate, a tin-plated steel plate, or a galvanized steel plate.
As a reference, in Example 5, the result of having observed the zinc mixture electrode before and behind a 200 cycle charging / discharging test by SEM is shown in FIG. 2, FIG.

(Example 6)
A solid electrolyte was produced in the same manner as in Example 5.
Next, zinc oxide (0.61 g), bismuth oxide nanoparticles (0.019 g: average particle diameter 87 nm), 60% polytetrafluoroethylene aqueous solution (0.033 g) and water were added and stirred in an agate mortar. A working electrode was produced in the same manner as in Example 5.
A charge / discharge test (charge / discharge time: 1 hour each) was performed in the same manner as in Example 5, and a cycle life of at least 200 cycles or more was observed (Coulomb efficiency of the 200th charge / discharge: 94.5%). Moreover, when the zinc mixture electrode after a 200-cycle charging / discharging test was observed by SEM, deterioration, such as a dendrite and a big active material form change, was not seen.

(Example 7)
A solid electrolyte was produced in the same manner as in Example 5.
Next, zinc oxide (0.61 g) and tin oxide (0.019 g) were added with a 60% polytetrafluoroethylene aqueous solution (0.033 g) and water, and the mixture was stirred in an agate mortar. A working electrode was prepared.
A charge / discharge test (charge / discharge time: 1 hour each) was performed in the same manner as in Example 5, and a cycle life of at least 200 cycles or more was observed (Coulomb efficiency of the 200th charge / discharge: 90.8%). Moreover, when the zinc mixture electrode after a 200-cycle charging / discharging test was observed by SEM, deterioration, such as a dendrite and a big active material form change, was not seen.
As a reference, the results of observing the zinc mixture electrode before and after the 200-cycle charge / discharge test in Example 7 with an SEM are shown in FIGS.

(Example 8)
Hydrotalcite [Mg _0.8 Al _0.2 (OH) ₂ ] (CO ₃ ²⁻ ) _0.1 · mH ₂ O (2.0 g) with 2% sodium polyacrylate (weight average molecular weight 1,500,000) (0.1 g), polytetrafluoroethylene (3 g) and water were added and stirred in an agate mortar. The obtained solid was pressed with a rolling mill and then rolled with a roll press to produce a solid electrolyte.
Next, 60% polytetrafluoroethylene aqueous solution (0.033 g) and water were added to zinc oxide (0.61 g) and bismuth oxide (0.019 g), and the mixture was stirred in an agate mortar. A working electrode was prepared.
A charge / discharge test (charge / discharge time: 1 hour each) was performed in the same manner as in Example 5, and a cycle life of at least 200 cycles or more was observed (Coulomb efficiency of the 200th charge / discharge: 92.8%). Moreover, when the zinc mixture electrode after a 200-cycle charging / discharging test was observed by SEM, deterioration, such as a dendrite and a big active material form change, was not seen.

Example 9
A solid electrolyte was produced in the same manner as in Example 5.
Next, zinc oxide (0.61 g) and indium oxide (0.019 g) were added with a 60% polytetrafluoroethylene aqueous solution (0.033 g) and water, and stirred in an agate mortar. A working electrode was prepared.
A charge / discharge test (charge / discharge time: 1 hour each) was performed in the same manner as in Example 5, and a cycle life of at least 200 cycles or more was observed (Coulomb efficiency of the 200th charge / discharge: 90.3%). Moreover, when the zinc mixture electrode after a 200-cycle charging / discharging test was observed by SEM, deterioration, such as a dendrite and a big active material form change, was not seen.
As a reference, the results of observing the zinc mixture electrode before and after the 200-cycle charge / discharge test in Example 9 by SEM are shown in FIGS.

(Example 10)
A solid electrolyte was produced in the same manner as in Example 5.
Next, a 60% polytetrafluoroethylene aqueous solution (0.033 g) and water were added to zinc oxide (0.61 g) and calcium oxide (0.019 g), and the mixture was stirred in an agate mortar. A working electrode was prepared.
A charge / discharge test (charge / discharge time: 1 hour each) was performed in the same manner as in Example 5, and a cycle life of at least 200 cycles or more was observed (Coulomb efficiency of the 200th charge / discharge: 89.8%). Moreover, when the zinc mixture electrode after a 200-cycle charging / discharging test was observed by SEM, deterioration, such as a dendrite and a big active material form change, was not seen.

