JP6246999B2 - Zinc negative electrode mixture and battery using the zinc negative electrode mixture - Google Patents

Description

The present invention relates to a zinc negative electrode mixture and a battery using the zinc negative electrode mixture. More specifically, the present invention relates to a zinc negative electrode mixture that can be suitably used for forming a negative electrode of a battery having zinc as a negative electrode active material and having high economy, safety, and performance, and a battery using the zinc negative electrode mixture.

A negative electrode mixture is a material for forming a negative electrode of a battery composed of a negative electrode active material. Among them, a zinc negative electrode mixture using zinc as a negative electrode active material has been studied for a long time with the spread of batteries. . Examples of batteries that use zinc as a negative electrode include primary batteries and secondary batteries (storage batteries). For example, air / zinc batteries that use oxygen in the air as the positive electrode active material, nickel that uses a nickel-containing compound as the positive electrode active material・ Zinc batteries, manganese / zinc batteries and zinc ion batteries that use manganese-containing compounds as positive electrode active materials, and silver / zinc batteries that use silver-containing compounds as positive electrode active materials have been researched and developed, especially air / zinc primary batteries, Manganese / zinc primary batteries and silver / zinc primary batteries have been put into practical use and are widely used worldwide. 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, as a battery using zinc as a negative electrode, which has been researched and developed, an alkaline zinc storage battery having a zinc electrode mainly containing zinc and zinc oxide and containing an oxide or hydroxide of cadmium and tin ( For example, refer to Patent Document 1.), an alkaline zinc storage battery (see, for example, Patent Document 2) including a zinc electrode containing zinc and zinc oxide as main components and containing tin oxide or hydroxide and titanium oxide. A zinc electrode for an alkaline storage battery in which at least one inorganic compound selected from calcium hydroxide, barium hydroxide, titanium oxide, zirconium oxide and magnesium oxide is added to a zinc active material containing a fluororesin and polyvinyl alcohol. (For example, refer to Patent Document 3.) The periphery of an electrode plate containing zinc and zinc oxide as main components and containing an alkali-resistant water-repellent synthetic resin binder. In addition, an alkaline zinc storage battery provided with a zinc electrode containing an electrochemically inert and non-conductive inorganic compound (see, for example, Patent Document 4), zinc or zinc oxide as a main component, and indium as an additive A zinc electrode containing at least one oxide or hydroxide selected from the group consisting of oxides or hydroxides of the above, thallium oxides or hydroxides and a metal group consisting of gallium, cadmium, lead, tin, bismuth and mercury And an alkaline zinc storage battery (see, for example, Patent Document 5) in which the total amount of additives is 1 to 15% by weight with respect to the zinc electrode. In addition, zinc, calcium hydroxide, thallium oxide, and water are kneaded, dried and pulverized to obtain a powder, and the powder includes zinc powder, zinc oxide powder, an additive, and a binder. There is disclosed a method for producing a zinc electrode for an alkaline storage battery (see, for example, Patent Document 6) in which an active material paste is prepared by kneading and the active material paste is applied to a current collector.
Furthermore, for the purpose of improving the charge / discharge cycle characteristics of the zinc electrode, the effects of adding metal oxides other than zinc to the zinc electrode active material and examining the effects thereof were obtained. Among them, it is disclosed that indium oxide and thallium oxide have a high effect of improving cycle characteristics (see, for example, Non-Patent Document 1). Non-Patent Document 2 reviews the history of research and development of conventional zinc electrodes for alkaline secondary batteries.

Also, it has a paste type zinc oxide negative electrode, a paste type nickel oxide positive electrode, an alkaline electrolyte, a positive electrode contains a mixture of coprecipitated cobalt oxide and finely divided cobalt metal, and a negative electrode contains an oxide other than zinc oxide An electrochemical cell (see, for example, Patent Document 8) including a zinc electrode containing nickel-zinc galvanicel (for example, see Patent Document 7), zinc oxide, a binder, and a fluoride is disclosed. An electrochemical cell having a zinc electrode containing a mixture of zinc oxide and an inorganic fiber containing silica and alumina and a buffer electrolyte (see, for example, Patent Document 9) has been disclosed, but zinc containing silica or alumina is disclosed. In our experiments, we confirmed that these compounds were easily dissolved in the system and deteriorated quickly.
Furthermore, zinc electrode containing zinc oxide, metal oxide, hydroxyethyl cellulose, oxide dispersant, liquid binder (see, for example, Patent Document 10), cathode containing zinc or zinc compound, nickel oxide, nickel hydroxide and / or Alternatively, a rechargeable nickel-zinc battery (see, for example, Patent Document 11), a positive electrode containing nickel oxyhydroxide, and an electrolyte containing phosphate, free alkali, and borate, ZnO, and zinc or zinc alloy, A method for producing a rechargeable battery, comprising a bismuth oxide, a zinc negative electrode material containing aluminum oxide, nickel hydroxide and / or nickel oxyhydroxide, zinc oxide, cobalt oxide, and a nickel positive electrode material containing a binder ( For example, refer to Patent Document 12.).

Also disclosed is a rechargeable nickel-zinc battery comprising an electrochemically active zinc, a zinc negative electrode made of carbon fiber coated with a surfactant, and a nickel positive electrode, where the coating is made with a surfactant. It is disclosed that the charge / discharge characteristics of a nickel / zinc battery are improved by using the carbon fiber thus prepared for a zinc negative electrode (see, for example, Patent Document 13). However, the carbon fiber substitute compound coated with the surfactant used in the comparative example is dissolved in a strong alkaline aqueous electrolyte, so that the zinc electrode is significantly deteriorated. Since it is a fiber, the superiority of carbon fiber coated with a surfactant cannot be truly explained. Carbon fiber coated with a surfactant is said to suppress hydrogen generation due to decomposition of the aqueous electrolyte, but carbon fiber coated with a surfactant has a high hydrogen overvoltage Pb (for example, Patent Documents). 14)), it is clear that hydrogen generation is suppressed and does not show the superiority of the carbon fiber itself coated with the surfactant. In addition, in order to improve the capacity density of the zinc electrode as much as possible, there has been room for a device to develop a conductive additive that does not use a surfactant coating.

JP 58-163159 A JP 58-163162 A JP 60-208053 A JP-A-61-61366 JP-A 61-96666 Japanese Patent Laid-Open No. 01-163967 Special table 2004-513501 gazette Japanese translation of PCT publication No. 2004-520683 JP-T-2004-522256 JP-T-2004-526286 JP 2007-214125 A Special table 2008-532249 gazette US Patent Application Publication No. 2011/0033747 Japanese Patent Publication No.51-32365

Mitsuko Nogami, 4 others, “Electrochemistry”, 1989, Vol. 57, No. 8, p. 810-814 F. R. McLanon, 1 other, “Journal of the Electrochemical Society”, 1991, Vol. 138, No. 2, p. 645-664

As described above, various types of batteries using a zinc 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 inventor has a possibility that such a zinc negative electrode battery is inexpensive and high in safety and also has a high energy density and can be suitably used in various applications from such a viewpoint. Focused on. And when the performance aspect of the zinc negative electrode battery was examined, in order to satisfy the performance required for the battery used in recent years, for example, when charging / discharging which is essential for the secondary battery of the battery is repeated, the negative electrode containing zinc Changes in the shape of the active material and the formation of passive state occur, the charge / discharge cycle characteristics (battery life) are inferior, and the self-discharge during storage in the charged state or in the charged state still remains. I found out. If such a problem is solved, there is a possibility that it can be used in many industries from portable devices to automobiles and the like as a battery that can achieve both economy, safety and performance.

This invention is made | formed in view of the said present condition, and it aims at providing the zinc negative mix for forming the negative electrode of the battery which was excellent in economical efficiency and safety | security, and excellent in battery performance.

The present inventor has made various studies on the zinc negative electrode mixture, and the zinc negative electrode mixture contains a zinc-containing compound as an active material and a conductive additive. Focused on the shape. Then, when the zinc-containing compound and / or the conductive auxiliary agent includes particles having a small particle diameter that is equal to or smaller than a specific average particle diameter, or elongated particles having a specific aspect ratio, such a zinc negative electrode composite. It has been found that a zinc negative electrode formed using an agent can suppress generation of hydrogen, which is a side reaction, and improve battery cycle characteristics, rate characteristics, and coulombic efficiency compared to conventional zinc negative electrodes. It was. Furthermore, it discovered that the shape change of the negative electrode active material containing zinc, formation of a passive state, and the self discharge at the time of a charge state and the preservation | save in a charge state were also suppressed. A zinc negative electrode having such characteristics can be more suitably used as a negative electrode for 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. Thus, in the zinc negative electrode mixture containing a zinc-containing compound and a conductive assistant, the zinc-containing compound and / or the conductive assistant is made of particles having an average particle diameter of 1000 μm or less and / or an aspect ratio (longitudinal). It was conceived that the above problem can be solved brilliantly by including particles having (/ lateral) of 1.1 or more, and the present invention has been achieved.

That is, the present invention is a zinc negative electrode mixture containing a zinc-containing compound and a conductive auxiliary agent, wherein the zinc-containing compound and / or the conductive auxiliary agent are particles having an average particle diameter of 1000 μm or less, and / or Or it is a zinc negative electrode mixture characterized by including the particle | grains whose aspect-ratio (length / width) is 1.1 or more.
Further, according to the present invention, the zinc negative electrode mixture further includes another component, and the other component is a compound having at least one element selected from the group consisting of elements belonging to Groups 1 to 17 of the periodic table. And the zinc negative electrode mixture comprising at least one selected from the group consisting of organic compounds and organic compound salts.
Furthermore, the present invention is a zinc negative electrode formed using the above zinc negative electrode mixture.
Moreover, this invention is a battery characterized by having the said zinc negative electrode.
The present invention can also be used for other electrochemical devices such as capacitors and hybrid capacitors.

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.

The zinc negative electrode mixture of the present invention contains a zinc-containing compound and a conductive auxiliary, and the zinc-containing compound and / or conductive auxiliary is particles having an average particle diameter of 1000 μm or less, and / or an aspect. It includes particles having a ratio (vertical / horizontal) of 1.1 or more.
The zinc negative electrode mixture of the present invention may contain other components as long as it contains a zinc-containing compound and a conductive additive. Moreover, each of these components may contain 1 type and may contain 2 or more types.

The zinc-containing compound and / or the conductive auxiliary agent include particles having an average particle diameter of 1000 μm or less and / or particles having an aspect ratio (vertical / horizontal) of 1.1 or more. And the zinc negative electrode formed from the zinc negative electrode mixture containing such a conductive support agent and a zinc containing compound can improve the cycling characteristics of a battery, a rate characteristic, and Coulomb efficiency. The reason can be considered as follows.
When the negative electrode of the battery is formed from a zinc negative electrode mixture containing a zinc-containing compound and a conductive additive, in order to function as a negative electrode (current flows), the zinc-containing compounds, the zinc-containing compound and the conductive auxiliary, It is preferable that the zinc-containing compound, the conductive additive, and the current collector are bound. However, if charging / discharging is repeated or rapid charging / discharging is performed, the zinc-containing compound and the zinc-containing compound and the conductive material inevitably are connected. Dissociation of the auxiliary agent, the zinc-containing compound, the conductive auxiliary agent, and the current collector or the passivation of the zinc-containing compound may proceed, leading to a decrease in battery performance. However, when zinc-containing compounds and / or particles having an average particle size of 1000 μm or less are used as the conductive assistant, the zinc-containing compounds, the zinc-containing compound and the conductive assistant, and the zinc-containing compound and the conductive assistant and the current collector are collected. The body can be efficiently contacted, the zinc-containing compounds, the zinc-containing compound and the conductive assistant, the number of the zinc-containing compound, the conductive assistant and the current collector can be completely dissociated, It becomes possible to suppress a decrease in battery performance. Further, when the zinc-containing compound and / or the conductive auxiliary agent includes particles having an aspect ratio (length / width) of 1.1 or more, such particles have an elongated shape, Dissociation between the zinc-containing compounds, the zinc-containing compound and the conductive additive, the zinc-containing compound, the conductive auxiliary agent, and the current collector is unlikely to occur, and as a result, it is possible to suppress a decrease in battery performance. Furthermore, it becomes possible to suppress the shape change of the zinc-containing compound as the active material.

In the present invention, either the zinc-containing compound or the conductive auxiliary agent is a particle having an average particle diameter of 1000 μm or less and / or a particle having an aspect ratio (vertical / horizontal) of 1.1 or more. The zinc-containing compound and the conductive auxiliary agent may both contain particles having an average particle diameter of 1000 μm or less and / or particles having an aspect ratio (vertical / horizontal) of 1.1 or more. May be included.
It is also preferable that the zinc-containing compound and the conductive additive include particles having an average particle diameter of 1000 μm or less and / or particles having an aspect ratio (length / width) of 1.1 or more. This is one of the embodiments.

As long as the zinc-containing compound and / or conductive additive in the present invention includes particles having an average particle diameter of 1000 μm or less and / or particles having an aspect ratio (vertical / horizontal) of 1.1 or more, other The particle | grains of the shape may be included. However, the total of particles having an average particle diameter of 1000 μm or less and particles having an aspect ratio (vertical / horizontal) of 1.1 or more is 10% by mass with respect to 100% by mass of the total amount of the zinc-containing compound and the conductive additive. The above is preferable. In this range, particles having an average particle diameter of 1000 μm or less and / or particles having an aspect ratio (length / width) of 1.1 or more with respect to the total amount of the zinc-containing compound and the conductive additive are included. As a result, the effects of the present invention are more fully exhibited. More preferably, it is 40 mass% or more, More preferably, it is 80 mass% or more. Particularly preferably, 100% by mass, that is, the zinc-containing compound and the conductive assistant are particles having an average particle diameter of 1000 μm or less and / or particles having an aspect ratio (vertical / horizontal) of 1.1 or more. That is.

The particles having a small particle diameter are those having an average particle diameter of 1000 μm or less, but the average particle diameter is preferably 500 μm or less, more preferably 200 μm or less, and even more preferably 100 μm or less. Yes, particularly preferably 75 μm or less, and most preferably 20 μm or less. On the other hand, the lower limit of the average particle diameter is preferably 1 nm. More preferably, it is 2 nm or more, More preferably, it is 5 nm or more.
The average particle diameter is an average particle diameter as a raw material for the zinc-containing compound and / or the conductive additive, and is prepared by analysis after ultrasonic irradiation dispersion for 1 to 20 minutes or a process described later. In the analysis of the zinc-containing compound and the conductive additive in the prepared zinc negative electrode mixture and the electrode using the same, the average particle diameter is preferably the above value.

The average particle diameter can be measured by a transmission electron microscope (TEM), a scanning electron microscope (SEM), a particle size distribution measuring device, powder X-ray diffraction (XRD), or the like.
Examples of the shape of the particles include fine powder, powder, granule, granule, scale, polyhedron, and rod. In addition, the particles having an average particle size in the above-described range are, for example, a method of pulverizing particles with a ball mill or the like, dispersing the obtained coarse particles in a dispersant to obtain a desired particle size, In addition to the method of selecting the particle diameter by sieving the coarse particles, etc., it is possible to optimize the preparation conditions at the stage of producing the particles to obtain (nano) particles having a desired particle diameter.

Here, when the particle group is composed of many particles having non-uniform diameters, when considering the particle diameter that represents the particle group, the particle diameter is defined as the average particle diameter. As for the particle diameter, the particle length measured according to a general rule is used as it is. For example, in the case of (i) microscopic observation, the major axis diameter and minor axis diameter of one particle are used. Measure two or more lengths, such as a constant direction diameter, and let the average value be the particle diameter. It is preferred to make measurements on at least 100 particles. (Ii) In the case of the image analysis method, the shading method, and the Coulter method, the amount directly measured as the particle size (projection area, volume) is converted into a regular shape (eg, circle, sphere) by a geometric formula. And the particle diameter (equivalent diameter). (Iii) In the case of the sedimentation method and laser diffraction scattering method, the measured amount is calculated by using a physical law (eg Mie theory) derived when a specific particle shape and a specific physical condition are assumed. Calculated as (effective diameter). (Iv) In the case of the dynamic light scattering method, the particle diameter is calculated by measuring the speed (diffusion coefficient) at which particles in the liquid diffuse due to Brownian motion.
In the analysis of the average particle size, the particles may be analyzed as they are, or may be analyzed after being subjected to ultrasonic irradiation dispersion for 1 to 20 minutes. It is preferable to become the said value. When measuring the average particle size with a particle size distribution measuring device, the particle size at the top of the frequency distribution graph where the frequency distribution value is the largest is the mode diameter, and the particle size corresponding to the integrated distribution value of 50% is the median size. .

The particles having a small particle diameter preferably have a specific surface area of 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 0.5 m < ² > / g or more. On the other hand, the upper limit of the specific surface area is preferably 1500 m ² / g. More preferably, it is 500 m < ² > / g or less, More preferably, it is 350 m < ² > / g or less, Most preferably, it is 250 m < ² > / g or less.
The specific surface area can be measured by a specific surface area measuring apparatus or the like by a nitrogen adsorption BET method.
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 elongated particles mainly include a rectangular parallelepiped type and a cylindrical type (fibrous type), and have an aspect ratio (vertical / horizontal) of 1.1 or more, but an aspect ratio (vertical / horizontal). Is preferably 20 or more, more preferably 50 or more, and still more preferably 60 or more. On the other hand, the upper limit of the aspect ratio (vertical / horizontal) is preferably 100,000, and more preferably 50,000.
The aspect ratio (vertical / horizontal) is, for example, from the shape of particles observed by TEM or SEM, in the case of a rectangular parallelepiped, the longest side is vertical, the second longest side is horizontal, and the vertical length is It can be obtained by dividing by the horizontal length. In the case of a cylinder type, spherical type, curved surface containing type, polyhedron type, etc., a certain part is placed on the bottom so that the aspect ratio is maximized, and it is projected from the direction that maximizes the aspect ratio. Measure the length of a point farthest away from a point in a two-dimensional shape that can sometimes be created, with the longest side as the vertical and the longest side of the straight line passing through the vertical center point as the horizontal. It can be obtained by dividing by the horizontal length.
In addition, particles having an aspect ratio (vertical / horizontal) in the above-described range are, for example, a method for selecting particles having such an aspect ratio, and optimization of preparation conditions at the stage of manufacturing the particles. It can be obtained by a method of obtaining selectively.
The above aspect ratio is the average particle diameter as a raw material for the zinc-containing compound and / or the conductive auxiliary agent, and was prepared by analysis after ultrasonically dispersing these for 1 to 20 minutes or by a process described later. In the analysis of the zinc-containing compound and the conductive additive in the zinc negative electrode mixture and the electrode using the same, the aspect ratio is preferably the above value.

The zinc-containing compound is not particularly limited as long as it can be used as a negative electrode active material. For example, zinc metal, zinc fiber, zinc oxide (1 type / 2 types / 3 types), conductive zinc oxide, Zinc hydroxide, zinc sulfide, tetrahydroxyzinc ion salt, zinc halide, zinc carboxylate compounds such as zinc acetate and zinc tartrate, magnesium zincate, calcium zincate, barium zincate, zinc borate, zinc silicate Zinc aluminate, zinc fluoride, zinc alloy, carbonate, hydrogen carbonate, nitrate, sulfate, zinc used in alkaline dry batteries and air zinc batteries, and the like. Among these, zinc metal, zinc oxide (1 type / 2 types / 3 types), conductive zinc oxide, zinc hydroxide, tetrahydroxy zinc ion salt, zinc halide, zinc borate, zinc fluoride, zinc alloy, Zinc used in alkaline dry batteries and air zinc batteries is preferred, more preferably zinc metal, zinc oxide (1 type / 2 types), conductive zinc oxide, zinc hydroxide, zinc borate, zinc fluoride, zinc alloy Zinc used in alkaline dry batteries and air zinc batteries, more preferably zinc oxide, zinc hydroxide, zinc alloys, zinc used in alkaline dry batteries and air zinc batteries, most preferably zinc oxide, water. Zinc oxide. The zinc-containing compound can be used alone or in combination of two or more.
When zinc oxide is used, the amount of Pb contained in the zinc oxide is preferably 0.03% by mass or less, and the amount of Cd is preferably 0.01% by mass or less. Pb and Cd are known as elements that suppress decomposition (hydrogen generation) of the electrolytic solution (water) at the zinc electrode, but it is preferable to reduce it as much as possible because of concerns over recent environmental problems. More preferably, the zinc oxide used for the zinc electrode satisfies the JIS standard. Moreover, it is better not to contain Hg.

As a compounding quantity 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%.

The zinc-containing compound preferably contains 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 500 μm to 1 nm, more preferably 100 μm to 5 nm, still more preferably 20 μm to 10 nm, and particularly preferably 10 μm to 100 nm.
When zinc oxide is used as the zinc compound, the average particle size is 100 μm to 100 nm when zinc oxide is added to ion-exchanged water and ultrasonically dispersed for 5 minutes and then measured with a particle size distribution analyzer. More preferably, it is 50 μm to 200 nm, more preferably 10 μm to 300 nm, and the mode diameter is preferably 20 μm to 50 nm, more preferably 10 μm to 70 nm, still more preferably, The median diameter is preferably 10 μm to 100 nm, more preferably 7 μm to 150 nm, and still more preferably 5 μm to 500 nm.
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 cylindrical shape, a spherical shape, a curved surface-containing shape, a polyhedral shape, a scale shape, a rod shape, or the like. , Preferably it is 100,000-1.1, More preferably, it is 50000-1.2, More preferably, it is 10000-1.5. 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 diameter and aspect ratio can be measured by the same method as described above.