(Example 11)
A solid electrolyte was produced in the same manner as in Example 5.
Next, 60% polytetrafluoroethylene aqueous solution (0.033 g) and water were added to zinc oxide (0.61 g) and yttrium oxide (0.019 g), and the mixture was stirred in an agate mortar. A working electrode was prepared.
A charge / discharge test (charge / discharge time: 1 hour each) was performed in the same manner as in Example 5, and a cycle life of at least 200 cycles or more was observed (Coulomb efficiency of the 200th charge / discharge: 91.0%). Moreover, when the zinc mixture electrode after a 200-cycle charging / discharging test was observed by SEM, deterioration, such as a dendrite and a big active material form change, was not seen.
As a reference, the results of observation of the zinc mixture electrode before and after the 200-cycle charge / discharge test in Example 11 by SEM are shown in FIGS.

(Example 12)
A solid electrolyte was produced in the same manner as in Example 5.
Next, zinc oxide (0.61 g) and lanthanum oxide (0.019 g) were added with a 60% aqueous polytetrafluoroethylene solution (0.033 g) and water, and stirred in an agate mortar. A working electrode was prepared.
A charge / discharge test (charge / discharge time: 1 hour each) was performed in the same manner as in Example 5, and a cycle life of at least 200 cycles or more was observed (Coulomb efficiency of the 200th charge / discharge: 92.2%). Moreover, when the zinc mixture electrode after a 200-cycle charging / discharging test was observed by SEM, deterioration, such as a dendrite and a big active material form change, was not seen.

(Example 13)
A solid electrolyte was produced in the same manner as in Example 5.
Next, 60% polytetrafluoroethylene aqueous solution (0.033 g) and water were added to zinc oxide (0.61 g) and cerium oxide (0.019 g), and the mixture was stirred in an agate mortar. A working electrode was prepared.
A charge / discharge test (charge / discharge time: 1 hour each) was performed in the same manner as in Example 5, and a cycle life of at least 200 cycles or more was observed (Coulomb efficiency of the 200th charge / discharge: 91.7%). Moreover, when the zinc mixture electrode after a 200-cycle charging / discharging test was observed by SEM, deterioration, such as a dendrite and a big active material form change, was not seen.

(Example 14)
A solid electrolyte was produced in the same manner as in Example 5.
Next, 60% polytetrafluoroethylene aqueous solution (0.033 g) and water were added to zinc oxide (0.61 g) and titanium oxide (0.019 g), and the mixture was stirred in an agate mortar. After pressing the obtained solid with a rolling mill, this is pressure-bonded to a copper mesh current collector with a roll press machine (active material layer thickness: about 300 μm on one side), and then the solid electrolyte is pressure-bonded with a roll press machine. A working electrode was produced in the same manner as in Example 5.
A charge / discharge test (charge / discharge time: 1 hour each) was performed in the same manner as in Example 5, and a cycle life of at least 200 cycles or more was observed (Coulomb efficiency of the 200th charge / discharge: 89.1%). Moreover, when the zinc mixture electrode after a 200-cycle charging / discharging test was observed by SEM, deterioration, such as a dendrite and a big active material form change, was not seen.

(Example 15)
A solid electrolyte was produced in the same manner as in Example 5.
Next, zinc oxide (0.61 g) and zirconium oxide (0.019 g) were added with a 60% polytetrafluoroethylene aqueous solution (0.033 g) and water, and the mixture was stirred in an agate mortar. A working electrode was prepared.
A charge / discharge test (charge / discharge time: 1 hour each) was performed in the same manner as in Example 5, and a cycle life of at least 200 cycles or more was observed (Coulomb efficiency of the 200th charge / discharge: 86.2%). Moreover, when the zinc mixture electrode after a 200-cycle charging / discharging test was observed by SEM, deterioration, such as a dendrite and a big active material form change, was not seen.
As a reference, the results of observing the zinc mixture electrode before and after the 200 cycle charge / discharge test in Example 15 by SEM are shown in FIGS.