In this specification, “when charged or stored in a charged state” means a full cell having a zinc electrode as a negative electrode (reaction in which zinc oxide is reduced to metallic zinc is charged, and metallic zinc is oxidized to zinc oxide. In the reaction (discharge), a state in which a part or all of the zinc-containing compound which is an active material is metallic zinc at the time of charge / discharge operation of the battery or storage thereof. In addition, in the discharge operation of the full cell and in the half cell using zinc metal as the counter electrode of the zinc electrode (the reaction in which zinc oxide is reduced to zinc metal is discharged, the reaction in which metal zinc is oxidized to zinc oxide is charged) If a part or all of the zinc-containing compound as the active material is in a state of being metallic zinc, they shall mean a charged state.

The zinc-containing compound preferably includes particles that satisfy the following specific surface area. Moreover, it is more preferable that the zinc-containing compound satisfies the following specific surface area.
The specific surface area of the zinc-containing compound is more preferably 0.01 m ² / g or more and 60 m ² / g or less, and still more preferably 0.1 m ² / g or more and 50 m ² / g or less. If the particles satisfying the specific surface area are not included, there is a possibility that cycle characteristics are deteriorated and self-discharge is likely to occur during charging or storage in a charged state.
The specific surface area can be measured by the same method as described above.

When zinc oxide is used as the zinc-containing compound, the true density value is preferably 5.50 to 6.50 g / cm ³ . More preferably from 5.60~6.30g / cm ^3, more preferably, a 5.70~6.20g / cm ^3, particularly preferably be a 5.89~6.20g / cm ³ Most preferably, it is 5.95-6.15 g / cm ³ . If the zinc oxide particles do not satisfy the above true density value, there is no significant effect on the capacity during charge / discharge, but depending on the average particle size, self-discharge during charging or storage in the charged state May be likely to occur.
The true density can be measured with a density measuring device or the like. When it is difficult to measure the true density of particles alone, such as when the zinc-containing compound is used in an electrode, it can be estimated by calculating the ratio of zinc to oxygen using a fluorescent X-ray analysis (XRF) apparatus or the like. it can.

As said conductive support agent, conductive carbon, conductive ceramics, metallic zinc, etc. can be used, for example.
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-wall / single-wall carbon nanotubes, vulcanized carbon, acetylene black, carbon treated with a hydrophilic treatment by introducing an oxygen-containing functional group, and metallic zinc are preferred. The metal zinc may be used for an actual battery such as an alkaline battery or an air battery, or may be one whose surface is coated with another element, carbon or the like.
The said conductive support agent can be used by 1 type, or 2 or more types. Conductive carbon is not coated with a low molecular weight surfactant in order to make the most of its conductivity.

Metallic zinc can also act as an active material.
Metallic zinc is added as a negative electrode mixture in the negative electrode preparation stage. When charging / discharging is performed, 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 during charging and discharging.
In order to suppress the side reaction, the conductive auxiliary agent may cause a water decomposition side reaction at the time of charge / discharge when a water-containing electrolyte is used when a storage battery is produced using the conductive auxiliary agent. A specific element may be introduced into the conductive additive. Specific elements include B, Ba, Bi, Br, Ca, Cd, Ce, Cl, F, Ga, Hg, In, La, Mn, N, Nb, Nd, P, Pb, Sc, Sn, Sb, Sr, Ti, Tl, Y, Zr, etc. are mentioned. When conductive carbon is used as one of the conductive assistants, specific elements include B, Bi, Br, Ca, Cd, Ce, Cl, F, In, La, Mn, N, Nb, and Nd. , P, Pb, Sc, 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%. Thus, in the zinc negative electrode mixture of the present invention, the blending amount of the conductive auxiliary is 0.0001 to 100% by mass with respect to 100% by mass of the zinc-containing compound in the zinc negative electrode mixture. 1 is one of the preferred embodiments of the present invention.
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 during charging / discharging from zinc oxide, zinc hydroxide or the like, which is a zinc-containing compound, will also function as a conductive aid in the system, but it is 0 when preparing a zinc negative electrode mixture or a zinc negative electrode. Since it is not a valent zinc metal, 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 conductive auxiliary agent preferably contains particles satisfying the following average particle diameter and / or aspect ratio. Moreover, it is more preferable that the conductive auxiliary agent satisfies the following average particle diameter and / or aspect ratio.
The average particle size of the conductive aid is preferably 500 μm to 1 nm, more preferably 200 μm to 5 nm, and still more preferably 100 μm to 10 nm.
The aspect ratio (vertical / horizontal) of the conductive aid is preferably 100,000 to 1.1, more preferably 80000 to 1.2, and still more preferably 50000 to 1.5.
The average particle diameter and aspect ratio can be measured by the same method as described above.

The conductive auxiliary agent preferably contains particles that satisfy the following specific surface area. Moreover, it is more preferable that the conductive assistant satisfies the following specific surface area.
The specific surface area of the conductive assistant is more preferably 0.1 m ² / g or more and 1500 m ² / g or less, still more preferably 1 m ² / g or more and 1200 m ² / g or less, and still more preferably. Is 1 m ² / g or more and 900 m ² / g or less, particularly preferably 1 m ² / g or more and 250 m ² / g or less, and most preferably 1 m ² / g or more and 50 m ² / g or less. is there.
By setting the specific surface area of the conductive aid to the above value, it is possible to suppress the shape change and passive formation of the zinc-containing compound that is the active material during charging and discharging, and further in the charged state and in the charged state. Self-discharge during storage can also be suppressed. The charge state or the storage state in the charged state means that in the full cell or the half cell, a part or all of the negative electrode active material is in a reduced state during the charge / discharge operation or the storage of the battery.

When conductive carbon is used as the conductive assistant, it is considered that the water decomposition side reaction also proceeds at the edge portion of the conductive carbon. Therefore, the specific surface area of the conductive carbon is preferably 0.1 m. ² / g or more and 1500 m ² / g or less, more preferably 1 m ² / g or more and 1200 m ² / g or less, still more preferably 1 m ² / g or more and 900 m ² / g or less. preferably, ^{1 m} 2 / g or more, 250 meters ² / g or less, and most preferably, ^{1 m} 2 / g or more and ^{50 m} 2 / g or less. Moreover, it is preferable that the average particle diameter of this conductive carbon is 20 micrometers-5 nm. More preferably, it is 15 μm to 10 nm.
It is also possible to reduce the edge part by graphitization treatment. A zinc negative electrode having a zinc negative electrode mixture using conductive carbon as a conductive additive is expected to be able to withstand charge / discharge conditions at a high rate, particularly when a storage battery using the zinc negative electrode is applied as an on-vehicle application. In addition, it is expected to exhibit good performance. In addition, it suppresses self-discharge during charging and storage in the charged state, and also suppresses changes in the shape of the zinc electrode active material by depositing zinc in the mesopores and micropores of the conductive carbon. It is also expected. Furthermore, since water may be decomposed at the edge part of conductive carbon during charging and discharging, high cycle characteristics, rate characteristics, and expression of Coulomb efficiency are expected by reducing the edge part by graphitization treatment. Is done.

The zinc negative electrode mixture of the present invention may contain components other than the zinc-containing compound and the conductive additive. As said other component, it is different from the said zinc containing compound and conductive support agent, The compound and organic compound which have at least 1 element selected from the group which consists of an element which belongs to the 1st-17th group of a periodic table And organic compound salts.
Here, in the case of a battery configured using a water-containing electrolyte as an electrolyte, it is preferable to an organic solvent-based electrolyte from the viewpoint of safety. A side reaction that a hydrogen decomposition reaction proceeds and hydrogen is generated may occur due to a chemical reaction or self-discharge during charging or storage in a charged state. However, the zinc negative electrode mixture of the present invention includes, as another component, a compound having at least one element selected from the group consisting of elements belonging to Groups 1 to 17 of the periodic table, an organic compound, and an organic compound salt Even when a battery is configured using a water-containing electrolyte, the zinc negative electrode formed from the zinc negative electrode mixture of the present invention is used as a negative electrode, and at least one selected from the group consisting of: It is possible to effectively suppress the generation of hydrogen due to the decomposition of water during discharge, and also suppress self-discharge during storage in the charged state, suppression of changes in the active material form of the zinc electrode, tetrahydroxy zinc ions, It is expected that effects such as suppression of solubility of zinc species due to salt formation with zinc species, improvement of affinity with water, improvement of anion conductivity, and improvement of electron conductivity will be exhibited at the same time. Ron efficiency will be greatly improved. In particular, the zinc negative electrode mixture of the present invention, as described above, is a zinc-containing compound and / or a conductive material having a particle size smaller than a specific average particle size and / or an elongated particle having a specific aspect ratio. Since it contains an auxiliary agent, the zinc negative electrode formed using such a zinc negative electrode mixture has excellent battery performance. On the other hand, side reactions such as water decomposition during charging and discharging, generation of hydrogen due to self-discharge during charging and storage in the charged state, and dissolution of the zinc negative electrode active material are completely thermodynamically performed. Therefore, when the specific zinc-containing compound and / or the conductive additive in the present invention is used as a component of the zinc negative electrode mixture, as other components, A particularly large technique for combining with a compound having at least one element selected from the group consisting of elements belonging to Group 1 to 17, an organic compound, and at least one selected from the group consisting of organic compound salts Is meaningful.
The zinc negative electrode mixture of the present invention further contains other components, and the other components are compounds having at least one element selected from the group consisting of elements belonging to Groups 1 to 17 of the periodic table, organic compounds And at least one selected from the group consisting of organic compound salts is also one preferred embodiment of the present invention.

When the zinc negative electrode mixture of the present invention further contains other components, the blending amount is preferably 0.01 to 100% by mass with respect to 100% by mass of the zinc-containing compound in the zinc negative electrode mixture. . More preferably, it is 0.05-80 mass%, More preferably, it is 0.1-60 mass%.
As described above, the zinc negative electrode mixture of the present invention is 0.01 to 100% by mass with respect to 100% by mass of the zinc-containing compound in the zinc negative electrode mixture. It is one of the preferred embodiments of the invention.

In addition, selected from the group consisting of a compound, an organic compound, and an organic compound salt having at least one element selected from the group consisting of elements belonging to Groups 1 to 17 of the periodic table contained in the other components. As the ratio of at least one kind, any of a compound, an organic compound, and an organic compound salt having at least one element selected from the group consisting of elements belonging to Groups 1 to 17 of the periodic table contained in other components It is preferable that the ratio of the total amount of those corresponding to the above is 0.1% by mass or more, more preferably 0.5% by mass or more, and still more preferably with respect to the total amount of other components of 100% by mass. 1.0% by mass or more. The upper limit is preferably 100% by mass.

Examples of the element in the compound having at least one element selected from the group consisting of elements belonging to Groups 1 to 17 of the periodic table include Ag, Al, Au, B, Ba, Be, Bi, Br, Ca, and Cd. , Ce, Cl, Co, Cr, Cs, Cu, F, Fe, Ga, Hg, In, K, La, Li, Mg, Mn, N, Na, Nb, Nd, Ni, P, Pb, Rb, S , Sc, Se, Si, Sn, Sr, Sb, Te, Ti, Tl, V, Y, Yb, and Zr, at least one element is preferable. More preferable elements are Ag, Al, Au, B, Ba, Bi, Br, Ca, Cd, Ce, Co, Cr, Cs, Cu, F, Fe, Ga, In, K, La, Mg, Mn, N , Na, Nb, Nd, P, Pb, Sc, Sn, Sb, at least one element selected from the group consisting of Ti, Tl, Y, and Zr. Further preferred elements are selected from the group consisting of Al, B, Ba, Bi, Ca, Ce, F, In, La, Mg, N, Nb, Nd, P, Pb, Sn, Ti, Tl, Y, Zr. At least one element. A particularly preferable element is at least one element selected from the group consisting of Al, Bi, Ca, Ce, F, In, La, Nb, P, Pb, Sc, Sn, Ti, Tl, Y, and Zr. The most preferred element is at least one element selected from the group consisting of Al, Ca, Ce, La, Nb, Nd, P, Sc, Y, and Zr.
The zinc negative electrode formed using the above zinc negative electrode mixture containing the above elements suppresses the water decomposition side reaction during charge / discharge and unnecessary dissolution reaction of the negative electrode active material containing zinc, and provides cycle characteristics and rate characteristics. In addition, the present inventors have newly found that the storage stability is remarkably improved by improving the coulomb efficiency and suppressing the self-discharge in the charged state or during storage in the charged state. Furthermore, it discovered that the shape change of the negative electrode active material containing zinc and formation of a passivity were suppressed more effectively.

Examples of the compound having at least one element selected from the group consisting of elements belonging to Groups 1 to 17 of the periodic table include Ag, Al, Au, B, Ba, Be, Bi, Br, Ca, Cd, and Ce. , Cl, Co, Cr, Cs, Cu, F, Fe, Ga, Hg, In, K, La, Li, Mg, Mn, N, Na, Nb, Nd, Ni, P, Pb, Rb, S, Sc Oxidation of at least one element selected from the group consisting of elements belonging to Groups 1 to 17 of the periodic table, such as Se, Si, Sn, Sr, Sb, Te, Ti, Tl, V, Y, Yb, Zr Compound oxide; layered double hydroxide; hydroxide; clay compound; solid solution; halide; carboxylate compound; carbonate; bicarbonate; nitrate; sulfate; Salt; phosphite; hypophosphite; borate; Ammonium salts; sulfide; onium compounds; hydrogen-absorbing compounds and the like.
Among these, an oxide of at least one element selected from the group consisting of elements belonging to Groups 1 to 17 of the periodic table; composite oxide; layered double hydroxide; hydroxide; clay compound; solid solution; Carboxylate compound; Carbonate; Sulfate; Sulfonate; Silicate; Phosphate; Borate; Ammonium salt; Sulfide; More preferably, an oxide of at least one element selected from the group consisting of elements belonging to Groups 1 to 17 of the periodic table; a composite oxide; a layered double hydroxide; a hydroxide; a clay compound; a solid solution; Sulfate compounds; sulfate salts; phosphate salts; borate salts; ammonium salts. That is, the other component is an oxide of at least one element selected from the group consisting of elements belonging to Groups 1 to 17 of the periodic table; composite oxide; layered double hydroxide; hydroxide; clay compound; The inclusion of a solid solution; a carboxylate compound; a sulfate; a sulfonate; a phosphate; a borate; an ammonium salt is also one preferred embodiment of the present invention.

Specific examples of the compound having at least one element selected from the group consisting of elements belonging to Groups 1 to 17 of the periodic table include silver oxide, aluminum oxide, barium oxide, bismuth oxide, and bismuth-containing composite oxidation. , Calcium oxide, calcium-containing composite oxide, cadmium oxide, cerium oxide, cerium-containing composite oxide, cobalt oxide, chromium oxide, cesium oxide, copper oxide, iron oxide, gallium oxide, mercury oxide, indium oxide, indium-containing composite Oxides, potassium oxide, lanthanum oxide, lithium oxide, magnesium oxide, manganese monoxide, manganese dioxide, sodium oxide, niobium oxide, neodymium oxide, lead oxide, rubidium oxide, silicon oxide, phosphorus oxide, tin oxide, scandium oxide, oxidation Strontium, antimony oxide, titanium oxide Tellurium oxide, vanadium oxide, yttrium oxide, ytterbium oxide, zirconium oxide, zirconium oxide stabilized with scandium oxide, zirconium oxide stabilized with yttrium oxide, zirconium-containing composite oxide, aluminum hydroxide, barium hydroxide, calcium hydroxide , Strontium hydroxide, cerium hydroxide, cesium hydroxide, indium hydroxide, potassium hydroxide, lanthanum hydroxide, lithium hydroxide, magnesium hydroxide, manganese hydroxide, sodium hydroxide, rubidium hydroxide, tin hydroxide, water Antimony oxide, titanium hydroxide, zirconium hydroxide, silver chloride, chloroauric acid, lithium chloride, magnesium chloride, sodium chloride, rubidium chloride, tin chloride, silver acetate, aluminum acetate, lithium acetate, barium acetate, bisacetate Calcium acetate, calcium tartrate, calcium glutamate, cadmium acetate, cerium acetate, cobalt acetate, chromium acetate, cesium acetate, copper acetate, iron acetate, gallium acetate, mercury acetate, indium acetate, potassium acetate, lanthanum acetate, magnesium acetate, Manganese acetate, sodium acetate, sodium tartrate, sodium glutamate, niobium acetate, neodymium acetate, lead acetate, rubidium acetate, tin acetate, strontium acetate, antimony acetate, tellurium acetate, silver carbonate, aluminum carbonate, barium carbonate, bismuth carbonate, calcium carbonate , Cerium carbonate, cobalt carbonate, cesium carbonate, gallium carbonate, indium carbonate, potassium carbonate, lanthanum carbonate, lithium carbonate, magnesium carbonate, sodium carbonate, lead carbonate, rubidium carbonate, tin carbonate, charcoal Strontium acid, antimony carbonate, aluminum sulfate, barium sulfate, bismuth sulfate, calcium sulfate, cesium sulfate, cerium sulfate, gallium sulfate, indium sulfate, potassium sulfate, lanthanum sulfate, lithium sulfate, magnesium sulfate, sodium sulfate, lead sulfate, rubidium sulfate , Tin sulfate, strontium sulfate, antimony sulfate, titanium sulfate, tellurium sulfate, vanadium sulfate, zirconium sulfate, calcium lignin sulfonate, sodium lignin sulfonate, aluminum nitrate, barium nitrate, bismuth nitrate, calcium nitrate, cesium nitrate, cerium nitrate, Gallium nitrate, indium nitrate, potassium nitrate, lanthanum nitrate, lithium nitrate, magnesium nitrate, sodium nitrate, lead nitrate, rubidium nitrate, tin nitrate, strontium nitrate, glass Antimony, titanium nitrate, tellurium nitrate, vanadium nitrate, zirconium nitrate, potassium silicate, calcium silicate, magnesium silicate, barium silicate, lithium phosphate, sodium phosphate, potassium phosphate, calcium phosphate, magnesium phosphate, phosphoric acid Barium, lithium borate, sodium borate, potassium borate, magnesium borate, calcium borate, barium borate, gold, silver, layered double hydroxide (hydrotalcite, etc.), clay compound, lipolite, hydroxyapatite, A solid solution such as cerium oxide-zirconium oxide, ettringite, and cement are more preferable.

Particularly preferably, silver oxide, aluminum oxide, barium oxide, bismuth oxide, calcium oxide, cerium oxide, cobalt oxide, chromium oxide, cesium oxide, gallium oxide, indium oxide, lanthanum oxide, manganese monoxide, manganese dioxide, niobium oxide, Lead oxide, rubidium oxide, silicon oxide, phosphorus oxide, tin oxide, antimony oxide, titanium oxide, tellurium oxide, vanadium oxide, zirconium oxide, zirconium oxide stabilized with scandium oxide, zirconium oxide stabilized with yttrium oxide, hydroxide Aluminum, barium hydroxide, calcium hydroxide, cerium hydroxide, cesium hydroxide, indium hydroxide, potassium hydroxide, lanthanum hydroxide, lithium hydroxide, magnesium hydroxide, sodium hydroxide, rubidium hydroxide, tin hydroxide, Strontium oxide, antimony hydroxide, titanium hydroxide, zirconium hydroxide, silver chloride, lithium chloride, magnesium chloride, sodium chloride, rubidium chloride, tin chloride, silver oxide, barium acetate, bismuth acetate, calcium acetate, cesium acetate, gallium acetate , Indium acetate, potassium acetate, cerium acetate, chromium acetate, lanthanum acetate, lithium acetate, magnesium acetate, sodium acetate, lead acetate, rubidium acetate, tin acetate, strontium acetate, antimony acetate, tellurium acetate, silver carbonate, barium carbonate, carbonate Bismuth, calcium carbonate, cobalt carbonate, cesium carbonate, gallium carbonate, indium carbonate, lead carbonate, tin carbonate, strontium carbonate, antimony carbonate, bismuth sulfate, calcium sulfate, cesium sulfate, gallium sulfate, indium sulfate Lead sulfate, tin sulfate, antimony sulfate, titanium sulfate, tellurium sulfate, vanadium sulfate, zirconium sulfate, calcium lignin sulfonate, sodium lignin sulfonate, bismuth nitrate, calcium nitrate, gallium nitrate, indium nitrate, lead nitrate, tin nitrate, nitric acid Antimony, titanium nitrate, tellurium nitrate, potassium silicate, calcium silicate, magnesium silicate, barium silicate, sodium phosphate, potassium phosphate, calcium phosphate, magnesium phosphate, barium phosphate, sodium borate, potassium borate, Magnesium borate, calcium borate, barium borate, layered double hydroxide (hydrotalcite, etc.), clay compound, lipolite, hydroxyapatite, cerium oxide-zirconium oxide solid solution, ettringite, cement is there.
Compounds such as cerium hydroxide, zirconium hydroxide, layered double hydroxides (hydrotalcite, etc.), hydroxyapatite, ettringite, etc. are used for decomposition reactions and self-decomposition of water at the zinc electrode during charge / discharge and storage in the charged state. It is considered that not only the discharge and the dissolution reaction of the negative electrode active material containing zinc are suppressed, but also the function of increasing the anion conductivity is assumed.
In addition, in the case of a primary battery or a secondary battery using a zinc-containing compound as a negative electrode and a water-containing electrolyte described later, further to the electrolyte, zinc oxide, zinc hydroxide, zinc phosphate, zinc pyrophosphate, boron It is preferable to add at least one zinc compound selected from zinc acid, zinc silicate, zinc aluminate, zinc metal, and tetrahydroxy zinc ion salt. 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. In this case, elements other than zinc are used as at least one element selected from the group consisting of elements belonging to Groups 1 to 17 of the periodic table. The zinc compound in the electrolytic solution is preferably from 0.0001 mol / L to a saturated concentration.

Moreover, the compound which has at least 1 element selected from the group which consists of an element which belongs to the 1st-17th group of the said periodic table is converted into a nanoparticulate etc., and the same as the said zinc containing compound and / or a conductive support agent. If the average particle diameter is small, side reactions that occur when a water-containing electrolytic solution is used as the above-described electrolytic solution can be further effectively suppressed. The compound having at least one element selected from the group consisting of elements belonging to Groups 1 to 17 of the periodic table is the zinc-containing compound before or after the preparation of the zinc negative electrode mixture or during the preparation of the zinc negative electrode mixture. In addition, at least one of a conductive additive, an organic compound, and an organic compound salt may be supported, coprecipitated, alloyed, solidified, or kneaded. It may be prepared by a sol-gel method.
Thus, the compound having at least one element selected from the group consisting of elements belonging to Groups 1 to 17 of the periodic table preferably has an average particle diameter of 1000 μm or less, more preferably 200 μm or less. More preferably, it is 100 μm or less, particularly preferably 75 μm or less, and most preferably 20 μm or less. On the other hand, the lower limit of the average particle diameter is preferably 1 nm. The average particle diameter can be measured in the same manner as the average particle diameter of the zinc-containing compound and the conductive auxiliary agent described above.
Examples of the shape of the particles include fine powder, powder, granule, granule, scale, polyhedron, and rod. In addition, the particles having an average particle size in the above-described range are, for example, a method of pulverizing particles with a ball mill or the like, dispersing the obtained coarse particles in a dispersant to obtain a desired particle size, In addition to the method of selecting the particle diameter by sieving the coarse particles, etc., it is possible to optimize the preparation conditions at the stage of producing the particles to obtain (nano) particles having a desired particle diameter.

The compound having at least one element selected from the group consisting of elements belonging to Groups 1 to 17 of the periodic table preferably has a specific surface area of 0.01 m ² / g or more, more preferably 0.8. 1 m ² / g or more, more preferably 0.5 m ² / g or more. On the other hand, the upper limit value of the specific surface area is preferably 200 m ² / g. The specific surface area can be measured in the same manner as the specific surface areas of the zinc-containing compound and the conductive additive described above.

Examples of the organic compound and organic compound salt include poly (meth) acrylic acid moiety-containing polymer, poly (meth) acrylate moiety-containing polymer, poly (meth) acrylate ester moiety-containing polymer, poly (α-hydroxymethylacrylic acid) Salt) site-containing polymer, poly (α-hydroxymethyl acrylate) site-containing polymer, polyacrylonitrile site-containing polymer, polyacrylamide site-containing polymer, polyvinyl chloride site-containing polymer, polyvinyl alcohol site-containing polymer, polyethylene oxide site-containing polymer , Polypropylene oxide moiety-containing polymer, polybutene oxide moiety-containing polymer, epoxy ring-opening moiety-containing polymer, polyethylene moiety-containing polymer, polypropylene moiety-containing polymer, polybutene moiety-containing polymer, Polyisoprenol moiety-containing polymer, polymethallyl alcohol moiety-containing polymer, polyallyl alcohol moiety-containing polymer, polyhexene moiety-containing polymer, polyoctene moiety-containing polymer, polybutadiene moiety-containing polymer, polyisoprene moiety-containing polymer, aromatic ring represented by polystyrene Site-containing polymer, polymaleimide site-containing polymer, polyvinylpyrrolidone site-containing polymer, polyacetylene site-containing polymer, polyetherketone site-containing polymer, ketone group site-containing polymer, ether group site-containing polymer, sulfide group-containing polymer, sulfone group-containing polymer, Carbamate group-containing polymer, thiocarbamate group-containing polymer, carbamide group-containing polymer, thiocarbamide group-containing polymer, thiocarboxylic acid (salt) group Artificial rubbers typified by organic polymer, ester group-containing polymer, cyclopolymerization site-containing polymer, analgen, benzene, trihydroxybenzene, toluene, piperonaldehyde, lignin, carbowax, natural rubber, styrene butadiene rubber (SBR), etc. , Agar, carbazole, amino acid, amino acid salt, glutaric acid, glutarate, betaine moiety-containing compound, gelatin, trialkyl phosphate, soap, soap derivative, cellulose, cellulose acetate, hydroxyalkyl cellulose, dextrin, carboxymethyl cellulose, hydroxyethyl cellulose , Ethylene glycol, ethylene glycol oligomer, polyethylene glycol chain-containing compound, polypropylene glycol chain-containing compound, polybutene glycol chain-containing compound, polyacetate Rene moiety-containing polymer, amino group-containing polymer such as polyethyleneimine, polyamide moiety-containing polymer, polypeptide moiety-containing polymer, polytetrafluoroethylene moiety-containing polymer, polyvinylidene fluoride moiety-containing polymer, poly (anhydride) maleic acid moiety-containing polymer, Polymaleate moiety-containing polymer, poly (anhydride) itaconic acid moiety-containing polymer, polyitaconate moiety-containing polymer, polymethylene glutarate moiety-containing polymer, polymethylene glutarate moiety-containing polymer, polymethylene lactone moiety-containing polymer, hydroxyl group-containing Polymers, ion exchange polymers used for cation / anion exchange membranes, sulfonates, poly (sodium 2-hydroxy-3-allyloxypropanesulfonate), poly (methallylsulfonate sodium) Um), poly (sodium 2-sulfoethyl methacrylate), poly (sodium isoprene sulfonate), poly (sodium 2-acrylamido-2-methylpropanesulfonate), polystyrene sulfonic acid, sodium polyvinyl sulfonate, etc. Sulfonate moiety-containing polymer, quaternary ammonium salt, quaternary ammonium salt moiety-containing polymer, quaternary phosphonium salt, quaternary phosphonium salt moiety-containing polymer, isocyanate group-containing polymer, isocyanate group-containing polymer, thioisocyanate Group-containing polymer, imide group site-containing polymer, sulfonimide group site-containing polymer, epoxy group site-containing polymer, oxetane group site-containing polymer, hydroxyl group site-containing polymer, liquid crystal, liquid crystal site-containing polymer, heterocyclic ring, and / or On of the heterocyclic ring moiety containing polymer, polymer alloy, heteroatom-containing polymers, low molecular weight surfactants. The above organic compounds and organic compound salts can be used alone or in combination of two or more. When the organic compound and the organic compound salt are polymers, the functional group may be in the main chain or in the side chain, and the main chain may be partially crosslinked.

When the organic compound or organic compound salt is a polymer, radical polymerization, radical (alternate) copolymerization, anion polymerization, anion (alternate) copolymerization, cationic polymerization, cation (cation) (cation ( (Alternate) copolymerization, graft polymerization, graft (alternate) copolymerization, living polymerization, living (alternate) copolymerization, dispersion polymerization, emulsion polymerization, suspension polymerization, ring-opening polymerization, cyclization polymerization, light, ultraviolet light and electron beam irradiation Can be obtained by polymerization or the like. At this time, the compound containing at least one element selected from the group consisting of the zinc-containing compound particles, the conductive auxiliary agent particles, and the elements belonging to Groups 1 to 17 of the periodic table, in the polymer and / or on the surface It is also possible to form a single particle. In addition, the polymer may cause a reaction such as hydrolysis in the electrolytic solution.
Organic compounds and organic compound salts not only improve the dispersibility of particles, but also bind the particles, the particles and the current collector, the thickener, and the zinc electrode active material. It is expected to function as a material that exhibits effects such as suppression of kinetic formation, suppression of dissolution of the active material of the zinc electrode, improvement of hydrophilicity / hydrophobicity balance, improvement of anion conductivity, and improvement of electron conductivity. If this occurs, side reactions during charging and discharging, where hydrogen decomposition occurs as a result of the water decomposition reaction that normally occurs thermodynamically, morphological changes and passive formation and corrosion reactions of zinc electrode active materials, and charging It also serves to suppress self-discharge during storage in a state or in a charged state, and to significantly improve charge / discharge characteristics, coulomb efficiency, and storage stability of the battery. One of the factors of this effect is that organic compounds and organic compound salts suitably cover or adsorb the surface on zinc-containing compounds, or that chemical interactions with zinc-containing compounds are manifested. It is thought to do. It was newly found in the present invention that such an effect is seen in organic compounds and organic compound salts.

Preferably, the organic compound or organic compound salt is a poly (meth) acrylic acid moiety-containing polymer, a poly (meth) acrylate moiety-containing polymer, a poly (meth) acrylic ester moiety-containing polymer, or poly (α-hydroxymethylacrylic). Acid salt) site-containing polymer, polyacrylonitrile site-containing polymer, polyacrylamide site-containing polymer, poly (N, N-dialkylacrylamide) site-containing polymer, polyvinyl alcohol site-containing polymer, polyethylene oxide site-containing polymer, polypropylene oxide site-containing polymer, Polybutene oxide moiety-containing polymer, epoxy ring-opening moiety-containing polymer, polyethylene moiety-containing polymer, polypropylene moiety-containing polymer, polybutene moiety-containing polymer, polyisoprenol moiety-containing polymer Polymer, polymethallyl alcohol moiety-containing polymer, polyallyl alcohol moiety-containing polymer, polybutadiene moiety-containing polymer, polyisoprene moiety-containing polymer, aromatic ring moiety-containing polymer represented by polystyrene, polyvinylpyrrolidone moiety-containing polymer, polyacetylene moiety-containing polymer, Polyetherketone site-containing polymer, ketone group site-containing polymer, ether group site-containing polymer, carbamate group site-containing polymer, thiocarbamate group site-containing polymer, carbamide group site-containing polymer, thiocarbamide group site-containing polymer, ester group-containing polymer, Cyclic polymerization site-containing polymer, polyvinyl alcohol site-containing polymer, natural rubber, artificial rubber typified by styrene butadiene rubber (SBR), agar, lignin, carbowa , Carbazole, amino acid, amino acid salt, glutaric acid, glutarate, betaine site-containing compound, gelatin, trialkyl phosphate, soap, soap derivative, cellulose, cellulose acetate, hydroxyalkyl cellulose, dextrin, carboxymethyl cellulose, hydroxyethyl cellulose, Ethylene glycol, ethylene glycol oligomer, polyethylene glycol chain-containing compound, polypropylene glycol chain-containing compound, polybutene glycol chain-containing compound, amino group-containing polymer such as polyethyleneimine, polyamide site-containing polymer, polypeptide site-containing polymer, polytetrafluoroethylene site -Containing polymer, polyvinylidene fluoride moiety-containing polymer, polymaleate moiety-containing polymer, polyitaconate moiety Polymers, ion-exchangeable polymers used for cation / anion exchange membranes, sulfonate group-containing polymers, poly (2-hydroxy-3-allyloxypropane sulfonate sodium) / poly (sodium methallyl sulfonate) ) ・ Poly (sodium 2-sulfoethyl methacrylate) ・ Poly (sodium isoprene sulfonate) ・ Poly (sodium 2-acrylamido-2-methylpropane sulfonate) ・ Polystyrene sulfonate sodium, polyvinyl sulfonate sodium, etc. Sulfonate moiety-containing polymer, quaternary ammonium salt, quaternary ammonium salt moiety-containing polymer, quaternary phosphonium salt, quaternary phosphonium salt moiety-containing polymer, heterocycle and / or ionized heterocycle moiety Polymer, polymer alloy, f It is a Russian atom-containing polymer.

The zinc negative electrode mixture of the present invention is a compound having at least one element selected from the group consisting of elements belonging to Groups 1 to 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 organic compounds and organic compound salts. For mixing, a mixer, blender, kneader, bead mill, ready mill, ball mill, or the like can be used. During mixing, water, an organic solvent such as methanol, ethanol, propanol, isopropanol, tetrahydrofuran, N-methylpyrrolidone, or a mixed solvent of water and an organic solvent may be added. After mixing, operations such as sieving may be performed in order to align the particles with a desired particle size. Mixing may be performed by either a wet method in which a liquid component such as water or an organic solvent is added to the solid component, or a dry method in which only the solid component is added without adding the liquid component. When mixing is performed by a wet method, after mixing, liquid components such as water and organic solvent may be removed by drying. Mixing can also be performed by combining a wet method and a dry method. For example, it is obtained by mixing a zinc-containing compound and a compound having at least one element selected from the group consisting of elements belonging to Groups 1 to 17 of the periodic table by a wet method and then removing the liquid component by drying. The zinc negative electrode mixture may be prepared by mixing the obtained solid mixture and the conductive additive by a dry method.

The zinc electrode of the present invention is formed using the above zinc negative electrode mixture. A zinc electrode formed using such a zinc negative electrode mixture of the present invention is also one aspect of the present invention. The zinc electrode of the present invention is preferably used as a negative electrode. Below, the zinc electrode of this invention used as a negative electrode is also called the zinc negative electrode of this invention.
The zinc negative electrode of the present invention can improve battery cycle characteristics, rate characteristics, and coulomb efficiency.

Examples of the method for preparing the zinc negative electrode include the following methods.
By the preparation method described above, the zinc negative electrode mixture of the present invention is obtained as a slurry or a paste mixture. Next, the obtained slurry or paste mixture is coated, pressure-bonded or bonded on the current collector so that the film thickness is as constant as possible.
As the current collector, copper foil, electrolytic copper, copper foil added with Ni, Sn, Pb, Hg, Bi, In, Tl, carbon, etc., Ni, Sn, Pb, Hg, Bi, In, Tl, carbon Copper foil plated with copper, copper mesh, Ni / Sn / Pb / Hg / Bi / In / Tl / carbon added copper mesh, Ni / Sn / Pb / Hg / Bi / In / Tl / carbon, etc. Plated copper mesh, foamed copper, foamed copper added with Ni, Sn, Pb, Hg, Bi, In, Tl, carbon, etc., plated with Ni, Sn, Pb, Hg, Bi, In, Tl, carbon, etc. Copper foam, copper alloy, nickel foil, nickel mesh, corrosion-resistant nickel, nickel mesh with Sn, Pb, Hg, Bi, In, Tl, carbon, etc., Sn, Pb, Hg, Bi, In, Tl, carbon, etc. Ni plated by Lumesh, zinc metal, corrosion resistant zinc metal, zinc metal with addition of Ni, Sn, Pb, Hg, Bi, In, Tl, carbon, etc., plated with Ni, Sn, Pb, Hg, Bi, In, Tl, carbon, etc. Zinc metal, zinc foil, zinc foil added with Ni, Sn, Pb, Hg, Bi, In, Tl, carbon, etc., zinc plated with Ni, Sn, Pb, Hg, Bi, In, Tl, carbon, etc. Foil, zinc mesh, zinc mesh added with Ni, Sn, Pb, Hg, Bi, In, Tl, carbon, etc., zinc mesh plated with Ni, Sn, Pb, Hg, Bi, In, Tl, carbon, etc. Examples include current collector materials used for silver, alkaline batteries and air zinc batteries.

The slurry or paste mixture may be applied, pressed or adhered to one side of the current collector, or may be applied, pressed or bonded to both sides. It dries at 0-250 degreeC during coating and / or after coating. More preferably, it is 15-200 degreeC as drying temperature. Drying may be performed by vacuum 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. at the pressure of 0.01-20 t after drying. More preferably, the pressing pressure is 0.1 to 15 t. You may apply the temperature of 10-500 degreeC at the time of a press.

The thus obtained zinc negative electrode (zinc mixture electrode) suppresses current concentration and water decomposition in the zinc negative electrode, particularly when used as a negative electrode for a secondary battery. To minimize deterioration due to morphological changes such as shape change and dendrite, dissolution, corrosion, passive formation, generation of hydrogen / oxygen during charge / discharge, and self-discharge during charge and storage in charge can do.
The film thickness of the zinc negative electrode is preferably 1 nm to 1000 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-100 micrometers, More preferably, it is 20 nm-50 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.
The form of the battery using the zinc electrode of the present invention as a negative electrode is as follows: primary battery; rechargeable secondary battery (storage battery); 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 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.
Thus, a battery having the zinc electrode of the present invention is also one aspect of the present invention.

The battery of the present invention can contain a positive electrode active material, an electrolytic solution and the like in addition to the zinc negative electrode. Moreover, as an electrolyte solution, a water-containing electrolyte solution is preferable as described later.
Therefore, a battery comprising the zinc negative electrode, the positive electrode active material, and the water-containing electrolyte of the present invention is also one aspect of the present invention. The battery of the present invention may include one of each of these components, or may include two or more.

As the positive electrode active material, those normally used as the positive electrode active material of a primary battery or a secondary battery can be used, and are not particularly limited. For example, oxygen (when oxygen becomes a positive electrode active material, Perovskite type compounds capable of reducing water 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, etc. Poles); nickel-containing compounds such as nickel oxyhydroxide, nickel hydroxide, cobalt-containing nickel hydroxide; manganese-containing compounds such as manganese dioxide; silver oxide, lithium cobaltate, lithium manganate, lithium iron phosphate, etc. Can be mentioned.
Among these, it is a battery using the zinc negative electrode mixture of the present invention, and the positive electrode active material is a nickel-containing compound, which is also a preferred embodiment of the present invention.
Moreover, it is a battery using the zinc negative electrode mixture of this invention, and it is also one of the suitable embodiment of this invention that positive electrode active materials, such as an air battery and a fuel cell, are oxygen. That is, it is also one of the preferred embodiments of the present invention that the positive electrode of the battery of the present invention is an electrode having oxygen reducing ability.

The electrolyte solution is not particularly limited as long as it is usually used as an electrolyte solution for a battery. Examples thereof include a water-containing electrolyte solution and an organic solvent-based electrolyte solution, and a water-containing electrolyte solution is preferable. 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 and the like. 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.
Examples of the organic solvent used in the organic solvent-based electrolyte include ethylene carbonate, propylene carbonate, dimethyl carbonate, diethyl carbonate, γ-butyrolactone, dimethoxymethane, diethoxymethane, dimethoxyethane, tetrahydrofuran, methyltetrahydrofuran, and diethoxyethane. Dimethyl sulfoxide, sulfolane, acetonitrile, 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. The electrolyte of the organic solvent-based electrolytic solution is not particularly limited, but LiPF ₆ , LiBF ₄ , LiB (CN) ₄ , lithium bis (fluorosulfonyl) imide (LiFSI), lithium bis (trifluoromethylsulfonyl) imide ( LiTFSI) and the like are preferable.
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.
Note that the electrolytic solution may or may not be circulated.

The electrolytic solution may contain an additive. When an aqueous electrolyte is used, a side reaction during charge and discharge in which hydrogen is generated by the progress of a water decomposition reaction, which can usually occur thermodynamically, a morphological change or passive formation of a zinc electrode active material, 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. It is considered that this is because the additive suitably interacts with the surface on the zinc oxide and suppresses side reactions, morphological changes and passive formation, dissolution, corrosion reaction, and self-discharge of the zinc electrode active material.
As an additive, for example, in the case of an aqueous electrolyte using potassium hydroxide as an electrolyte, carbon, lithium hydroxide, sodium hydroxide, magnesium hydroxide, barium hydroxide, calcium hydroxide, strontium hydroxide, magnesium oxide , Barium oxide, calcium oxide, strontium oxide, strontium acetate, magnesium acetate, barium acetate, calcium acetate, bismuth oxide, zinc oxide, zinc hydroxide, zinc pyrophosphate, zinc metal, zinc fluoride, tetrahydroxyzinc ion, sodium carbonate , Potassium carbonate, calcium carbonate, magnesium carbonate, barium carbonate, magnesium chloride, barium chloride, calcium chloride, lithium fluoride, sodium fluoride, potassium fluoride, rubidium fluoride, cesium fluoride, beryllium fluoride, fluorine Magnesium, calcium fluoride, strontium fluoride, barium fluoride, potassium acetate, potassium chloride, potassium bromide, potassium iodide, boric acid, potassium metaborate, potassium borate, potassium hydrogen borate, sodium borate, boric acid Sodium hydrogen, magnesium borate, calcium borate, barium borate, borofluoric acid, stannous borofluoride, phosphoric acid, potassium phosphate, potassium hydrogen phosphate, potassium dihydrogen phosphate, sodium phosphate, sodium hydrogen phosphate Sodium dihydrogen phosphate, potassium pyrophosphate, potassium phosphite, sodium phosphite, potassium hypophosphite, sodium hypophosphite, potassium arsenate, potassium oleate, sodium oleate, potassium oxalate, Sodium acid, potassium stearate, Sodium allate, potassium silicate, sodium silicate, potassium sulfide, sodium sulfide, potassium sulfate, sodium sulfate, potassium thiosulfate, sodium thiosulfate, cadmium oxide, cobalt hydroxide, titanium oxide, zirconium oxide, aluminum oxide, lead oxide , Lead acetate, tellurium oxide, iron oxide, cobalt oxide, germanium oxide, tin oxide, tin hydroxide, tin chloride, indium sulfate, indium oxide, indium hydroxide, sorbitol and other sugars, soap, soap derivatives, trialkyl Phosphoric acid, quaternary ammonium salt-containing compound, quaternary phosphonium salt-containing compound, caprolactam compound, carboxylic acid-containing compound, carboxylate-containing compound, polyethylene glycol chain-containing compound, polypropylene glycol chain-containing compound, polybutene glycol Cole chain-containing compound, chelating agent, methanol, ethanol, 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, organic compounds, polymers containing organic compound salts, gel compounds, and the like. Can be mentioned.
A compound having at least one element selected from the group consisting of elements belonging to Groups 1 to 17 of the periodic table may be added to the electrolytic solution. One type or two or more types of additives can be used.