(Example 16)
A solid electrolyte was produced in the same manner as in Example 5.
Next, zinc oxide (0.61 g) and niobium oxide (0.019 g) were added with a 60% aqueous polytetrafluoroethylene solution (0.033 g) and water, and the mixture was stirred in an agate mortar. A working electrode was prepared.
A charge / discharge test (charge / discharge time: 1 hour each) was performed in the same manner as in Example 5, and a cycle life of at least 200 cycles or more was observed (Coulomb efficiency of the 200th charge / discharge: 94.5%). Moreover, when the zinc mixture electrode after a 200-cycle charging / discharging test was observed by SEM, deterioration, such as a dendrite and a big active material form change, was not seen.

(Example 17)
A solid electrolyte was produced in the same manner as in Example 5.
Next, zinc oxide (0.61 g) and boric acid (0.019 g) were added with a 60% polytetrafluoroethylene aqueous solution (0.033 g) and water, and the mixture was stirred in an agate mortar. A working electrode was prepared.
A charge / discharge test (charge / discharge time: 1 hour each) was performed in the same manner as in Example 5, and a cycle life of at least 200 cycles or more was observed (Coulomb efficiency of the 200th charge / discharge: 88.3%). Moreover, when the zinc mixture electrode after a 200-cycle charging / discharging test was observed by SEM, deterioration, such as a dendrite and a big active material form change, was not seen.

(Example 18)
A solid electrolyte was produced in the same manner as in Example 5.
Next, 60% polytetrafluoroethylene aqueous solution (0.033 g) and water were added to zinc oxide (0.61 g) and aluminum oxide (0.019 g), and the mixture was stirred in an agate mortar. A working electrode was prepared.
A charge / discharge test (charge / discharge time: 1 hour each) was performed in the same manner as in Example 5, and a cycle life of at least 200 cycles or more was observed (Coulomb efficiency of the 200th charge / discharge: 92.9%). Moreover, when the zinc mixture electrode after a 200-cycle charging / discharging test was observed by SEM, deterioration, such as a dendrite and a big active material form change, was not seen.

(Example 19)
A solid electrolyte was produced in the same manner as in Example 5.
Next, 60% polytetrafluoroethylene aqueous solution (0.033 g) and water were added to zinc oxide (0.61 g) and gallium oxide (0.019 g), and the mixture was stirred in an agate mortar. A working electrode was prepared.
A charge / discharge test (charge / discharge time: 1 hour each) was performed in the same manner as in Example 5, and a cycle life of at least 200 cycles or more was observed (Coulomb efficiency of the 200th charge / discharge: 92.8%). Moreover, when the zinc mixture electrode after a 200-cycle charging / discharging test was observed by SEM, deterioration, such as a dendrite and a big active material form change, was not seen.

(Example 20)
A solid electrolyte was produced in the same manner as in Example 5.
Next, 60% polytetrafluoroethylene aqueous solution (0.033 g) and water were added to zinc oxide (0.61 g) and hydroxyapatite (0.019 g), and the mixture was stirred in an agate mortar. A working electrode was prepared.
A charge / discharge test (charge / discharge time: 1 hour each) was conducted in the same manner as in Example 5, and a cycle life of at least 200 cycles or more was observed (Coulomb efficiency of the 200th charge / discharge: 89.2%). Moreover, when the zinc mixture electrode after a 200-cycle charging / discharging test was observed by SEM, deterioration, such as a dendrite and a big active material form change, was not seen.