In addition, when using a water-containing electrolyte including the coexistence of an organic solvent electrolyte, the dissolved oxygen concentration value (mg / L) (at 25 ° C.) of only the aqueous electrolyte to be used is α = It is preferably not more than the α value calculated by the formula −0.26375 × β + 8.11 (β is a hydroxide ion concentration <mol / L> in the aqueous electrolyte solution to be used). More preferably, the amount of dissolved oxygen is as close to 0 mg / L as possible. By reducing the dissolved oxygen concentration, it becomes possible to reduce the dissolution of the zinc electrode active material into the electrolyte, suppressing the shape change, dissolution, corrosion, and passivation of the zinc electrode active material, and reducing the life of the electrode. Will improve. In order to make the dissolved oxygen concentration equal to or less than a predetermined amount, it can be achieved by operations such as deaeration of an electrolyte or a solvent used in the electrolyte, or bubbling of an inert gas such as nitrogen or argon. 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 equation of the dissolved oxygen concentration value is an equation derived from the corrosion state of dissolved oxygen and zinc metal. Further, 8.11 in the above formula is the saturation solubility of oxygen in pure water (25 ° C.). Furthermore, in 4M and 8M KOH aqueous solutions, a 4M and 8M KOH aqueous solution in which an arbitrary amount of oxygen (25 ° C) was dissolved (with an arbitrary amount of dissolved oxygen) was created, and the corrosion of zinc metal immersed in the liquid was created. The above equation is derived by observing the presence or absence with an SEM. By setting the dissolved oxygen amount to be equal to or less than the α value, the reaction represented by the formula of Zn + 1 / 2O ₂ + H ₂ O → Zn (OH) ₂ is suppressed, so that it is considered that corrosion hardly occurs.

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. In addition, in the case of a storage battery using a zinc negative electrode, the zinc electrode active material is prevented from being altered or dendrite is formed, the positive and negative electrodes are moistened, and liquid drainage is avoided.
The separator is not particularly limited, but non-woven fabric, filter paper, polyethylene, polypropylene, polytetrafluoroethylene, polyvinylidene fluoride, cellulose, fibrillated cellulose, viscose rayon, cellulose acetate, hydroxyalkyl cellulose, carboxymethyl cellulose, polyvinyl alcohol, High molecular weight polymers such as cellophane, polystyrene, polyacrylonitrile, polyacrylamide, polyvinyl chloride, polyamide, polyimide, vinylon, nylon, poly (meth) acrylic acid, copolymers thereof, agar, gel compounds, organic inorganic Hybrid (composite) compounds, ion-exchange membrane polymers and their copolymers, cyclized polymers and their copolymers, poly (meth) acrylate-containing polymers and their copolymers , Sulfonate-containing polymers and their copolymers, quaternary ammonium salt-containing polymers and their copolymers, quaternary phosphonium salts polymers and their copolymers, inorganic such as ceramics.
In the separator, silver oxide, aluminum oxide, zinc oxide, zinc hydroxide, tetrahydroxy zinc ion, zinc fluoride, barium oxide, barium hydroxide, calcium oxide, calcium hydroxide, magnesium oxide, magnesium hydroxide, barium oxide, Barium hydroxide, calcium phosphate, hydrotalcite, hydroxyapatite, ettringite, cement, cadmium, cerium oxide, cerium hydroxide, niobium oxide, cobalt oxide, manganese monoxide, manganese dioxide, titanium oxide, zirconium oxide, zirconium hydroxide, oxidation Copper, iron oxide, magnesium silicate, calcium silicate, nickel, strontium hydroxide, boric acid, potassium borate, calcium borate, lithium fluoride, sodium fluoride, potassium fluoride, rubidium fluoride , Cesium fluoride, beryllium fluoride, magnesium fluoride, calcium fluoride, strontium fluoride, barium fluoride, potassium titanate, calcium zincate, surfactants may include the electrolyte solution or the like.
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.

As described above, a battery having a zinc electrode prepared from the zinc negative electrode mixture is also one aspect of the present invention. More preferably, the battery has a zinc negative electrode prepared from the zinc negative electrode mixture. The positive electrode is more preferably a nickel 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 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 (Ni-hydrogen storage alloy battery), a nickel * cadmium battery, etc. The inner wall of the assembly and holding container should be made of a material that will not deteriorate due to corrosion, reaction during charging / discharging, etc. 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 in a strip shape are alternately sandwiched between pleated separators, a sealed type, an open type, or a bent type good. You may have the site | part which reserves the gas generated at the time of charging / discharging.

The manufacturing process of the storage battery may be a wet process or a dry process. In the wet process, for example, the positive electrode current collector sheet and the negative electrode current collector sheet 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 is performed. After cleaning, the cut electrode sheet and separator are stacked in layers to form a storage battery assembly. The dry process is, for example, a process using electrode component powder or a granular dry mixture instead of slurry or paste. (1) Applying a zinc negative electrode material to a conductive support, (2) Nickel positive electrode material in a dry state (3) A separator is placed between the sheets (1) and (2) to form a layered structure to form a storage battery assembly, and (4) (3) the storage battery assembly is wrapped. Alternatively, it undergoes a process such as folding to form a three-dimensional structure. The electrode may be wrapped with a separator or gel electrolyte, or coated with them. 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. In the manufacturing process or storage of the storage battery, the storage battery may be charged or discharged.

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, it is 0.05C or more and 80C or less, More preferably, it is 0.1C or more and 60C or less, Especially preferably, it is 0.1C 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. For example, in the case of a nickel zinc battery, the capacity of the zinc negative electrode may be larger, smaller, or the same as the capacity of the nickel positive electrode, and either overcharge or overdischarge may occur. When using this storage battery for in-vehicle use, it is preferable to set the charging depth and / or the discharging depth shallow. Thereby, while being able to extend the lifetime of a zinc negative electrode and a nickel zinc storage battery, generation | occurrence | production of oxygen by a side reaction can also be suppressed significantly. In a storage battery using a zinc electrode, it is preferable that oxygen generated in the system is consumed by (i) a bond with zinc of the negative electrode or (ii) a reaction at a third electrode different from the positive electrode / negative electrode. However, by selecting charging / discharging conditions and fundamentally suppressing oxygen generation, it is possible to easily achieve a long life and sealing of the storage battery. The nickel electrode may be a nickel electrode used in a nickel / cadmium battery or a nickel / metal hydride battery. By adding carbon, a lanthanoid compound, or the like to the nickel electrode, it is possible to increase the oxygen overvoltage and suppress oxygen generation as much as possible. Additives contained in the electrolytic solution and the gel electrolyte can also improve the performance of the nickel electrode. In addition, the polyvalent ions and / or inorganic compounds and / or electrolytes contained in the gel electrolyte suppress oxygen generation as much as possible, or the gel electrolyte has a flexible skeleton structure as compared with conventional gel electrolytes. The gas diffuses at a high speed, and it can be expected that the generated oxygen can be quickly transported to the counter electrode or the third electrode.

The zinc negative electrode mixture of the present invention has the above-described structure, and when this is used to form a zinc negative electrode, the cycle characteristics, rate characteristics and coulomb efficiency of the battery are improved as compared with the conventional zinc negative electrode. In addition, when a water-containing electrolyte is used, the battery is highly safe. From these facts, the zinc negative electrode mixture of the present invention can be suitably used for forming a negative electrode of a battery that is excellent in economic efficiency, safety, stability, and storage stability and battery performance. is there. Furthermore, by including the above-mentioned other components in the zinc negative electrode mixture, even when the battery is configured using a water-containing electrolyte, the water decomposition reaction proceeds and hydrogen is generated during charge / discharge Side reactions, morphological changes of zinc active materials, corrosion, formation of passives, and self-discharge during charging and storage in a charged state, and tetrahydroxyzinc ions, etc. It is expected that effects such as suppression of solubility of zinc species due to salt formation with zinc species, improvement of hydrophilicity / hydrophobicity balance, improvement of anion conductivity, and improvement of electron conductivity will be exhibited at the same time. Can be improved.

FIG. 1 is a graph showing the results of the charge / discharge test of Example 1, showing a discharge curve for the first cycle and charge curves for the 20, 40, 60, 80, and 100th cycles. FIG. 2 is a graph showing the results of the charge / discharge test of Example 2, showing the discharge curve of the first cycle and the charge curves of the 200th cycle and the 250th cycle. FIG. 3 is a graph showing the results of the charge / discharge test of Example 3, and shows the discharge curve of the first cycle and the charge curves of the 100th, 200th, 300th, 400th, and 500th cycles. FIG. 4 is a graph showing the results of the charge / discharge test of Example 4, showing the discharge curve of the first cycle and the charge curves of the 20, 40, 60, and 100th cycles. FIG. 5 is a graph showing the results of the charge / discharge test of Example 5, showing the discharge curve of the first cycle and the charge curves of the first and 60th cycles. FIG. 6 is a graph showing the results of the charge / discharge test of Example 6, showing the discharge curve of the first cycle and the charge curves of the 6, 100, 250, and 500th cycles. FIG. 7 is a graph showing the results of the charge / discharge test of Example 7, showing the discharge curve of the first cycle and the charge curves of the 6th, 30th, and 60th cycles. FIG. 8 is a graph showing the results of the charge / discharge test of Example 8, showing the discharge curve of the first cycle and the charge curves of the 5th, 30th, and 60th cycles. FIG. 9 is a graph showing the results of the charge / discharge test of Example 9, showing the discharge curve of the first cycle and the charge curves of the 6th, 30th, and 60th cycles. FIG. 10 is a graph showing the results of the charge / discharge test of Example 10, and shows the discharge curve of the first cycle and the charge curves of the 6th, 30th, and 60th cycles. FIG. 11 is a graph showing the results of the charge / discharge test of Example 11, showing the discharge curve of the first cycle and the charge curves of the 3, 30 and 60 cycles. FIG. 12 is a graph showing the results of the charge / discharge test of Example 12, showing the discharge curve of the first cycle and the charge curves of the 3, 30, and 60th cycles. FIG. 13 is a graph showing the results of the charge / discharge test of Example 13, showing the discharge curves for the first cycle and the charge curves for the first, thirty, and sixty cycles. FIG. 14 is a graph showing the results of the charge / discharge test of Example 14, showing the discharge curve of the first cycle and the charge curves of the 4th and 30th cycles. FIG. 15 is a graph showing the results of the charge / discharge test of Example 15, showing the discharge curve of the first cycle and the charge curves of the 8th and 30th cycles. FIG. 16 is a graph showing the results of the charge / discharge test of Example 16, showing the discharge curve of the first cycle and the charge curves of the 4, 30 and 60 cycles. FIG. 17 is a graph showing the results of the charge / discharge test of Example 17, showing the discharge curve of the first cycle and the charge curves of the 1st, 30th and 60th cycles. FIG. 18 is a graph showing the results of the charge / discharge test of Example 18, showing the discharge curve of the first cycle and the charge curves of the 6th, 30th, and 60th cycles. FIG. 19 is a graph showing the results of the charge / discharge test of Example 19, showing the discharge curve of the first cycle and the charge curves of the 3, 30, and 60th cycles. FIG. 20 is a graph showing the results of the charge / discharge test of Example 20, showing the discharge curve of the first cycle and the charge curves of the 4, 30, and 60th cycles. FIG. 21 is a graph showing the results of the charge / discharge test of Example 21, showing the discharge curve of the first cycle and the charge curves of the 3, 30, and 60th cycles. FIG. 22 is a graph showing the results of the charge / discharge test of Example 22, showing the discharge curve of the first cycle and the charge curves of the 3, 30, and 60th cycles. FIG. 23 is a graph showing the results of the charge / discharge test of Example 23, showing the discharge curve of the first cycle and the charge curves of the 2, 30 and 60 cycles. FIG. 24 is a graph showing the results of the charge / discharge test of Example 24, showing the discharge curve of the first cycle and the charge curves of the 3, 30, and 60th cycles. FIG. 25 is a graph showing the results of the charge / discharge test of Example 25, showing the discharge curve of the first cycle and the charge curves of the 3, 30, and 60th cycles. FIG. 26 is a graph showing the results of the charge / discharge test of Example 26, showing the discharge curves for the first cycle and the charge curves for the 3, 30, and 60 cycles. FIG. 27 is a graph showing the results of the charge / discharge test of Example 27, showing the discharge curve of the first cycle and the charge curves of the 3, 30, and 60th cycles. FIG. 28 is a graph showing the results of the charge / discharge test of Example 28, showing the discharge curve of the first cycle and the charge curves of the 4, 30, and 60 cycles. FIG. 29 is a graph showing the results of the charge / discharge test of Example 29, showing the discharge curve of the first cycle and the charge curves of the 3, 30 and 60 cycles. FIG. 30 is a graph showing the results of the charge / discharge test of Example 30, showing a charge curve and a discharge curve at the 20th cycle. FIG. 31 is a graph showing the results of the charge / discharge test of Example 31, showing a charge curve and a discharge curve at the 10th cycle. FIG. 32 is a graph showing the results of the charge / discharge test of Example 32, showing a charge curve and a discharge curve for the sixth cycle. FIG. 33 is a photograph showing the results of the corrosion test of Example 33. Pre-test zinc metal, zinc metal immersed in 8M potassium hydroxide aqueous solution (oxygen concentration: 3.5 mg / L) for 5 hours, 8M hydroxide The SEM photograph of the zinc metal immersed in potassium aqueous solution (oxygen concentration: 6.8 mg / L) for 5 hours is shown. FIG. 34 is a graph showing the results of the charge / discharge test of Example 43, showing the discharge curve of the first cycle and the charge curves of the 3, 30, and 60th cycles. FIG. 35 is a graph showing the results of the charge / discharge test of Example 44, showing the charge curves of the 3rd cycle, 30th cycle and 60th cycle. FIG. 36 is a graph showing the results of the charge / discharge test of Example 45, showing the charge curves of the 3rd, 30th, and 60th cycles. FIG. 37 is a graph showing the results of the charge / discharge test of Example 46, showing the charge curves of the 3rd cycle, 30th cycle and 60th cycle. FIG. 38 is a graph showing the results of the charge / discharge test of Example 47, showing the charge curves of the 3rd cycle, 30th cycle and 60th cycle. FIG. 39 is a graph showing the results of the charge / discharge test of Example 48, showing the charge curves of the 3rd, 30th and 60th cycles. FIG. 40 is a graph showing the results of the charge / discharge test of Example 49, showing a discharge curve for 3 cycles, and a charge curve for 30th cycle and 60th cycle. FIG. 41 is a graph showing the results of the charge / discharge test of Example 51, showing the charge curves of the 3rd, 30th, and 60th cycles. FIG. 42 is a graph showing the results of the charge / discharge test of Example 53, showing the charge curves of the 3rd, 30th, and 60th cycles. FIG. 43 is a graph showing the results of the charge / discharge test of Example 55, showing the charge curves of the 3rd, 30th, and 60th cycles. FIG. 44 is a graph showing the results of the charge / discharge test of Example 57, showing the charge curves of the 5th cycle, 30th cycle and 60th cycle. FIG. 45 is a graph showing the results of the charge / discharge test of Example 58, showing the charge curves of the 5th cycle, 30th cycle and 60th cycle. FIG. 46 is a graph showing the results of the charge / discharge test of Example 59, showing the charge curves of the 5th cycle, 30th cycle and 60th cycle. FIG. 47 is a graph showing the results of the charge / discharge test of Example 60, showing the charge curves of the 5th, 30th, and 60th cycles. FIG. 48 is a graph showing the results of the charge / discharge test of Example 61, showing the charge curves of the 5th cycle, 30th cycle and 60th cycle. FIG. 49 is a graph showing the results of the charge / discharge test of Example 62, showing the charge curves of the 1st, 3rd, 30th and 60th cycles. FIG. 50 is a graph showing the results of the charge / discharge test of Example 63, and shows a charge curve and a discharge curve in the second cycle.

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 following examples, each physical property value is a measured value according to the following method or, in the case of a commercial product, a nominal value in a catalog. Further, zinc oxide is one kind of zinc oxide unless otherwise specified.
The average particle diameter other than the average particle diameter of zinc oxide of Examples 5, 6, 9-18, 21-32, 34-37, 39-63, and the aspect ratio are S-3500 type manufactured by Hitachi High-Technologies Corporation. Using a scanning electron microscope (SEM), 200 typical particles were measured, and the average value of the observed values was calculated.
The average particle diameter, mode diameter, and median diameter of the zinc oxides of Examples 5, 6, 9-18, 21-32, 34-37, and 39-63 are laser analysis / scattering type particle size distribution measuring apparatus manufactured by HORIBA. It measured using LA-950V2 Wet, the particle | grains were scattered in ion-exchange water, and the measured value after ultrasonic irradiation for 5 minutes was described.
The true density was measured using Accupic II-1340 manufactured by Shimadzu Corporation.
The specific surface area was measured using a fully automatic BET specific surface area measuring device manufactured by Mountec.
The amount of dissolved oxygen was measured using an oxygen meter (UC-12-SOL type / used electrode: UC-203 type) manufactured by Central Science Co., Ltd.

Example 1
Zinc oxide (average particle size: 20 nm, specific surface area: about 20 m ^{2 /} g) 10.6 g, vapor grown carbon fiber (multi-walled carbon nanotube) (aspect ratio (vertical / horizontal): 100, specific surface area: about 10 m ² / g) g, average fiber length: about 15 μm (0.35 g) and bismuth oxide (average particle diameter: about 50 μm) 0.87 g were put in a bottle, and pulverized for 12 hours by a ball mill using zirconia balls. The obtained solid was sieved to make the average particle size 25 μm or less. 1.3 g of this solid, 2.2 g of a 12% polyvinylidene fluoride / N-methylpyrrolidone solution, and 1.0 g of N-methylpyrrolidone were added to a glass vial, and the mixture was stirred overnight with a stirrer using a stirrer bar. The obtained slurry was coated on a copper foil using an automatic coating apparatus, dried at 80 ° C. for 12 hours, and then dried in vacuum (room temperature) for 6 hours. The copper foil coated with the zinc mixture was pressed at a press pressure of 1 t, and the film thickness of the zinc mixture was 10 μm. This was punched out with a punching machine (diameter: 15.95 mm) to form a zinc mixture electrode, and the working electrode (zinc mixture weight: 2.55 mg) having an apparent area of 0.48 cm ² was used. A zinc electrode is used for the counter electrode, a zinc wire is used for the reference electrode, and a 4 mol / L potassium hydroxide aqueous solution (dissolved oxygen amount 5.2 mg / L) in which zinc oxide is dissolved is used for the electrolyte. Using the cell, a charge / discharge test was conducted at a current value of 1.38 mA (charge / discharge time: 1 hour each / cut off at -0.2V and 0.4V).

(Example 2)
Zinc oxide (average particle size: 20 nm, specific surface area: about 20 m ^{2 /} g) 10.5 g, acetylene black (AB) (average particle size: about 40 nm, specific surface area: about 70 m ^{2 /} g) 0.36 g, tin oxide (Average particle diameter: about 5 μm, specific surface area: about 5 m ² / g or less) 0.87 g was put in a bottle, and pulverized for 12 hours by a ball mill using zirconia balls. The obtained solid was sieved to make the average particle size 25 μm or less. 1.29 g of this solid, 2.17 g of a 12% polyvinylidene fluoride / N-methylpyrrolidone solution, and 1.2 g of N-methylpyrrolidone were added to a glass vial, and the mixture was stirred overnight with a stirrer using a stirrer bar. The obtained slurry was coated on a copper foil using an automatic coating apparatus, dried at 80 ° C. for 12 hours, and then dried in vacuum (room temperature) for 6 hours. The copper foil coated with the zinc mixture was pressed at a press pressure of 1 t, and the film thickness of the zinc mixture was 10 μm. This was punched out with a punching machine (diameter: 15.95 mm) to form a zinc mixture electrode, and the working electrode having an apparent area of 0.48 cm ² (zinc mixture weight: 2.88 mg) was used. A zinc electrode is used for the counter electrode, a zinc wire is used for the reference electrode, and a 4 mol / L potassium hydroxide aqueous solution (dissolved oxygen amount 5.2 mg / L) in which zinc oxide is dissolved is used for the electrolyte. Using the cell, a charge / discharge test was performed at a current value of 1.52 mA (charge / discharge time: 1 hour each / cut off at −0.1 V and 0.4 V).

(Example 3)
The zinc mixture electrode was prepared in the same process as in Example 2. The working electrode (zinc mixture weight: 2.64 mg) having an apparent area of 0.48 cm ² was used. A zinc electrode is used for the counter electrode, a zinc wire is used for the reference electrode, and a 4 mol / L potassium hydroxide aqueous solution (dissolved oxygen amount 5.2 mg / L) in which zinc oxide is dissolved is used for the electrolyte. Using the cell, a charge / discharge test was performed at a current value of 3.83 mA (charge / discharge time: 1 hour / -0.1V and 0.4V cut off).

Example 4
10.5 g of zinc oxide (average particle size: 1200 μm) and 0.36 g of acetylene black (average particle size: about 40 nm, specific surface area: about 70 m ² / g) were put in a bottle and stirred for 2 hours by a self-revolving mixer. 1.2 g of the obtained solid, 2.0 g of a 12% polyvinylidene fluoride / N-methylpyrrolidone solution, and 1.1 g of N-methylpyrrolidone were added to a glass vial, and the mixture was stirred overnight with a stirrer using a stirrer bar. The obtained slurry was coated on a copper foil using an automatic coating apparatus, dried at 80 ° C. for 12 hours, and then dried in vacuum (room temperature) for 6 hours. The copper foil coated with the zinc mixture was pressed at a press pressure of 1 t, and the film thickness of the zinc mixture was 10 μm. This was punched out with a punching machine (diameter: 15.95 mm) to form a zinc mixture electrode, which was used as a working electrode with an apparent area of 0.48 cm ² (zinc mixture weight: 2.67 mg). A zinc electrode is used for the counter electrode, a zinc wire is used for the reference electrode, and a 4 mol / L potassium hydroxide aqueous solution (dissolved oxygen amount 5.2 mg / L) in which zinc oxide is dissolved is used for the electrolyte. Using the cell, a charge / discharge test was performed at a current value of 1.45 mA (charge / discharge time: 1 hour each / cut off at -0.2V and 0.4V). When the surface of the zinc mixture electrode after the charge / discharge test was observed by SEM, it was found that the shape of the zinc electrode active material was changed.

(Example 5)
Zinc oxide (average particle diameter: about 1.1 μm, mode diameter: about 820 nm, median diameter: about 760 nm, true density: about 5.98 g / cm ³ , specific surface area: about 4 m ² / g) 27.6 g, acetylene black (Average particle diameter: about 40 nm, specific surface area: about 70 m ² / g) 0.90 g, indium (III) oxide (manufactured by Nacalai Tesque) 2.4 g, ethanol (99.5%, Wako Pure Chemical Industries, Ltd.) 92.7 g) and 92.7 g of water were added to the ball mill, and ball mill mixing was performed. 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 the mixture was stirred overnight with a stirrer using a stirrer bar. The obtained slurry was coated on a copper foil using an automatic coating apparatus and dried at 80 ° C. for 12 hours. The copper foil coated with the zinc mixture was pressed at a press pressure of 3 t so that the film thickness of the zinc mixture was 10 μm or less. This was punched out with a punching machine (diameter: 15.95 mm) to form a zinc mixture electrode, which was used as a working electrode having an apparent area of 0.48 cm ² (zinc mixture weight: 1.75 mg). A zinc electrode is used for the counter electrode, a zinc wire is used for the reference electrode, and a 4 mol / L potassium hydroxide aqueous solution (dissolved oxygen amount 5.2 mg / L) in which zinc oxide is dissolved is used for the electrolyte. Using the cell, a charge / discharge test was performed at a current value of 0.834 mA (charge / discharge time: 1 hour each / cut off at −0.1 V and 0.4 V).

(Example 6)
Zinc oxide (average particle diameter: about 1.1 μm, mode diameter: about 820 nm, median diameter: about 760 nm, true density: about 5.98 g / cm ³ , specific surface area: about 4 m ² / g) 27.6 g, acetylene black (Average particle size: about 50 nm, specific surface area: about 40 m ² / g) 0.90 g, indium (III) oxide (manufactured by Nacalai Tesque) 2.4 g, ethanol (99.5%, Wako Pure Chemical Industries, Ltd.) 92.7 g) and 92.7 g of water were added to the ball mill, and ball mill mixing was performed. 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 the mixture was stirred overnight with a stirrer using a stirrer bar. The obtained slurry was coated on a copper foil using an automatic coating apparatus and dried at 80 ° C. for 12 hours. The copper foil coated with the zinc mixture was pressed at a press pressure of 3 t so that the film thickness of the zinc mixture was 10 μm or less. This was punched with a punching machine (diameter: 15.95 mm) to make a zinc mixture electrode, and used as a working electrode having an apparent area of 0.48 cm ² (zinc mixture weight: 1.24 mg). A zinc electrode is used for the counter electrode, a zinc wire is used for the reference electrode, and a 4 mol / L potassium hydroxide aqueous solution (dissolved oxygen amount 5.2 mg / L) in which zinc oxide is dissolved is used for the electrolyte. A charge / discharge test was conducted using the cell at a current value of 0.590 mA (charge / discharge time: 1 hour / -0.1 V and 0.4 V cut off).

(Example 7)
Zinc oxide (average particle diameter: 1.7 μm, true density: about 5.95 g / cm ³ ) 27.6 g, acetylene black (average particle diameter: about 50 nm, specific surface area: about 40 m ² / g) 0.90 g, oxidation 2.4 g of indium (III) (manufactured by Nacalai Tesque Co., Ltd.), 92.7 g of ethanol (99.5%, manufactured by Wako Pure Chemical Industries, Ltd.) and 92.7 g of water were added to the ball mill, and ball mill mixing was performed. . 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 the mixture was stirred overnight with a stirrer using a stirrer bar. The obtained slurry was coated on a copper foil using an automatic coating apparatus and dried at 80 ° C. for 12 hours. The copper foil coated with the zinc mixture was pressed at a press pressure of 3 t so that the film thickness of the zinc mixture was 10 μm or less. This was punched out with a punching machine (diameter: 15.95 mm) to form a zinc mixture electrode, and the working electrode (zinc mixture weight: 0.80 mg) having an apparent area of 0.48 cm ² was used. A zinc electrode is used for the counter electrode, a zinc wire is used for the reference electrode, and a 4 mol / L potassium hydroxide aqueous solution (dissolved oxygen amount 5.2 mg / L) in which zinc oxide is dissolved is used for the electrolyte. Using the cell, a charge / discharge test was performed at a current value of 0.501 mA (charge / discharge time: 1 hour each / cut off at −0.1 V and 0.4 V).

(Example 8)
Zinc oxide (average particle size: 5.5 μm, true density: about 5.75 g / cm ³ ) 27.6 g, acetylene black (average particle size: about 50 nm, specific surface area: about 40 m ² / g) 0.90 g, oxidation 2.4 g of indium (III) (manufactured by Nacalai Tesque Co., Ltd.), 92.7 g of ethanol (99.5%, manufactured by Wako Pure Chemical Industries, Ltd.) and 92.7 g of water were added to the ball mill, and ball mill mixing was performed. . 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 the mixture was stirred overnight with a stirrer using a stirrer bar. The obtained slurry was coated on a copper foil using an automatic coating apparatus and dried at 80 ° C. for 12 hours. The copper foil coated with the zinc mixture was pressed at a press pressure of 3 t so that the film thickness of the zinc mixture was 10 μm or less. This was punched out with a punching machine (diameter: 15.95 mm) to form a zinc mixture electrode, which was used as a working electrode having an apparent area of 0.48 cm ² (zinc mixture weight: 1.16 mg). A zinc electrode is used for the counter electrode, a zinc wire is used for the reference electrode, and a 4 mol / L potassium hydroxide aqueous solution (dissolved oxygen amount 5.2 mg / L) in which zinc oxide is dissolved is used for the electrolyte. A charge / discharge test was conducted using the cell at a current value of 0.554 mA (charge / discharge time: 1 hour / -0.1V and 0.4V cut off).

Example 9
Zinc oxide (average particle diameter: about 1.1 μm, mode diameter: about 820 nm, median diameter: about 760 nm, true density: about 5.98 g / cm ³ , specific surface area: about 4 m ² / g) 27.6 g, acetylene black (Average particle diameter: about 50 nm, specific surface area: about 40 m ² / g) 0.90 g, bismuth oxide (III) (99.9%, manufactured by Wako Pure Chemical Industries, Ltd.) 2.4 g, ethanol (99.5% 92.7 g, manufactured by Wako Pure Chemical Industries, Ltd.) and 92.7 g of water were added to the ball mill, followed by ball mill mixing. 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 the mixture was stirred overnight with a stirrer using a stirrer bar. The obtained slurry was coated on a copper foil using an automatic coating apparatus and dried at 80 ° C. for 12 hours. The copper foil coated with the zinc mixture was pressed at a press pressure of 3 t so that the film thickness of the zinc mixture was 10 μm or less. This was punched out with a punching machine (diameter: 15.95 mm) to form a zinc mixture electrode, and the working electrode having an apparent area of 0.48 cm ² (zinc mixture weight: 1.32 mg) was used. A zinc electrode is used for the counter electrode, a zinc wire is used for the reference electrode, and a 4 mol / L potassium hydroxide aqueous solution (dissolved oxygen amount 5.2 mg / L) in which zinc oxide is dissolved is used for the electrolyte. Using the cell, a charge / discharge test was performed at a current value of 0.675 mA (charge / discharge time: 1 hour each / cut off at −0.1 V and 0.4 V).

(Example 10)
Zinc oxide (average particle diameter: about 1.1 μm, mode diameter: about 820 nm, median diameter: about 760 nm, true density: about 5.98 g / cm ³ , specific surface area: about 4 m ² / g) 27.6 g, acetylene black (Average particle diameter: about 50 nm, specific surface area: about 40 m ² / g) 0.90 g, titanium (IV) oxide (anatase type, manufactured by Wako Pure Chemical Industries, Ltd.) 2.4 g, ethanol (99.5%, sum) 92.7 g and 92.7 g of water were added to the ball mill and mixed with the ball mill. 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 the mixture was stirred overnight with a stirrer using a stirrer bar. The obtained slurry was coated on a copper foil using an automatic coating apparatus and dried at 80 ° C. for 12 hours. The copper foil coated with the zinc mixture was pressed at a press pressure of 3 t so that the film thickness of the zinc mixture was 10 μm or less. This was punched out with a punching machine (diameter: 15.95 mm) to form a zinc mixture electrode, and the working electrode (zinc mixture weight: 1.09 mg) having an apparent area of 0.48 cm ² was used. A zinc electrode is used for the counter electrode, a zinc wire is used for the reference electrode, and a 4 mol / L potassium hydroxide aqueous solution (dissolved oxygen amount 5.2 mg / L) in which zinc oxide is dissolved is used for the electrolyte. Using the cell, a charge / discharge test was performed at a current value of 0.519 mA (charge / discharge time: 1 hour each / cut off at −0.1 V and 0.4 V).

(Example 11)
Zinc oxide (average particle diameter: about 1.1 μm, mode diameter: about 820 nm, median diameter: about 760 nm, true density: about 5.98 g / cm ³ , specific surface area: about 4 m ² / g) 27.6 g, acetylene black (Average particle diameter: about 50 nm, specific surface area: about 40 m ² / g) 0.90 g, niobium oxide (V) (99.9%, manufactured by Wako Pure Chemical Industries, Ltd.) 2.4 g, ethanol (99.5% 92.7 g, manufactured by Wako Pure Chemical Industries, Ltd.) and 92.7 g of water were added to the ball mill, followed by ball mill mixing. 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 the mixture was stirred overnight with a stirrer using a stirrer bar. The obtained slurry was coated on a copper foil using an automatic coating apparatus and dried at 80 ° C. for 12 hours. The copper foil coated with the zinc mixture was pressed at a press pressure of 3 t so that the film thickness of the zinc mixture was 10 μm or less. This was punched out with a punching machine (diameter: 15.95 mm) to form a zinc mixture electrode, which was used as a working electrode having an apparent area of 0.48 cm ² (zinc mixture weight: 1.47 mg). A zinc electrode is used for the counter electrode, a zinc wire is used for the reference electrode, and a 4 mol / L potassium hydroxide aqueous solution (dissolved oxygen amount 5.2 mg / L) in which zinc oxide is dissolved is used for the electrolyte. Using the cell, a charge / discharge test was conducted at a current value of 0.703 mA (charge / discharge time: 1 hour each / cut off at −0.1 V and 0.4 V). When the surface of the zinc mixture electrode after the charge / discharge test was observed by SEM, it was found that the shape of the zinc electrode active material was not changed at all, and no passivation was formed.

(Example 12)
Zinc oxide (average particle diameter: about 1.1 μm, mode diameter: about 820 nm, median diameter: about 760 nm, true density: about 5.98 g / cm ³ , specific surface area: about 4 m ² / g) 27.6 g, acetylene black (Average particle diameter: about 50 nm, specific surface area: about 40 m ² / g) 0.90 g, cerium (IV) oxide (manufactured by Wako Pure Chemical Industries, Ltd.) 2.4 g, ethanol (99.5%, Wako Pure Chemical Industries, Ltd.) 92.7 g) (manufactured by Co., Ltd.) and 92.7 g of water were added to the ball mill and mixed with the ball mill. 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). 1.1 g of the obtained solid, 12 g of a 12% polyvinylidene fluoride / N-methylpyrrolidone solution, and 0.9 g of N-methylpyrrolidone were added to a glass vial, and the mixture was stirred overnight with a stirrer using a stirrer bar. The obtained slurry was coated on a copper foil using an automatic coating apparatus and dried at 80 ° C. for 12 hours. The copper foil coated with the zinc mixture was pressed at a press pressure of 3 t so that the film thickness of the zinc mixture was 10 μm or less. This was punched with a punching machine (diameter: 15.95 mm) to make a zinc mixture electrode, and used as a working electrode (zinc mixture weight: 1.28 mg) with an apparent area of 0.48 cm ² . A zinc electrode is used for the counter electrode, a zinc wire is used for the reference electrode, and a 4 mol / L potassium hydroxide aqueous solution (dissolved oxygen amount 5.2 mg / L) in which zinc oxide is dissolved is used for the electrolyte. Using the cell, a charge / discharge test was performed at a current value of 0.610 mA (charge / discharge time: 1 hour each / cut off at −0.1 V and 0.4 V). When the surface of the zinc mixture electrode after the charge / discharge test was observed by SEM, it was found that the shape of the zinc electrode active material was not changed at all, and no passivation was formed.

(Example 13)
Zinc oxide (average particle size: about 1.1 μm, mode size: about 820 nm, median size: about 760 nm, true density: about 5.98 g / cm ³ , specific surface area: about 4 m ² / g) 27.6 g, indium oxide (III) 2.4 g (manufactured by Nacalai Tesque Co., Ltd.) and 180.0 g of water were added to the ball mill, and ball mill mixing was performed. 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. 0.82 g of metal zinc powder (manufactured by Wako Pure Chemical Industries, Ltd.) is added to 27.4 g of the dried solid, and pulverized for 60 seconds at a rotational speed of 18000 rpm using a pulverizer (X-TREME MX1200XTM manufactured by WARING). While mixing. 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 the mixture was stirred overnight with a stirrer using a stirrer bar. The obtained slurry was coated on a copper foil using an automatic coating apparatus and dried at 80 ° C. for 12 hours. The copper foil coated with the zinc mixture was pressed at a press pressure of 3 t so that the film thickness of the zinc mixture was 10 μm or less. This was punched out with a punching machine (diameter: 15.95 mm) to form a zinc mixture electrode, which was used as a working electrode having an apparent area of 0.48 cm ² (zinc mixture weight: 1.46 mg). A zinc electrode is used for the counter electrode, a zinc wire is used for the reference electrode, and a 4 mol / L potassium hydroxide aqueous solution (dissolved oxygen amount 5.2 mg / L) in which zinc oxide is dissolved is used for the electrolyte. Using the cell, a charge / discharge test was conducted at a current value of 0.699 mA (charge / discharge time: 1 hour each / cut off at −0.1 V and 0.4 V).

(Example 14)
Zinc oxide (average particle diameter: about 1.1 μm, mode diameter: about 820 nm, median diameter: about 760 nm, true density: about 5.98 g / cm ³ , specific surface area: about 4 m ² / g) 27.6 g, acetylene black (Average particle diameter: about 50 nm, specific surface area: about 40 m ² / g) 0.90 g, manganese (II) oxide (made by Kishida Chemical Co., Ltd.) 2.4 g, ethanol (99.5%, Wako Pure Chemical Industries, Ltd.) 92.7 g) and 92.7 g of water were added to the ball mill, and ball mill mixing was performed. 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 the mixture was stirred overnight with a stirrer using a stirrer bar. The obtained slurry was coated on a copper foil using an automatic coating apparatus and dried at 80 ° C. for 12 hours. The copper foil coated with the zinc mixture was pressed at a press pressure of 3 t so that the film thickness of the zinc mixture was 10 μm or less. This was punched out with a punching machine (diameter: 15.95 mm) to form a zinc mixture electrode, which was used as a working electrode having an apparent area of 0.48 cm ² (zinc mixture weight: 1.47 mg). A zinc electrode is used for the counter electrode, a zinc wire is used for the reference electrode, and a 4 mol / L potassium hydroxide aqueous solution (dissolved oxygen amount 5.2 mg / L) in which zinc oxide is dissolved is used for the electrolyte. Using the cell, a charge / discharge test was conducted at a current value of 0.701 mA (charge / discharge time: 1 hour each / cut off at −0.1 V and 0.4 V).

(Example 15)
Zinc oxide (average particle diameter: about 1.1 μm, mode diameter: about 820 nm, median diameter: about 760 nm, true density: about 5.98 g / cm ³ , specific surface area: about 4 m ² / g) 27.6 g, acetylene black (Average particle diameter: about 50 nm, specific surface area: about 40 m ² / g) 0.90 g, manganese (IV) oxide (99.5%, manufactured by Wako Pure Chemical Industries, Ltd.) 2.4 g, ethanol (99.5% 92.7 g, manufactured by Wako Pure Chemical Industries, Ltd.) and 92.7 g of water were added to the ball mill, followed by ball mill mixing. 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). 1.1 g of the obtained solid, 12 g of a 12% polyvinylidene fluoride / N-methylpyrrolidone solution, and 0.9 g of N-methylpyrrolidone were added to a glass vial, and the mixture was stirred overnight with a stirrer using a stirrer bar. The obtained slurry was coated on a copper foil using an automatic coating apparatus and dried at 80 ° C. for 12 hours. The copper foil coated with the zinc mixture was pressed at a press pressure of 3 t so that the film thickness of the zinc mixture was 10 μm or less. This was punched out with a punching machine (diameter: 15.95 mm) to form a zinc mixture electrode, and the working electrode (zinc mixture weight: 1.15 mg) having an apparent area of 0.48 cm ² was used. A zinc electrode is used for the counter electrode, a zinc wire is used for the reference electrode, and a 4 mol / L potassium hydroxide aqueous solution (dissolved oxygen amount 5.2 mg / L) in which zinc oxide is dissolved is used for the electrolyte. Using the cell, a charge / discharge test was performed at a current value of 0.547 mA (charge / discharge time: 1 hour each / cut off at −0.1 V and 0.4 V).

(Example 16)
Zinc oxide (average particle diameter: about 1.1 μm, mode diameter: about 820 nm, median diameter: about 760 nm, true density: about 5.98 g / cm ³ , specific surface area: about 4 m ² / g) 27.6 g, acetylene black (Average particle diameter: about 50 nm, specific surface area: about 40 m ² / g) 0.9 g, zirconium oxide (IV) (manufactured by Wako Pure Chemical Industries, Ltd.) 2.4 g, ethanol (99.5%, Wako Pure Chemical Industries, Ltd.) 92.7 g) (manufactured by Co., Ltd.) and 92.7 g of water were added to the ball mill and mixed with the ball mill. 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). 1.1 g of the obtained solid, 12 g of a 12% polyvinylidene fluoride / N-methylpyrrolidone solution, and 0.9 g of N-methylpyrrolidone were added to a glass vial, and the mixture was stirred overnight with a stirrer using a stirrer bar. The obtained slurry was coated on a copper foil using an automatic coating apparatus and dried at 80 ° C. for 12 hours. The copper foil coated with the zinc mixture was pressed at a press pressure of 3 t so that the film thickness of the zinc mixture was 10 μm or less. This was punched out with a punching machine (diameter: 15.95 mm) to form a zinc mixture electrode, and the working electrode having an apparent area of 0.48 cm ² (zinc mixture weight: 1.51 mg) was used. A zinc electrode is used for the counter electrode, a zinc wire is used for the reference electrode, and a 4 mol / L potassium hydroxide aqueous solution (dissolved oxygen amount 5.2 mg / L) in which zinc oxide is dissolved is used for the electrolyte. A charge / discharge test was conducted using the cell at a current value of 0.720 mA (charge / discharge time: 1 hour / -0.1V and 0.4V cut off). When the surface of the zinc mixture electrode after the charge / discharge test was observed by SEM, it was found that the shape of the zinc electrode active material was not changed at all, and no passivation was formed.

(Example 17)
Zinc oxide (average particle diameter: about 1.1 μm, mode diameter: about 820 nm, median diameter: about 760 nm, true density: about 5.98 g / cm ³ , specific surface area: about 4 m ² / g) 27.6 g, acetylene black (Average particle diameter: about 50 nm, specific surface area: about 40 m ² / g) 0.9 g, calcium hydroxide (Wako Pure Chemical Industries, Ltd.) 2.4 g, ethanol (99.5%, Wako Pure Chemical Industries, Ltd.) 92.7 g) and 92.7 g of water were added to the ball mill, and ball mill mixing was performed. 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). 1.1 g of the obtained solid, 12 g of a 12% polyvinylidene fluoride / N-methylpyrrolidone solution, and 0.9 g of N-methylpyrrolidone were added to a glass vial, and the mixture was stirred overnight with a stirrer using a stirrer bar. The obtained slurry was coated on a copper foil using an automatic coating apparatus and dried at 80 ° C. for 12 hours. The copper foil coated with the zinc mixture was pressed at a press pressure of 3 t so that the film thickness of the zinc mixture was 10 μm or less. This was punched out with a punching machine (diameter: 15.95 mm) to form a zinc mixture electrode, and the working electrode (zinc mixture weight: 1.38 mg) having an apparent area of 0.48 cm ² was used. A zinc electrode is used for the counter electrode, a zinc wire is used for the reference electrode, and a 4 mol / L potassium hydroxide aqueous solution (dissolved oxygen amount 5.2 mg / L) in which zinc oxide is dissolved is used for the electrolyte. A charge / discharge test was conducted using the cell at a current value of 0.658 mA (charge / discharge time: 1 hour / -0.1 V and 0.4 V cut off).

(Example 18)
27.6 g of zinc oxide (two types of zinc oxide, average particle size: about 1.9 μm, mode size: about 820 nm, median size: about 906 nm, true density: about 5.89 g / cm ³ , average particle size: 500 nm), Acetylene black (average particle size: about 50 nm, specific surface area: about 40 m ² / g) 0.9 g, indium (III) oxide (manufactured by Nacalai Tesque) 2.4 g, ethanol (99.5%, Wako Pure Chemical Industries, Ltd.) 92.7 g) (manufactured by Co., Ltd.) and 92.7 g of water were added to the ball mill and mixed with the ball mill. 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). 1.1 g of the obtained solid, 12 g of a 12% polyvinylidene fluoride / N-methylpyrrolidone solution, and 0.9 g of N-methylpyrrolidone were added to a glass vial, and the mixture was stirred overnight with a stirrer using a stirrer bar. The obtained slurry was coated on a copper foil using an automatic coating apparatus and dried at 80 ° C. for 12 hours. The copper foil coated with the zinc mixture was pressed at a press pressure of 3 t so that the film thickness of the zinc mixture was 10 μm or less. This was punched out with a punching machine (diameter: 15.95 mm) to form a zinc mixture electrode, and the working electrode (zinc mixture weight: 1.59 mg) having an apparent area of 0.48 cm ² was used. A zinc electrode is used for the counter electrode, a zinc wire is used for the reference electrode, and a 4 mol / L potassium hydroxide aqueous solution (dissolved oxygen amount 5.2 mg / L) in which zinc oxide is dissolved is used for the electrolyte. Using the cell, a charge / discharge test was performed at a current value of 0.759 mA (charge / discharge time: 1 hour each / cut off at −0.1 V and 0.4 V).