(Example 21)
A solid electrolyte was produced in the same manner as in Example 5.
Next, 60% polytetrafluoroethylene aqueous solution (0.033 g) and water were added to zinc oxide (0.61 g) and sodium dodecyl sulfate (0.0063 g), and the mixture was stirred in an agate mortar. Working electrode was prepared.
A charge / discharge test (charge / discharge time: 1 hour each) was performed in the same manner as in Example 5, and a cycle life of at least 200 cycles was observed (Coulomb efficiency of the 200th charge / discharge: 75.6%). Moreover, when the zinc mixture electrode after a 200-cycle charging / discharging test was observed by SEM, deterioration, such as a dendrite and a big active material form change, was not seen.
As a reference, the results of observing the zinc mixture electrode before and after the 200-cycle charge / discharge test in Example 21 by SEM are shown in FIGS.

(Example 22)
A solid electrolyte was produced in the same manner as in Example 5.
Next, 60% polytetrafluoroethylene aqueous solution (0.033 g) and water were added to zinc oxide (0.61 g) and tetrabutylammonium bromide (0.0063 g), and the mixture was stirred in an agate mortar. A working electrode was produced in the same manner.
A charge / discharge test (charge / discharge time: 1 hour each) was performed in the same manner as in Example 5, and a cycle life of at least 200 cycles or more was observed (Coulomb efficiency of the 200th charge / discharge: 86.4%). Moreover, when the zinc mixture electrode after a 200 cycle charging / discharging test was observed by SEM, deterioration, such as a big active material form change, was not seen.
As a reference, the results of observation of the zinc mixture electrode before and after the 200-cycle charge / discharge test in Example 22 by SEM are shown in FIGS.

(Example 23)
A solid electrolyte was produced in the same manner as in Example 5.
Next, 60% polytetrafluoroethylene aqueous solution (0.033 g) and water were added to zinc oxide (0.61 g) and thiourea (0.019 g), and the mixture was stirred in an agate mortar. A working electrode was prepared.
A charge / discharge test (charge / discharge time: 1 hour each) was performed in the same manner as in Example 5, and a cycle life of at least 200 cycles or more was observed (Coulomb efficiency of the 200th charge / discharge: 87.0%). Moreover, when the zinc mixture electrode after a 200-cycle charging / discharging test was observed by SEM, deterioration, such as a dendrite and a big active material form change, was not seen.

(Example 24)
A solid electrolyte was produced in the same manner as in Example 5.
Next, zinc oxide (0.61 g), bismuth oxide nanoparticles (0.0095 g: average particle diameter 87 nm) and cerium oxide nanoparticles (0.0095 g: average particle diameter 15 nm) were added to a 60% polytetrafluoroethylene aqueous solution (0. 033 g), water was added, and the mixture was stirred in an agate mortar to prepare a working electrode in the same manner as in Example 5.
A charge / discharge test (charge / discharge time: 1 hour each) was performed in the same manner as in Example 5, and a cycle life of at least 200 cycles or more was observed (Coulomb efficiency of the 200th charge / discharge: 86.5%). Moreover, when the zinc mixture electrode after a 200-cycle charging / discharging test was observed by SEM, deterioration, such as a dendrite and a big active material form change, was not seen.
For reference, in Example 24, the results of observation of the zinc mixture electrode before and after the 200-cycle charge / discharge test by SEM are shown in FIGS. 16 and 17.

(Example 25)
A solid electrolyte was produced in the same manner as in Example 5.
Next, zinc oxide (28.5 g), bismuth oxide (1.5 g), 27% aqueous polyolefin solution (1 g) were added with 60% aqueous polytetrafluoroethylene solution (2.0 g) and water, and the mixture was stirred in an agate mortar. . After pressing the obtained solid with a rolling mill, this is pressure-bonded to a copper mesh current collector with a roll press machine (theoretical capacity: 80 mAh / cm ² ), and then the solid electrolyte is pressure-bonded with a roll press machine. The zinc mixture electrode having a solid electrolyte on the active material was used so as to be a working electrode having an apparent area of 1.95 cm ² .
8 mol / L potassium hydroxide aqueous solution in which zinc oxide is dissolved as an electrolytic solution until saturation,
Use non-woven fabric as separator, nickel electrode as counter electrode (active material: cobalt-coated nickel hydroxide, capacity is set to 1 times that of zinc electrode), and electrode charged 50% of the same electrode as positive electrode (counter electrode) as reference electrode Using a triode cell, a charge / discharge test (charge / discharge time: 1 hour each) was performed at a current value of 20 mA / cm ² , and a cycle life of at least 200 cycles or more was observed. Moreover, when the zinc mixture electrode after a 200-cycle charging / discharging test was observed by SEM, deterioration, such as a dendrite and a big active material form change, was not seen.