(Example 19)
Acicular zinc oxide (average major axis diameter: 100 nm, average minor axis system: 20 nm, average aspect ratio: 5, specific surface area: 30 m ^{2 /} g), 27.6 g, acetylene black (average particle diameter: about 50 nm, specific surface area: About 40 m ² / g) 0.9 g, cerium (IV) oxide (made by Wako Pure Chemical Industries, Ltd.) 2.4 g, ethanol (99.5%, manufactured by Wako Pure Chemical Industries, Ltd.) 92.7 g, water 92. 7 g was added to the ball mill, and ball mill mixing was performed. 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). 1.1 g of the obtained solid, 12 g of a 12% polyvinylidene fluoride / N-methylpyrrolidone solution, and 0.9 g of N-methylpyrrolidone were added to a glass vial, and the mixture was stirred overnight with a stirrer using a stirrer bar. The obtained slurry was coated on a copper foil using an automatic coating apparatus and dried at 80 ° C. for 12 hours. The copper foil coated with the zinc mixture was pressed at a press pressure of 3 t so that the film thickness of the zinc mixture was 10 μm or less. This was punched out with a punching machine (diameter: 15.95 mm) to form a zinc mixture electrode, which was used as a working electrode having an apparent area of 0.48 cm ² (zinc mixture weight: 3.71 mg). A zinc electrode is used for the counter electrode, a zinc wire is used for the reference electrode, and a 4 mol / L potassium hydroxide aqueous solution (dissolved oxygen amount 5.2 mg / L) in which zinc oxide is dissolved is used for the electrolyte. Using the cell, a charge / discharge test was performed at a current value of 1.77 mA (charge / discharge time: 1 hour each / cut off at −0.1 V and 0.4 V).

(Example 20)
Acicular zinc oxide (average major axis diameter: 900 nm, average minor axis system: 60 nm, average aspect ratio: 15, specific surface area: 4 m ^{2 /} g), 27.6 g, acetylene black (average particle diameter: about 50 nm, specific surface area: About 40 m ² / g) 0.9 g, cerium (IV) oxide (made by Wako Pure Chemical Industries, Ltd.) 2.4 g, ethanol (99.5%, manufactured by Wako Pure Chemical Industries, Ltd.) 92.7 g, water 92. 7 g was added to the ball mill, and ball mill mixing was performed. 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). 1.1 g of the obtained solid, 12 g of a 12% polyvinylidene fluoride / N-methylpyrrolidone solution, and 0.9 g of N-methylpyrrolidone were added to a glass vial, and the mixture was stirred overnight with a stirrer using a stirrer bar. The obtained slurry was coated on a copper foil using an automatic coating apparatus and dried at 80 ° C. for 12 hours. The copper foil coated with the zinc mixture was pressed at a press pressure of 3 t so that the film thickness of the zinc mixture was 10 μm or less. This was punched out with a punching machine (diameter: 15.95 mm) to form a zinc mixture electrode, which was used as a working electrode having an apparent area of 0.48 cm ² (zinc mixture weight: 1.64 mg). A zinc electrode is used for the counter electrode, a zinc wire is used for the reference electrode, and a 4 mol / L potassium hydroxide aqueous solution (dissolved oxygen amount 5.2 mg / L) in which zinc oxide is dissolved is used for the electrolyte. Using the cell, a charge / discharge test was performed at a current value of 0.784 mA (charge / discharge time: 1 hour each / cut off at −0.1 V and 0.4 V).

(Example 21)
Zinc oxide (average particle diameter: about 2.0 μm, mode diameter: about 710 nm, median diameter: about 1.0 μm, true density: about 5.91 g / cm ³ , specific surface area: 3.5 m ² / g) 22.1 g , Acicular zinc oxide (average major axis diameter: 100 nm, average minor axis system: 20 nm, average aspect ratio: 5, specific surface area: 30 m ^{2 /} g), acetylene black (average particle diameter: about 50 nm, specific surface area) : About 40 m ² / g) 0.9 g, cerium (IV) oxide (Wako Pure Chemical Industries, Ltd.) 2.4 g, ethanol (99.5%, Wako Pure Chemical Industries, Ltd.) 92.7 g, water 92 0.7 g was added to the ball mill and mixed with the ball mill. 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). 1.1 g of the obtained solid, 12 g of a 12% polyvinylidene fluoride / N-methylpyrrolidone solution, and 0.9 g of N-methylpyrrolidone were added to a glass vial, and the mixture was stirred overnight with a stirrer using a stirrer bar. The obtained slurry was coated on a copper foil using an automatic coating apparatus and dried at 80 ° C. for 12 hours. The copper foil coated with the zinc mixture was pressed at a press pressure of 3 t so that the film thickness of the zinc mixture was 10 μm or less. This was punched out with a punching machine (diameter: 15.95 mm) to form a zinc mixture electrode, and the working electrode having an apparent area of 0.48 cm ² (zinc mixture weight: 1.78 mg) was used. A zinc electrode is used for the counter electrode, a zinc wire is used for the reference electrode, and a 4 mol / L potassium hydroxide aqueous solution (dissolved oxygen amount 5.2 mg / L) in which zinc oxide is dissolved is used for the electrolyte. Using the cell, a charge / discharge test was performed at a current value of 0.848 mA (charge / discharge time: 1 hour / -0.1V and 0.4V cut off).

(Example 22)
Zinc oxide (average particle diameter: about 2.0 μm, mode diameter: about 710 nm, median diameter: about 1.0 μm, true density: about 5.91 g / cm ³ ) 22.1 g, zinc oxide (average particle diameter: 5. 5 μm, true density: about 5.75 g / cm ³ ) 5.5 g, acetylene black (average particle size: about 50 nm, specific surface area: about 40 m ² / g), 0.9 g, cerium (IV) oxide (Wako Pure Chemical Industries, Ltd.) 2.4 g, 99.5% of ethanol (99.5%, manufactured by Wako Pure Chemical Industries, Ltd.) and 92.7 g of water were added to the ball mill and mixed with the ball mill. 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). 1.1 g of the obtained solid, 12 g of a 12% polyvinylidene fluoride / N-methylpyrrolidone solution, and 0.9 g of N-methylpyrrolidone were added to a glass vial, and the mixture was stirred overnight with a stirrer using a stirrer bar. The obtained slurry was coated on a copper foil using an automatic coating apparatus and dried at 80 ° C. for 12 hours. The copper foil coated with the zinc mixture was pressed at a press pressure of 3 t so that the film thickness of the zinc mixture was 10 μm or less. This was punched out with a punching machine (diameter: 15.95 mm) to form a zinc mixture electrode, and the working electrode (zinc mixture weight: 1.66 mg) having an apparent area of 0.48 cm ² was used. A zinc electrode is used for the counter electrode, a zinc wire is used for the reference electrode, and a 4 mol / L potassium hydroxide aqueous solution (dissolved oxygen amount 5.2 mg / L) in which zinc oxide is dissolved is used for the electrolyte. Using the cell, a charge / discharge test was conducted at a current value of 0.792 mA (charge / discharge time: 1 hour each / cut off at −0.1 V and 0.4 V).

(Example 23)
Zinc oxide (average particle diameter: about 1.1 μm, mode diameter: about 820 nm, median diameter: about 760 nm, true density: about 5.98 g / cm ³ , specific surface area: about 4 m ² / g) 27.6 g, conductivity Carbon black (average particle size: about 25 nm, specific surface area: about 225 m ² / g, manufactured by Tokai Carbon Co., Ltd.) 0.9 g, cerium oxide (IV) (manufactured by Wako Pure Chemical Industries, Ltd.) 2.4 g, ethanol (99 (5%, manufactured by Wako Pure Chemical Industries, Ltd.) 92.7 g and 92.7 g of water were added to the ball mill, followed by ball mill mixing. 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). 1.1 g of the obtained solid, 12 g of a 12% polyvinylidene fluoride / N-methylpyrrolidone solution, and 0.9 g of N-methylpyrrolidone were added to a glass vial, and the mixture was stirred overnight with a stirrer using a stirrer bar. The obtained slurry was coated on a copper foil using an automatic coating apparatus and dried at 80 ° C. for 12 hours. The copper foil coated with the zinc mixture was pressed at a press pressure of 3 t so that the film thickness of the zinc mixture was 10 μm or less. This was punched out with a punching machine (diameter: 15.95 mm) to form a zinc mixture electrode, and the working electrode (zinc mixture weight: 1.55 mg) having an apparent area of 0.48 cm ² was used. A zinc electrode is used for the counter electrode, a zinc wire is used for the reference electrode, and a 4 mol / L potassium hydroxide aqueous solution (dissolved oxygen amount 5.2 mg / L) in which zinc oxide is dissolved is used for the electrolyte. A charge / discharge test was conducted using the cell at a current value of 0.739 mA (charge / discharge time: 1 hour / -0.1V and 0.4V cut off).

(Example 24)
Zinc oxide (average particle diameter: about 1.1 μm, mode diameter: about 820 nm, median diameter: about 760 nm, true density: about 5.98 g / cm ³ , specific surface area: about 4 m ² / g) 27.6 g, artificial graphite Fine powder (average particle size: about 3 μm, specific surface area: about 40 m ² / g, Showa Denko KK) 0.9 g, cerium (IV) oxide (Wako Pure Chemical Industries, Ltd.) 2.4 g, ethanol (99 (5%, manufactured by Wako Pure Chemical Industries, Ltd.) 92.7 g and 92.7 g of water were added to the ball mill, followed by ball mill mixing. 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). 1.1 g of the obtained solid, 12 g of a 12% polyvinylidene fluoride / N-methylpyrrolidone solution, and 0.9 g of N-methylpyrrolidone were added to a glass vial, and the mixture was stirred overnight with a stirrer using a stirrer bar. The obtained slurry was coated on a copper foil using an automatic coating apparatus and dried at 80 ° C. for 12 hours. The copper foil coated with the zinc mixture was pressed at a press pressure of 3 t so that the film thickness of the zinc mixture was 10 μm or less. This was punched out with a punching machine (diameter: 15.95 mm) to form a zinc mixture electrode, which was used as a working electrode having an apparent area of 0.48 cm ² (zinc mixture weight: 1.46 mg). A zinc electrode is used for the counter electrode, a zinc wire is used for the reference electrode, and a 4 mol / L potassium hydroxide aqueous solution (dissolved oxygen amount 5.2 mg / L) in which zinc oxide is dissolved is used for the electrolyte. A charge / discharge test was conducted using the cell at a current value of 0.696 mA (charge / discharge time: 1 hour / -0.1V and 0.4V cut off).

(Example 25)
Zinc oxide (average particle diameter: about 1.1 μm, mode diameter: about 820 nm, median diameter: about 760 nm, true density: about 5.98 g / cm ³ , specific surface area: about 4 m ² / g) 27.6 g, artificial graphite Fine powder (average particle size: about 10 μm, specific surface area: about 15 m ² / g, manufactured by Showa Denko KK) 0.9 g, cerium (IV) oxide (manufactured by Wako Pure Chemical Industries, Ltd.) 2.4 g, ethanol (99 (5%, manufactured by Wako Pure Chemical Industries, Ltd.) 92.7 g and 92.7 g of water were added to the ball mill, followed by ball mill mixing. 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). 1.1 g of the obtained solid, 12 g of a 12% polyvinylidene fluoride / N-methylpyrrolidone solution, and 0.9 g of N-methylpyrrolidone were added to a glass vial, and the mixture was stirred overnight with a stirrer using a stirrer bar. The obtained slurry was coated on a copper foil using an automatic coating apparatus and dried at 80 ° C. for 12 hours. The copper foil coated with the zinc mixture was pressed at a press pressure of 3 t so that the film thickness of the zinc mixture was 10 μm or less. This was punched out with a punching machine (diameter: 15.95 mm) to make a zinc mixture electrode, and used as a working electrode having an apparent area of 0.48 cm ² (zinc mixture weight: 1.22 mg). A zinc electrode is used for the counter electrode, a zinc wire is used for the reference electrode, and a 4 mol / L potassium hydroxide aqueous solution (dissolved oxygen amount 5.2 mg / L) in which zinc oxide is dissolved is used for the electrolyte. A charge / discharge test was conducted using the cell at a current value of 0.583 mA (charge / discharge time: 1 hour / -0.1V and 0.4V cut off).

(Preparation example)
Into a 5 L separable flask, 88.9 g of calcium hydroxide (manufactured by Wako Pure Chemical Industries, Ltd.) and 1930 g of water were added and stirred to obtain an aqueous suspension. The aqueous suspension was heated to 60 ° C., and 684.3 g of 10 mass% aluminum sulfate aqueous solution was added to the separable flask while maintaining stirring, and stirring and mixing were performed for 4 hours while maintaining the liquid temperature at 60 ° C. Continued. Subsequently, stirring was stopped, and the mixture was allowed to stand overnight with cooling to lower the liquid temperature to room temperature. Next, the precipitate was separated by filtration. The resulting precipitate was identified by X-ray diffraction, the precipitate was confirmed to be ettringite _{(Ca 6 Al 2 (SO 4} ) 3 (OH) 12 · 26H 2 O). The obtained precipitate was dried at 100 ° C. for 1 day in a stationary drier, and then pulverized for 60 seconds at 18000 rpm using a pulverizer (X-TREME MX1200XTM manufactured by WARING). A dry dehydrated powder was obtained.

(Example 26)
Zinc oxide (average particle diameter: about 1.1 μm, mode diameter: about 820 nm, median diameter: about 760 nm, true density: about 5.98 g / cm ³ , specific surface area: about 4 m ² / g) 27.6 g, acetylene black (Average particle size: about 50 nm, specific surface area: about 40 m ^{2 /} g) 0.9 g, 2.4 g of dry dehydrated powder of ettringite obtained in the above preparation example, ethanol (99.5%, Wako Pure Chemical Industries, Ltd.) 92.7 g) and 92.7 g of water were added to the ball mill, and ball mill mixing was performed. 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). 1.1 g of the obtained solid, 12 g of a 12% polyvinylidene fluoride / N-methylpyrrolidone solution, and 0.9 g of N-methylpyrrolidone were added to a glass vial, and the mixture was stirred overnight with a stirrer using a stirrer bar. The obtained slurry was coated on a copper foil using an automatic coating apparatus and dried at 80 ° C. for 12 hours. The copper foil coated with the zinc mixture was pressed at a press pressure of 3 t so that the film thickness of the zinc mixture was 10 μm or less. This was punched out with a punching machine (diameter: 15.95 mm) to form a zinc mixture electrode, and the working electrode (zinc mixture weight: 1.13 mg) having an apparent area of 0.48 cm ² was used. A zinc electrode is used for the counter electrode, a zinc wire is used for the reference electrode, and a 4 mol / L potassium hydroxide aqueous solution (dissolved oxygen amount 5.2 mg / L) in which zinc oxide is dissolved is used for the electrolyte. A charge / discharge test was conducted using the cell at a current value of 0.540 mA (charge / discharge time: 1 hour / -0.1 V and 0.4 V cut off). When the surface of the zinc mixture electrode after the charge / discharge test was observed by SEM, it was found that the shape of the zinc electrode active material was not changed at all, and no passivation was formed.

(Example 27)
Zinc oxide (average particle diameter: about 1.1 μm, mode diameter: about 820 nm, median diameter: about 760 nm, true density: about 5.98 g / cm ³ , specific surface area: about 4 m ² / g) 27.6 g, graphitization Carbon black (average particle size: about 70 nm, specific surface area: about 27 m ² / g, manufactured by Tokai Carbon Co., Ltd.) 0.9 g, cerium oxide (IV) (manufactured by Wako Pure Chemical Industries, Ltd.) 2.4 g, ethanol (99 (5%, manufactured by Wako Pure Chemical Industries, Ltd.) 92.7 g and 92.7 g of water were added to the ball mill, followed by ball mill mixing. 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). 1.1 g of the obtained solid, 12 g of a 12% polyvinylidene fluoride / N-methylpyrrolidone solution, and 0.9 g of N-methylpyrrolidone were added to a glass vial, and the mixture was stirred overnight with a stirrer using a stirrer bar. The obtained slurry was coated on a copper foil using an automatic coating apparatus and dried at 80 ° C. for 12 hours. The copper foil coated with the zinc mixture was pressed at a press pressure of 3 t so that the film thickness of the zinc mixture was 10 μm or less. This was punched out with a punching machine (diameter: 15.95 mm) to form a zinc mixture electrode, which was used as a working electrode having an apparent area of 0.48 cm ² (zinc mixture weight: 1.29 mg). A zinc electrode is used for the counter electrode, a zinc wire is used for the reference electrode, and a 4 mol / L potassium hydroxide aqueous solution (dissolved oxygen amount 5.2 mg / L) in which zinc oxide is dissolved is used for the electrolyte. Using the cell, a charge / discharge test was performed at a current value of 0.597 mA (charge / discharge time: 1 hour each / cut off at −0.1 V and 0.4 V).

(Example 28)
Zinc oxide (average particle diameter: about 1.1 μm, mode diameter: about 820 nm, median diameter: about 760 nm, true density: about 5.98 g / cm ³ , specific surface area: about 4 m ² / g) 27.6 g, Ketjen Black (average particle size: about 40 nm, specific surface area: about 800 m ² / g) 0.9 g, cerium (IV) oxide (made by Wako Pure Chemical Industries, Ltd.) 2.4 g, ethanol (99.5%, Wako Pure Chemical) 92.7 g of Kogyo Co., Ltd. and 92.7 g of water were added to the ball mill and mixed with the ball mill. 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). 1.1 g of the obtained solid, 12 g of a 12% polyvinylidene fluoride / N-methylpyrrolidone solution, and 0.9 g of N-methylpyrrolidone were added to a glass vial, and the mixture was stirred overnight with a stirrer using a stirrer bar. The obtained slurry was coated on a copper foil using an automatic coating apparatus and dried at 80 ° C. for 12 hours. The copper foil coated with the zinc mixture was pressed at a press pressure of 3 t so that the film thickness of the zinc mixture was 10 μm or less. This was punched out with a punching machine (diameter: 15.95 mm) to form a zinc mixture electrode, and the working electrode (zinc mixture weight: 1.21 mg) having an apparent area of 0.48 cm ² was used. A zinc electrode is used for the counter electrode, a zinc wire is used for the reference electrode, and a 4 mol / L potassium hydroxide aqueous solution (dissolved oxygen amount 5.2 mg / L) in which zinc oxide is dissolved is used for the electrolyte. A charge / discharge test was conducted using the cell at a current value of 0.580 mA (charge / discharge time: 1 hour / -0.1V and 0.4V cut off).

(Example 29)
Zinc oxide (average particle diameter: about 1.1 μm, mode diameter: about 820 nm, median diameter: about 760 nm, true density: about 5.98 g / cm ³ , specific surface area: about 4 m ² / g) 27.6 g, carbon black (Average particle diameter: about 30 nm, specific surface area: about 250 m ² / g) 0.9 g, cerium (IV) oxide (made by Wako Pure Chemical Industries, Ltd.) 2.4 g, ethanol (99.5%, Wako Pure Chemical Industries, Ltd.) 92.7 g) (manufactured by Co., Ltd.) and 92.7 g of water were added to the ball mill and mixed with the ball mill. 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). 1.1 g of the obtained solid, 12 g of a 12% polyvinylidene fluoride / N-methylpyrrolidone solution, and 0.9 g of N-methylpyrrolidone were added to a glass vial, and the mixture was stirred overnight with a stirrer using a stirrer bar. The obtained slurry was coated on a copper foil using an automatic coating apparatus and dried at 80 ° C. for 12 hours. The copper foil coated with the zinc mixture was pressed at a press pressure of 3 t so that the film thickness of the zinc mixture was 10 μm or less. This was punched out with a punching machine (diameter: 15.95 mm) to form a zinc mixture electrode, which was used so as to have a working electrode (zinc mixture weight: 0.875 mg) with an apparent area of 0.48 cm ² . A zinc electrode is used for the counter electrode, a zinc wire is used for the reference electrode, and a 4 mol / L potassium hydroxide aqueous solution (dissolved oxygen amount 5.2 mg / L) in which zinc oxide is dissolved is used for the electrolyte. Using the cell, a charge / discharge test was performed at a current value of 0.418 mA (charge / discharge time: 1 hour each / cut off at −0.1 V and 0.4 V).

(Example 30)
The zinc mixture electrode prepared in Example 12 was used so as to have a working electrode (zinc mixture weight: 1.82 mg) having an apparent area of 0.79 cm ² . The counter electrode is a nickel electrode for the counter electrode (active material: nickel hydroxide, the capacity is set to more than three times that of the zinc electrode), and 7.3 mol / L hydroxide in which the zinc oxide is dissolved until the electrolyte is saturated. Using a potassium +1.0 mol / L potassium fluoride aqueous solution (dissolved oxygen amount 2.9 mg / L), a charge / discharge test was conducted at a current value of 1.20 mA using a bipolar cell (charge / discharge time: 1 each) Time / cut off at 1.9V and 1.2V). It was also confirmed that this charge / discharge test can be stably performed for at least 300 cycles.

(Example 31)
The zinc mixture electrode prepared in Example 12 was used so as to be a working electrode (zinc mixture weight: 6.21 mg) having an apparent area of 2.0 cm ² . The counter electrode is a nickel electrode (active material: cobalt-coated nickel hydroxide, the capacity is set to be at least three times that of the zinc electrode), and the electrolyte is a 7.3 mol / L potassium hydroxide aqueous solution in which zinc oxide is dissolved until saturation. (Dissolved oxygen amount of 3.2 mg / L), a non-woven fabric (2 sheets) and a polypropylene microporous film (1 sheet) are sandwiched between a zinc electrode and a nickel electrode as a separator, and a current of 3.01 mA using a coin cell The charge / discharge test was conducted using the values (charge / discharge time: cut off at 1 hour / 1.9 V and 1.2 V each).

(Example 32)
The zinc mixture electrode prepared in Example 12 was used so as to be a working electrode having an apparent area of 2.0 cm ² (zinc mixture weight: 10.3 mg). The counter electrode is a nickel electrode (active material: cobalt-coated nickel hydroxide, the capacity is set to be at least three times that of the zinc electrode), and the electrolyte is a 7.3 mol / L potassium hydroxide aqueous solution in which zinc oxide is dissolved until saturation. (Dissolved oxygen amount of 3.2 mg / L), a non-woven fabric (2 sheets) and a polypropylene microporous film (1 sheet) are sandwiched between a zinc electrode and a nickel electrode as a separator, and a current of 1.49 mA using a coin cell The charge / discharge test was performed with the values (charge / discharge time: 3 hours 20 minutes / 1.9 V and 1.2 V cut off each).

(Example 33)
The zinc plate was immersed in an 8M KOH aqueous solution (dissolved oxygen concentration: 3.5 mg / L or 6.8 mg / L) for 5 hours, and the surface of the zinc plate was observed using Miniscope TM3000 (manufactured by Hitachi High-Technologies Corporation). .

(Example 34)
A zinc mixture electrode was prepared according to the formulation of Example 11, and a charge / discharge test was performed using the same apparatus and conditions as in Example 11 (10 cycles). The charge capacity at the 10th cycle was 657 mAh / g. Next, the discharge operation was performed under the same conditions, and all the zinc oxide in the zinc mixture electrode was converted into metal zinc, and then left for 24 hours, and then the charge operation was performed under the same conditions. The discharge capacity at this time was 657 mAh / g, and it was found that no self-discharge occurred.

(Example 35)
A zinc mixture electrode was prepared according to the formulation of Example 12, and a charge / discharge test was performed using the same apparatus and conditions as in Example 12 (10 cycles). The charge capacity at the 10th cycle was 655 mAh / g. Next, the discharge operation was performed under the same conditions, and all the zinc oxide in the zinc mixture electrode was converted into metal zinc, and then left for 24 hours, and then the charge operation was performed under the same conditions. The discharge capacity at this time was 630 mAh / g, and it was found that self-discharge hardly occurred.

(Example 36)
A zinc mixture electrode was prepared according to the formulation of Example 16, and a charge / discharge test was performed using the same apparatus and conditions as in Example 16 (10 cycles). The charge capacity at the 10th cycle was 658 mAh / g. Next, the discharge operation was performed under the same conditions, and all the zinc oxide in the zinc mixture electrode was converted into metal zinc, and then left for 24 hours, and then the charge operation was performed under the same conditions. The discharge capacity at this time was 658 mAh / g, and it was found that no self-discharge occurred.

(Example 37)
A zinc mixture electrode was prepared according to the formulation of Example 24, and a charge / discharge test was performed using the same apparatus and conditions as in Example 24 (10 cycles). The charge capacity at the 10th cycle was 650 mAh / g. Next, the discharge operation was performed under the same conditions, and all the zinc oxide in the zinc mixture electrode was converted into metal zinc, and then left for 24 hours, and then the charge operation was performed under the same conditions. The discharge capacity at this time was 574 mAh / g, and it was found that self-discharge was effectively suppressed.

(Example 38)
A zinc mixture electrode was prepared according to the formulation of Example 4, and a charge / discharge test was performed using the same apparatus and conditions as in Example 4 (10 cycles). The charge capacity at the 10th cycle was 380 mAh / g. Next, the discharge operation was performed under the same conditions, and all the zinc oxide in the zinc mixture electrode was converted into metal zinc, and then left for 24 hours, and then the charge operation was performed under the same conditions. The discharge capacity at this time was 0 mAh / g, and it was found that self-discharge occurred.

(Example 39)
Zinc oxide (average particle diameter: about 1.1 μm, mode diameter: about 820 nm, median diameter: about 760 nm, true density: about 5.98 g / cm ³ , specific surface area: about 4 m ² / g) 27.6 g, conductivity Carbon black (average particle size: about 25 nm, specific surface area: about 225 m ² / g, manufactured by Tokai Carbon Co., Ltd.) 0.9 g, zirconium oxide (IV) (manufactured by Wako Pure Chemical Industries, Ltd.) 2.4 g, ethanol (99 (5%, manufactured by Wako Pure Chemical Industries, Ltd.) 92.7 g and 92.7 g of water were added to the ball mill, followed by ball mill mixing. 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). 1.1 g of the obtained solid, 12 g of a 12% polyvinylidene fluoride / N-methylpyrrolidone solution, and 0.9 g of N-methylpyrrolidone were added to a glass vial, and the mixture was stirred overnight with a stirrer using a stirrer bar. The obtained slurry was coated on a copper foil using an automatic coating apparatus and dried at 80 ° C. for 12 hours. The copper foil coated with the zinc mixture was pressed at a press pressure of 3 t so that the film thickness of the zinc mixture was 10 μm or less. This was punched with a punching machine (diameter: 15.95 mm) to make a zinc mixture electrode, and used as a working electrode having an apparent area of 0.48 cm ² (zinc mixture weight: 1.57 mg). A zinc electrode is used for the counter electrode, a zinc wire is used for the reference electrode, and a 4 mol / L potassium hydroxide aqueous solution (dissolved oxygen amount 5.2 mg / L) in which zinc oxide is dissolved is used for the electrolyte. A charge / discharge test was performed using the cell at a current value of 0.762 mA (charge / discharge time: 1 hour / -0.1V and 0.4V cut off). The charge capacity at the 10th cycle was 654 mAh / g. Next, the discharge operation was performed under the same conditions, and all the zinc oxide in the zinc mixture electrode was converted into metal zinc, and then left for 24 hours, and then the charge operation was performed under the same conditions. The discharge capacity at this time was 655 mAh / g, and it was found that no self-discharge occurred.

(Example 40)
Zinc oxide (average particle diameter: about 1.1 μm, mode diameter: about 820 nm, median diameter: about 760 nm, true density: about 5.98 g / cm ³ , specific surface area: about 4 m ² / g) 27.6 g, graphitization Carbon black (average particle size: about 70 nm, specific surface area: about 27 m ² / g, manufactured by Tokai Carbon Co., Ltd.) 0.9 g, zirconium oxide (IV) (manufactured by Wako Pure Chemical Industries, Ltd.) 2.4 g, ethanol (99 (5%, manufactured by Wako Pure Chemical Industries, Ltd.) 92.7 g and 92.7 g of water were added to the ball mill, followed by ball mill mixing. 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). 1.1 g of the obtained solid, 12 g of a 12% polyvinylidene fluoride / N-methylpyrrolidone solution, and 0.9 g of N-methylpyrrolidone were added to a glass vial, and the mixture was stirred overnight with a stirrer using a stirrer bar. The obtained slurry was coated on a copper foil using an automatic coating apparatus and dried at 80 ° C. for 12 hours. The copper foil coated with the zinc mixture was pressed at a press pressure of 3 t so that the film thickness of the zinc mixture was 10 μm or less. This was punched with a punching machine (diameter: 15.95 mm) to make a zinc mixture electrode, and used as a working electrode with an apparent area of 0.48 cm ² (zinc mixture weight: 2.45 mg). A zinc electrode is used for the counter electrode, a zinc wire is used for the reference electrode, and a 4 mol / L potassium hydroxide aqueous solution (dissolved oxygen amount 5.2 mg / L) in which zinc oxide is dissolved is used for the electrolyte. Using the cell, a charge / discharge test was performed at a current value of 1.19 mA (charge / discharge time: 1 hour each / cut off at −0.1 V and 0.4 V). The charge capacity at the 10th cycle was 658 mAh / g. Next, the discharge operation was performed under the same conditions, and all the zinc oxide in the zinc mixture electrode was converted into metal zinc, and then left for 24 hours, and then the charge operation was performed under the same conditions. The discharge capacity at this time was 638 mAh / g, and it was found that self-discharge hardly occurred.

(Example 41)
Zinc oxide (average particle diameter: about 1.1 μm, mode diameter: about 820 nm, median diameter: about 760 nm, true density: about 5.98 g / cm ³ , specific surface area: about 4 m ² / g) 27.6 g, artificial graphite Fine powder (average particle size: about 3 μm, specific surface area: about 40 m ² / g, manufactured by Showa Denko KK) 0.9 g, zirconium oxide (IV) (manufactured by Wako Pure Chemical Industries, Ltd.) 2.4 g, ethanol (99 (5%, manufactured by Wako Pure Chemical Industries, Ltd.) 92.7 g and 92.7 g of water were added to the ball mill, followed by ball mill mixing. 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). 1.1 g of the obtained solid, 12 g of a 12% polyvinylidene fluoride / N-methylpyrrolidone solution, and 0.9 g of N-methylpyrrolidone were added to a glass vial, and the mixture was stirred overnight with a stirrer using a stirrer bar. The obtained slurry was coated on a copper foil using an automatic coating apparatus and dried at 80 ° C. for 12 hours. The copper foil coated with the zinc mixture was pressed at a press pressure of 3 t so that the film thickness of the zinc mixture was 10 μm or less. This was punched out with a punching machine (diameter: 15.95 mm) to form a zinc mixture electrode, and the working electrode (zinc mixture weight: 2.85 mg) having an apparent area of 0.48 cm ² was used. A zinc electrode is used for the counter electrode, a zinc wire is used for the reference electrode, and a 4 mol / L potassium hydroxide aqueous solution (dissolved oxygen amount 5.2 mg / L) in which zinc oxide is dissolved is used for the electrolyte. A charge / discharge test was conducted using the cell at a current value of 1.38 mA (charge / discharge time: 1 hour each / cut off at −0.1 V and 0.4 V). The charge capacity at the 10th cycle was 647 mAh / g. Next, the discharge operation was performed under the same conditions, and all the zinc oxide in the zinc mixture electrode was converted into metal zinc, and then left for 24 hours, and then the charge operation was performed under the same conditions. The discharge capacity at this time was 620 mAh / g, and it was found that self-discharge hardly occurred.

(Example 42)
Zinc oxide (average particle diameter: about 1.1 μm, mode diameter: about 820 nm, median diameter: about 760 nm, true density: about 5.98 g / cm ³ , specific surface area: about 4 m ² / g) 27.6 g, Ketjen Black (average particle size: about 40 nm, specific surface area: about 800 m ² / g) 0.9 g, zirconium (IV) oxide (made by Wako Pure Chemical Industries, Ltd.) 2.4 g, ethanol (99.5%, Wako Pure Chemical) 92.7 g of Kogyo Co., Ltd. and 92.7 g of water were added to the ball mill and mixed with the ball mill. 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). 1.1 g of the obtained solid, 12 g of a 12% polyvinylidene fluoride / N-methylpyrrolidone solution, and 0.9 g of N-methylpyrrolidone were added to a glass vial, and the mixture was stirred overnight with a stirrer using a stirrer bar. The obtained slurry was coated on a copper foil using an automatic coating apparatus and dried at 80 ° C. for 12 hours. The copper foil coated with the zinc mixture was pressed at a press pressure of 3 t so that the film thickness of the zinc mixture was 10 μm or less. This was punched out with a punching machine (diameter: 15.95 mm) to form a zinc mixture electrode, and the working electrode (zinc mixture weight: 1.59 mg) having an apparent area of 0.48 cm ² was used. A zinc electrode is used for the counter electrode, a zinc wire is used for the reference electrode, and a 4 mol / L potassium hydroxide aqueous solution (dissolved oxygen amount 5.2 mg / L) in which zinc oxide is dissolved is used for the electrolyte. A charge / discharge test was performed using the cell at a current value of 0.769 mA (charge / discharge time: 1 hour each / cut off at −0.1 V and 0.4 V). The charge capacity at the 10th cycle was 647 mAh / g. Next, the discharge operation was performed under the same conditions, and all the zinc oxide in the zinc mixture electrode was converted into metal zinc, and then left for 24 hours, and then the charge operation was performed under the same conditions. The discharge capacity at this time was 620 mAh / g, and it was found that self-discharge hardly occurred.

(Example 43)
Zinc oxide (average particle diameter: about 1.1 μm, mode diameter: about 820 nm, median diameter: about 760 nm, true density: about 5.98 g / cm ³ , specific surface area: about 4 m ² / g) 27.6 g, carbon black (Average particle diameter: about 12 nm, specific surface area: about 1200 m ² / g) 0.9 g, cerium (IV) oxide (made by Wako Pure Chemical Industries, Ltd.) 2.4 g, ethanol (99.5%, Wako Pure Chemical Industries, Ltd.) 92.7 g) (manufactured by Co., Ltd.) and 92.7 g of water were added to the ball mill and mixed with the ball mill. 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). 1.1 g of the obtained solid, 12 g of a 12% polyvinylidene fluoride / N-methylpyrrolidone solution, and 0.9 g of N-methylpyrrolidone were added to a glass vial, and the mixture was stirred overnight with a stirrer using a stirrer bar. The obtained slurry was coated on a copper foil using an automatic coating apparatus and dried at 80 ° C. for 12 hours. The copper foil coated with the zinc mixture was pressed at a press pressure of 3 t so that the film thickness of the zinc mixture was 10 μm or less. This was punched out with a punching machine (diameter: 15.95 mm) to form a zinc mixture electrode, and the working electrode (zinc mixture weight: 2.06 mg) having an apparent area of 0.48 cm ² was used. A zinc electrode is used for the counter electrode, a zinc wire is used for the reference electrode, and a 4 mol / L potassium hydroxide aqueous solution (dissolved oxygen amount 5.2 mg / L) in which zinc oxide is dissolved is used for the electrolyte. Using the cell, a charge / discharge test was conducted at a current value of 0.991 mA (charge / discharge time: 1 hour each / cut off at −0.1 V and 0.4 V).

(Example 44)
Zinc oxide (average particle diameter: about 1.1 μm, mode diameter: about 820 nm, median diameter: about 760 nm, true density: about 5.98 g / cm ³ , specific surface area: about 4 m ² / g) 27.6 g, scaly Natural graphite (average particle size: about 6.5 μm) 0.9 g, cerium (IV) oxide (Wako Pure Chemical Industries, Ltd.) 2.4 g, ethanol (99.5%, Wako Pure Chemical Industries, Ltd.) 92 0.7 g and 92.7 g of water were added to the ball mill, and ball mill mixing was performed. 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). 1.1 g of the obtained solid, 12 g of a 12% polyvinylidene fluoride / N-methylpyrrolidone solution, and 0.9 g of N-methylpyrrolidone were added to a glass vial, and the mixture was stirred overnight with a stirrer using a stirrer bar. The obtained slurry was coated on a copper foil using an automatic coating apparatus and dried at 80 ° C. for 12 hours. The copper foil coated with the zinc mixture was pressed at a press pressure of 3 t so that the film thickness of the zinc mixture was 10 μm or less. This was punched out with a punching machine (diameter: 15.95 mm) to form a zinc mixture electrode, which was used as a working electrode having an apparent area of 0.48 cm ² (zinc mixture weight: 2.74 mg). A zinc electrode is used for the counter electrode, a zinc wire is used for the reference electrode, and a 4 mol / L potassium hydroxide aqueous solution (dissolved oxygen amount 5.2 mg / L) in which zinc oxide is dissolved is used for the electrolyte. Using the cell, a charge / discharge test was performed at a current value of 1.33 mA (charge / discharge time: 1 hour each / cut off at −0.1 V and 0.4 V).

(Example 45)
Zinc oxide (average particle size: about 1.1 μm, mode size: about 820 nm, median size: about 760 nm, true density: about 5.98 g / cm ³ , specific surface area: about 4 m ² / g) 27.6 g, bulk natural Graphite (average particle size: about 7.8 μm) 0.9 g, cerium (IV) oxide (Wako Pure Chemical Industries, Ltd.) 2.4 g, ethanol (99.5%, Wako Pure Chemical Industries, Ltd.) 92. 7 g and 92.7 g of water were added to the ball mill, and ball mill mixing was performed. 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). 1.1 g of the obtained solid, 12 g of a 12% polyvinylidene fluoride / N-methylpyrrolidone solution, and 0.9 g of N-methylpyrrolidone were added to a glass vial, and the mixture was stirred overnight with a stirrer using a stirrer bar. The obtained slurry was coated on a copper foil using an automatic coating apparatus and dried at 80 ° C. for 12 hours. The copper foil coated with the zinc mixture was pressed at a press pressure of 3 t so that the film thickness of the zinc mixture was 10 μm or less. This was punched with a punching machine (diameter: 15.95 mm) to make a zinc mixture electrode, and used as a working electrode having an apparent area of 0.48 cm ² (zinc mixture weight: 1.57 mg). A zinc electrode is used for the counter electrode, a zinc wire is used for the reference electrode, and a 4 mol / L potassium hydroxide aqueous solution (dissolved oxygen amount 5.2 mg / L) in which zinc oxide is dissolved is used for the electrolyte. A charge / discharge test was performed using the cell at a current value of 0.762 mA (charge / discharge time: 1 hour / -0.1V and 0.4V cut off).

(Example 46)
Zinc oxide (average particle size: about 1.1 μm, mode size: about 820 nm, median size: about 760 nm, true density: about 5.98 g / cm ³ , specific surface area: about 4 m ² / g) 27.6 g, thermal decomposition Graphite (average particle size: about 6.9 μm) 0.9 g, cerium (IV) oxide (made by Wako Pure Chemical Industries, Ltd.) 2.4 g, ethanol (99.5%, made by Wako Pure Chemical Industries, Ltd.) 92. 7 g and 92.7 g of water were added to the ball mill, and ball mill mixing was performed. 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). 1.1 g of the obtained solid, 12 g of a 12% polyvinylidene fluoride / N-methylpyrrolidone solution, and 0.9 g of N-methylpyrrolidone were added to a glass vial, and the mixture was stirred overnight with a stirrer using a stirrer bar. The obtained slurry was coated on a copper foil using an automatic coating apparatus and dried at 80 ° C. for 12 hours. The copper foil coated with the zinc mixture was pressed at a press pressure of 3 t so that the film thickness of the zinc mixture was 10 μm or less. This was punched out with a punching machine (diameter: 15.95 mm) to form a zinc mixture electrode, and the working electrode having an apparent area of 0.48 cm ² (zinc mixture weight: 1.80 mg) was used. A zinc electrode is used for the counter electrode, a zinc wire is used for the reference electrode, and a 4 mol / L potassium hydroxide aqueous solution (dissolved oxygen amount 5.2 mg / L) in which zinc oxide is dissolved is used for the electrolyte. Using the cell, a charge / discharge test was performed at a current value of 0.872 mA (charge / discharge time: 1 hour each / cut off at −0.1 V and 0.4 V).

(Example 47)
Zinc oxide (average particle diameter: about 1.1 μm, mode diameter: about 820 nm, median diameter: about 760 nm, true density: about 5.98 g / cm ³ , specific surface area: about 4 m ² / g) 27.6 g, spherical graphite (Average particle size: about 8.6 μm) 0.9 g, Cerium (IV) oxide (Wako Pure Chemical Industries, Ltd.) 2.4 g, Ethanol (99.5%, Wako Pure Chemical Industries, Ltd.) 92.7 g 92.7 g of water was added to the ball mill, and ball mill mixing was performed. 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). 1.1 g of the obtained solid, 12 g of a 12% polyvinylidene fluoride / N-methylpyrrolidone solution, and 0.9 g of N-methylpyrrolidone were added to a glass vial, and the mixture was stirred overnight with a stirrer using a stirrer bar. The obtained slurry was coated on a copper foil using an automatic coating apparatus and dried at 80 ° C. for 12 hours. The copper foil coated with the zinc mixture was pressed at a press pressure of 3 t so that the film thickness of the zinc mixture was 10 μm or less. This was punched out with a punching machine (diameter: 15.95 mm) to form a zinc mixture electrode, and the working electrode (zinc mixture weight: 2.00 mg) having an apparent area of 0.48 cm ² was used. A zinc electrode is used for the counter electrode, a zinc wire is used for the reference electrode, and a 4 mol / L potassium hydroxide aqueous solution (dissolved oxygen amount 5.2 mg / L) in which zinc oxide is dissolved is used for the electrolyte. Using the cell, a charge / discharge test was performed at a current value of 0.968 mA (charge / discharge time: 1 hour each / cut off at −0.1 V and 0.4 V).

(Example 48)
Zinc oxide (average particle diameter: about 1.1 μm, mode diameter: about 820 nm, median diameter: about 760 nm, true density: about 5.98 g / cm ³ , specific surface area: about 4 m ² / g) 27.6 g, graphitization Treated carbon microspheres (average particle size: about 270 nm) 0.9 g, cerium (IV) oxide (Wako Pure Chemical Industries, Ltd.) 2.4 g, ethanol (99.5%, Wako Pure Chemical Industries, Ltd.) 92 0.7 g and 92.7 g of water were added to the ball mill, and ball mill mixing was performed. 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). 1.1 g of the obtained solid, 12 g of a 12% polyvinylidene fluoride / N-methylpyrrolidone solution, and 0.9 g of N-methylpyrrolidone were added to a glass vial, and the mixture was stirred overnight with a stirrer using a stirrer bar. The obtained slurry was coated on a copper foil using an automatic coating apparatus and dried at 80 ° C. for 12 hours. The copper foil coated with the zinc mixture was pressed at a press pressure of 3 t so that the film thickness of the zinc mixture was 10 μm or less. This was punched out with a punching machine (diameter: 15.95 mm) to form a zinc mixture electrode, and the working electrode (zinc mixture weight: 1.84 mg) with an apparent area of 0.48 cm ² was used. A zinc electrode is used for the counter electrode, a zinc wire is used for the reference electrode, and a 4 mol / L potassium hydroxide aqueous solution (dissolved oxygen amount 5.2 mg / L) in which zinc oxide is dissolved is used for the electrolyte. Using the cell, a charge / discharge test was performed at a current value of 0.890 mA (charge / discharge time: 1 hour each / cut off at −0.1 V and 0.4 V).