(Example 26)
A solid electrolyte was produced in the same manner as in Example 5.
Next, 60% polytetrafluoroethylene aqueous solution (2 g) and water are added to zinc oxide (28.5 g), bismuth oxide (1.5 g), 100% polyethyleneimine (2.0 g), and the mixture is stirred in an agate mortar. A working electrode was produced in the same manner as in Example 25.
A charge / discharge test (charge / discharge time: 1 hour each) was performed in the same manner as in Example 25, and a cycle life of at least 150 cycles or more was observed. Moreover, when the zinc mixture electrode after a 150 cycle charging / discharging test was observed by SEM, degradation, such as a dendrite and a big active material form change, was not seen.

(Example 27)
A solid electrolyte was produced in the same manner as in Example 5.
Next, zinc oxide (28.5 g), bismuth oxide (1.5 g), 2% sodium polyacrylate aqueous solution (15 g), 60% polytetrafluoroethylene aqueous solution (2.0 g) and water were added, and an agate mortar The working electrode was produced in the same manner as in Example 25.
A charge / discharge test (charge / discharge time: 1 hour each) was performed in the same manner as in Example 25, and a cycle life of at least 200 cycles or more was observed. Moreover, when the zinc mixture electrode after a 200-cycle charging / discharging test was observed by SEM, deterioration, such as a dendrite and a big active material form change, was not seen.

The following was found from the results of the examples.
A zinc negative electrode comprising a current collector and an active material layer containing a zinc species, wherein the zinc negative electrode contains a solid electrolyte on and / or in the active material layer, The solid electrolyte includes polyvalent ions and / or inorganic compounds, and the polyvalent ions and / or inorganic compounds include Li, Na, K, Rb, Cs, Groups 2 to 14, P, The zinc negative electrode containing at least one element selected from Sb, Bi, Group 16 and Group 17 sufficiently suppresses the change in shape and form of the active material, and the battery performance is sufficiently improved. It has been demonstrated that a battery can be formed.
In addition, in the said Example, although a specific inorganic compound is used as a polyvalent ion and / or an inorganic compound, the zinc negative electrode of this invention is solid on the active material layer and / or in this layer. It contains an electrolyte and sufficiently suppresses the change in shape and form of the active material. Further, the solid electrolyte is Li, Na, K, Rb, Cs, Group 2 to Group 14, P, Sb, Bi of the periodic table. If it contains a polyvalent ion and / or an inorganic compound containing at least one element selected from Group 16, and Group 17, the expansion and contraction of the solid electrolyte can be suppressed, and the electrons It is possible to maintain the conduction path and prevent the occurrence of defects such as cracks in the electrode active material layer. Further, such polyvalent ions and / or inorganic compounds can make the ion conductivity sufficiently excellent. Thus, it is possible to form a battery with sufficiently improved battery performance. Li, Na, K, Rb, Cs, Group 2 to Group 14 of the periodic table, P, Sb, Bi, 16th It can be said that all are the same when multivalent ions and / or inorganic compounds containing at least one element selected from Group 17 and Group 17 are used.
Therefore, it can be said from the results of the above-described embodiments that the present invention can be applied in the entire technical scope of the present invention and in various forms disclosed in this specification, and can exhibit advantageous effects.

Claims (3)

A zinc negative electrode comprising a current collector and an active material layer containing a zinc- containing compound ,
The zinc negative electrode contains a solid electrolyte on the active material layer ,
The zinc electrolyte characterized in that the solid electrolyte contains a layered double hydroxide and / or hydroxide containing magnesium . The zinc negative electrode according to claim 1, wherein the solid electrolyte is an electrolyte containing a polymer. Zinc anode according to claim 1 or 2, a positive electrode, a separator, and a battery, characterized in that it is constructed using the electrolyte.