(Example 49)
Zinc oxide (average particle diameter: about 1.1 μm, mode diameter: about 820 nm, median diameter: about 760 nm, true density: about 5.98 g / cm ³ , specific surface area: about 4 m ² / g) 30 g, acetylene black (average Particle diameter: about 40 nm, specific surface area: about 70 m ^{2 /} g) 0.90 g, ethanol (99.5%, manufactured by Wako Pure Chemical Industries, Ltd.) 92.7 g, water 92.7 g were added to the ball mill. Mixing was performed. 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 the mixture was stirred overnight with a stirrer using a stirrer bar. The obtained slurry was coated on a copper foil using an automatic coating apparatus and dried at 80 ° C. for 12 hours. The copper foil coated with the zinc mixture was pressed at a press pressure of 3 t so that the film thickness of the zinc mixture was 10 μm or less. This was punched out with a punching machine (diameter: 15.95 mm) to form a zinc mixture electrode, which was used as a working electrode having an apparent area of 0.48 cm ² (zinc mixture weight: 2.74 mg). A zinc electrode is used for the counter electrode, a zinc wire is used for the reference electrode, and a 4 mol / L potassium hydroxide aqueous solution (dissolved oxygen amount 5.2 mg / L) in which zinc oxide is dissolved is used for the electrolyte. Using the cell, a charge / discharge test was performed at a current value of 1.33 mA (charge / discharge time: 1 hour each / cut off at −0.1 V and 0.4 V). When the surface of the zinc mixture electrode after the charge / discharge test was observed by SEM, it was found that the shape of the zinc electrode active material was changed.

(Example 50)
A zinc mixture electrode was prepared according to the formulation of Example 49, and a charge / discharge test was performed using the same apparatus and conditions as in Example 49 (10 cycles). The charge capacity at the 10th cycle was 582 mAh / g. Next, the discharge operation was performed under the same conditions, and all the zinc oxide in the zinc mixture electrode was converted into metal zinc, and then left for 24 hours, and then the charge operation was performed under the same conditions. The discharge capacity at this time was 0 mAh / g, and it was found that self-discharge occurred.

(Example 51)
Zinc oxide (3 types of zinc oxide, average particle diameter: about 800 nm, mode diameter: about 107 nm, median diameter: about 368 nm, true density: about 5.85 g / cm ³ , specific surface area: about 4 m ² / g) 27.6 g Acetylene black (average particle size: about 50 nm, specific surface area: about 40 m ² / g) 0.9 g, cerium (IV) oxide (manufactured by Wako Pure Chemical Industries, Ltd.) 2.4 g, ethanol (99.5%, sum) 92.7 g and 92.7 g of water were added to the ball mill and mixed with the ball mill. 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). 1.1 g of the obtained solid, 12 g of a 12% polyvinylidene fluoride / N-methylpyrrolidone solution, and 0.9 g of N-methylpyrrolidone were added to a glass vial, and the mixture was stirred overnight with a stirrer using a stirrer bar. The obtained slurry was coated on a copper foil using an automatic coating apparatus and dried at 80 ° C. for 12 hours. The copper foil coated with the zinc mixture was pressed at a press pressure of 3 t so that the film thickness of the zinc mixture was 10 μm or less. This was punched out with a punching machine (diameter: 15.95 mm) to form a zinc mixture electrode, which was used as a working electrode having an apparent area of 0.48 cm ² (zinc mixture weight: 1.90 mg). A zinc electrode is used for the counter electrode, a zinc wire is used for the reference electrode, and a 4 mol / L potassium hydroxide aqueous solution (dissolved oxygen amount 5.2 mg / L) in which zinc oxide is dissolved is used for the electrolyte. Using the cell, a charge / discharge test was performed at a current value of 0.919 mA (charge / discharge time: 1 hour each / cut off at −0.1 V and 0.4 V).

(Example 52)
A zinc mixture electrode was prepared according to the formulation of Example 51, and a charge / discharge test was performed using the same apparatus and conditions as in Example 51 (10 cycles). The charge capacity at the 10th cycle was 470 mAh / g. Next, the discharge operation was performed under the same conditions, and all the zinc oxide in the zinc mixture electrode was converted into metal zinc, and then left for 24 hours, and then the charge operation was performed under the same conditions. The discharge capacity at this time was 0 mAh / g, and it was found that self-discharge occurred.

(Example 53)
Zinc oxide (2 types of zinc oxide, average particle diameter: about 1.1 μm, mode diameter: about 930 nm, median diameter: about 810 nm, true density: about 5.70 g / cm ³ , specific surface area: about 4 m ² / g) 27 1.6 g, acetylene black (average particle size: about 50 nm, specific surface area: about 40 m ² / g) 0.9 g, cerium (IV) oxide (manufactured by Wako Pure Chemical Industries, Ltd.) 2.4 g, ethanol (99.5% 92.7 g, manufactured by Wako Pure Chemical Industries, Ltd.) and 92.7 g of water were added to the ball mill, followed by ball mill mixing. 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). 1.1 g of the obtained solid, 12 g of a 12% polyvinylidene fluoride / N-methylpyrrolidone solution, and 0.9 g of N-methylpyrrolidone were added to a glass vial, and the mixture was stirred overnight with a stirrer using a stirrer bar. The obtained slurry was coated on a copper foil using an automatic coating apparatus and dried at 80 ° C. for 12 hours. The copper foil coated with the zinc mixture was pressed at a press pressure of 3 t so that the film thickness of the zinc mixture was 10 μm or less. This was punched out with a punching machine (diameter: 15.95 mm) to form a zinc mixture electrode, and the working electrode (zinc mixture weight: 2.19 mg) having an apparent area of 0.48 cm ² was used. A zinc electrode is used for the counter electrode, a zinc wire is used for the reference electrode, and a 4 mol / L potassium hydroxide aqueous solution (dissolved oxygen amount 5.2 mg / L) in which zinc oxide is dissolved is used for the electrolyte. Using the cell, a charge / discharge test was performed at a current value of 1.06 mA (charge / discharge time: 1 hour each / cut off at −0.1 V and 0.4 V).

(Example 54)
A zinc mixture electrode was prepared according to the formulation of Example 53, and a charge / discharge test was performed using the same apparatus and conditions as in Example 53 (10 cycles). The charge capacity at the 10th cycle was 610 mAh / g. Next, the discharge operation was performed under the same conditions, and all the zinc oxide in the zinc mixture electrode was converted into metal zinc, and then left for 24 hours, and then the charge operation was performed under the same conditions. The discharge capacity at this time was 0 mAh / g, and it was found that self-discharge occurred.

(Example 55)
Zinc oxide (2 types of zinc oxide, average particle diameter: about 1.1 μm, mode diameter: about 820 nm, median diameter: about 880 nm, true density: about 6.00 g / cm ³ , specific surface area: about 4 m ² / g) 27 1.6 g, acetylene black (average particle size: about 50 nm, specific surface area: about 40 m ² / g) 0.9 g, cerium (IV) oxide (manufactured by Wako Pure Chemical Industries, Ltd.) 2.4 g, ethanol (99.5% 92.7 g, manufactured by Wako Pure Chemical Industries, Ltd.) and 92.7 g of water were added to the ball mill, followed by ball mill mixing. 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). 1.1 g of the obtained solid, 12 g of a 12% polyvinylidene fluoride / N-methylpyrrolidone solution, and 0.9 g of N-methylpyrrolidone were added to a glass vial, and the mixture was stirred overnight with a stirrer using a stirrer bar. The obtained slurry was coated on a copper foil using an automatic coating apparatus and dried at 80 ° C. for 12 hours. The copper foil coated with the zinc mixture was pressed at a press pressure of 3 t so that the film thickness of the zinc mixture was 10 μm or less. This was punched with a punching machine (diameter: 15.95 mm) to make a zinc mixture electrode, and used as a working electrode having an apparent area of 0.48 cm ² (zinc mixture weight: 2.03 mg). A zinc electrode is used for the counter electrode, a zinc wire is used for the reference electrode, and a 4 mol / L potassium hydroxide aqueous solution (dissolved oxygen amount 5.2 mg / L) in which zinc oxide is dissolved is used for the electrolyte. Using the cell, a charge / discharge test was performed at a current value of 0.982 mA (charge / discharge time: 1 hour each / cut off at −0.1 V and 0.4 V).

(Example 56)
A zinc mixture electrode was prepared according to the formulation of Example 55, and a charge / discharge test was performed using the same apparatus and conditions as in Example 55 (10 cycles). The charge capacity at the 10th cycle was 658 mAh / g. Next, the discharge operation was performed under the same conditions, and all the zinc oxide in the zinc mixture electrode was converted into metal zinc, and then left for 24 hours, and then the charge operation was performed under the same conditions. The discharge capacity at this time was 658 mAh / g, and it was found that no self-discharge occurred.

(Example 57)
Zinc oxide (average particle diameter: about 1.1 μm, mode diameter: about 820 nm, median diameter: about 760 nm, true density: about 5.98 g / cm ³ , specific surface area: about 4 m ² / g) 27.6 g, acetylene black (Average particle diameter: about 50 nm, specific surface area: about 40 m ² / g) 0.90 g, lanthanum oxide (Wako Pure Chemical Industries, Ltd.) 2.4 g, ethanol (99.5%, Wako Pure Chemical Industries, Ltd.) ) 92.7 g and water 92.7 g were added to the ball mill, and ball mill mixing was performed. 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). 1.1 g of the obtained solid, 12 g of a 12% polyvinylidene fluoride / N-methylpyrrolidone solution, and 0.9 g of N-methylpyrrolidone were added to a glass vial, and the mixture was stirred overnight with a stirrer using a stirrer bar. The obtained slurry was coated on a copper foil using an automatic coating apparatus and dried at 80 ° C. for 12 hours. The copper foil coated with the zinc mixture was pressed at a press pressure of 3 t so that the film thickness of the zinc mixture was 10 μm or less. This was punched out with a punching machine (diameter: 15.95 mm) to form a zinc mixture electrode, and the working electrode (zinc mixture weight: 2.25 mg) having an apparent area of 0.48 cm ² was used. A zinc electrode is used for the counter electrode, a zinc wire is used for the reference electrode, and a 4 mol / L potassium hydroxide aqueous solution (dissolved oxygen amount 5.2 mg / L) in which zinc oxide is dissolved is used for the electrolyte. Using the cell, a charge / discharge test was performed at a current value of 1.07 mA (charge / discharge time: 1 hour each / cut off at −0.1 V and 0.4 V).

(Example 58)
Zinc oxide (average particle diameter: about 1.1 μm, mode diameter: about 820 nm, median diameter: about 760 nm, true density: about 5.98 g / cm ³ , specific surface area: about 4 m ² / g) 27.6 g, acetylene black (Average particle diameter: about 50 nm, specific surface area: about 40 m ² / g) 0.90 g, hydroxyapatite (Wako Pure Chemical Industries, Ltd.) 2.4 g, ethanol (99.5%, Wako Pure Chemical Industries, Ltd.) ) 92.7 g and water 92.7 g were added to the ball mill, and ball mill mixing was performed. 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). 1.1 g of the obtained solid, 12 g of a 12% polyvinylidene fluoride / N-methylpyrrolidone solution, and 0.9 g of N-methylpyrrolidone were added to a glass vial, and the mixture was stirred overnight with a stirrer using a stirrer bar. The obtained slurry was coated on a copper foil using an automatic coating apparatus and dried at 80 ° C. for 12 hours. The copper foil coated with the zinc mixture was pressed at a press pressure of 3 t so that the film thickness of the zinc mixture was 10 μm or less. This was punched out with a punching machine (diameter: 15.95 mm) to form a zinc mixture electrode, and the working electrode having an apparent area of 0.48 cm ² (zinc mixture weight: 2.60 mg) was used. A zinc electrode is used for the counter electrode, a zinc wire is used for the reference electrode, and a 4 mol / L potassium hydroxide aqueous solution (dissolved oxygen amount 5.2 mg / L) in which zinc oxide is dissolved is used for the electrolyte. A charge / discharge test was conducted using the cell at a current value of 1.24 mA (charge / discharge time: 1 hour each / cut off at −0.1 V and 0.4 V).

(Example 59)
Zinc oxide (average particle diameter: about 1.1 μm, mode diameter: about 820 nm, median diameter: about 760 nm, true density: about 5.98 g / cm ³ , specific surface area: about 4 m ² / g) 27.6 g, acetylene black (Average particle size: about 50 nm, specific surface area: about 40 m ² / g) 0.90 g, 2.4 g of zirconium oxide stabilized with yttrium oxide, ethanol (99.5%, manufactured by Wako Pure Chemical Industries, Ltd.) 92 0.7 g and 92.7 g of water were added to the ball mill, and ball mill mixing was performed. 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). 1.1 g of the obtained solid, 12 g of a 12% polyvinylidene fluoride / N-methylpyrrolidone solution, and 0.9 g of N-methylpyrrolidone were added to a glass vial, and the mixture was stirred overnight with a stirrer using a stirrer bar. The obtained slurry was coated on a copper foil using an automatic coating apparatus and dried at 80 ° C. for 12 hours. The copper foil coated with the zinc mixture was pressed at a press pressure of 3 t so that the film thickness of the zinc mixture was 10 μm or less. This was punched out with a punching machine (diameter: 15.95 mm) to form a zinc mixture electrode, and the working electrode (zinc mixture weight: 2.34 mg) with an apparent area of 0.48 cm ² was used. A zinc electrode is used for the counter electrode, a zinc wire is used for the reference electrode, and a 4 mol / L potassium hydroxide aqueous solution (dissolved oxygen amount 5.2 mg / L) in which zinc oxide is dissolved is used for the electrolyte. Using the cell, a charge / discharge test was performed at a current value of 1.11 mA (charge / discharge time: 1 hour each / cut off at −0.1 V and 0.4 V).

(Example 60)
Zinc oxide (average particle diameter: about 1.1 μm, mode diameter: about 820 nm, median diameter: about 760 nm, true density: about 5.98 g / cm ³ , specific surface area: about 4 m ² / g) 27.6 g, acetylene black (Average particle size: about 50 nm, specific surface area: about 40 m ² / g) 0.90 g, 2.4 g of zirconium oxide stabilized with scandium oxide, ethanol (99.5%, manufactured by Wako Pure Chemical Industries, Ltd.) 92 0.7 g and 92.7 g of water were added to the ball mill, and ball mill mixing was performed. 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). 1.1 g of the obtained solid, 12 g of a 12% polyvinylidene fluoride / N-methylpyrrolidone solution, and 0.9 g of N-methylpyrrolidone were added to a glass vial, and the mixture was stirred overnight with a stirrer using a stirrer bar. The obtained slurry was coated on a copper foil using an automatic coating apparatus and dried at 80 ° C. for 12 hours. The copper foil coated with the zinc mixture was pressed at a press pressure of 3 t so that the film thickness of the zinc mixture was 10 μm or less. This was punched out with a punching machine (diameter: 15.95 mm) to form a zinc mixture electrode, and the working electrode having an apparent area of 0.48 cm ² (zinc mixture weight: 1.71 mg) was used. A zinc electrode is used for the counter electrode, a zinc wire is used for the reference electrode, and a 4 mol / L potassium hydroxide aqueous solution (dissolved oxygen amount 5.2 mg / L) in which zinc oxide is dissolved is used for the electrolyte. A charge / discharge test was performed using the cell at a current value of 0.81 mA (charge / discharge time: 1 hour each / cut off at −0.1 V and 0.4 V).

(Example 61)
Zinc oxide (average particle diameter: about 1.1 μm, mode diameter: about 820 nm, median diameter: about 760 nm, true density: about 5.98 g / cm ³ , specific surface area: about 4 m ² / g) 27.6 g, acetylene black (Average particle diameter: about 50 nm, specific surface area: about 40 m ² / g) 0.90 g, cerium oxide-zirconium oxide solid solution (CeO ₂ / ZrO ₂ / Y ₂ O ₃ = 25/74/1) 2.4 g, ethanol (99.5%, manufactured by Wako Pure Chemical Industries, Ltd.) 92.7 g and 92.7 g of water were added to the ball mill, and ball mill mixing was performed. 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). 1.1 g of the obtained solid, 12 g of a 12% polyvinylidene fluoride / N-methylpyrrolidone solution, and 0.9 g of N-methylpyrrolidone were added to a glass vial, and the mixture was stirred overnight with a stirrer using a stirrer bar. The obtained slurry was coated on a copper foil using an automatic coating apparatus and dried at 80 ° C. for 12 hours. The copper foil coated with the zinc mixture was pressed at a press pressure of 3 t so that the film thickness of the zinc mixture was 10 μm or less. This was punched out with a punching machine (diameter: 15.95 mm) to form a zinc mixture electrode, and the working electrode (zinc mixture weight: 2.47 mg) having an apparent area of 0.48 cm ² was used. A zinc electrode is used for the counter electrode, a zinc wire is used for the reference electrode, and a 4 mol / L potassium hydroxide aqueous solution (dissolved oxygen amount 5.2 mg / L) in which zinc oxide is dissolved is used for the electrolyte. Using the cell, a charge / discharge test was performed at a current value of 1.17 mA (charge / discharge time: 1 hour each / cut off at −0.1 V and 0.4 V).

(Example 62)
Into a 2 L beaker, 58.7 g of zinc chloride (special grade reagent, manufactured by Wako Pure Chemical Industries, Ltd.) and 900 g of water were completely dissolved. A solution in which 0.9 g of indium oxide (manufactured by Nacalai Tesque Co., Ltd.) 0.9 was dissolved in 1 g was added to the beaker and mixed with stirring to obtain a uniform aqueous solution. Next, 14 mass% aqueous ammonia was gradually added to the aqueous solution until the pH reached 8 while stirring the aqueous solution. Stirring was continued for 15 minutes after the addition of ammonia water was completed, and then stirring was stopped, and the mixture was allowed to stand for 2 hours to confirm the formation of a precipitate. Subsequently, the precipitate and the supernatant were separated by filtration. The obtained precipitate was sufficiently washed with water and ethanol, and then the washed precipitate was dried overnight at 60 ° C. under reduced pressure. The obtained dry solid (powder) was baked at 500 ° C. for 2 hours in the air to obtain zinc oxide powder doped with indium oxide. The composition (weight ratio) of this powder was ZnO / In ₂ O ₃ = 97.5 / 2.5.
30.0 g of zinc oxide powder doped with indium oxide obtained above, acetylene black (average particle size: about 50 nm, specific surface area: about 40 m ^{2 /} g), ethanol (99.5%, sum) 92.7 g and 92.7 g of water were added to the ball mill and mixed with the ball mill. Thereafter, a zinc mixture electrode was prepared in the same manner as in Example 5 and used so as to have a working electrode (zinc mixture weight: 1.80 mg) having an apparent area of 0.48 cm ² . Similarly to Example 5, a charge / discharge test was conducted using a triode cell at a current value of 0.87 mA (charge / discharge time: 1 hour each).

(Example 63)
The zinc mixture electrode prepared in Example 12 was used so as to be a working electrode (zinc mixture weight: 1.26 mg) having an apparent area of 0.50 cm ² . The counter electrode is an air electrode (QSI-Nano manganese gas diffusion electrode manufactured by Sakai Kogyo Co., Ltd.) with an air hole in the counter electrode, and 8 mol / L potassium hydroxide in which zinc oxide is dissolved until the electrolyte is saturated. Using a +20 g / L lithium hydroxide aqueous solution (dissolved oxygen amount 2.9 mg / L), a charge / discharge test was conducted at a current value of 0.829 mA using a bipolar cell (charge / discharge time: 20 minutes / 2 each) Cut off at 0V and 0.5V).

The following was found from the results of the examples.
A zinc negative electrode mixture in which the zinc-containing compound and / or the conductive auxiliary agent includes particles having an average particle diameter of 1000 μm or less and / or particles having an aspect ratio (vertical / horizontal) of 1.1 or more. The storage battery constituted by using a negative electrode for zinc and using the negative electrode is excellent in the cycle characteristics of the battery, and the deterioration of the battery performance is suppressed even when repeated charge and discharge are repeated. It was proved that the coulomb efficiency was excellent.
In particular, a zinc negative electrode mixture in which the zinc-containing compound and the conductive auxiliary agent include particles having an average particle diameter of 1000 μm or less and / or particles having an aspect ratio (vertical / horizontal) of 1.1 or more was used. In this case, it was found that a storage battery constituted by forming a zinc negative electrode from such a zinc negative electrode mixture and using the negative electrode has extremely excellent cycle characteristics of the battery.
Further, in the zinc negative electrode mixture, the other components (compounds having at least one element selected from the group consisting of elements belonging to groups 1 to 17 of the periodic table, organic compounds, and organic compound salts) By containing at least one selected from the above, it is possible to effectively suppress side reactions and corrosion reactions in which hydrogen is generated by the decomposition of water even when the battery is configured using a water-containing electrolyte. Thus, it was found that the charge / discharge characteristics and the coulomb efficiency could be remarkably improved, and further, the shape change and passive formation of the zinc electrode active material were suppressed.
Furthermore, it was found that by using a zinc-containing compound having a specific median diameter or a specific true density, self-discharge during charging or storage in a charged state is suppressed.
In addition, in the said Example, although the zinc negative electrode is formed using the zinc negative electrode mixture containing a specific zinc containing compound and a conductive support agent, zinc of this invention is used as the zinc negative electrode mixture which forms a zinc negative electrode. By using a negative electrode mixture, a battery constructed using such a zinc negative electrode has excellent battery performance such as cycle characteristics, rate characteristics, coulomb efficiency, and self-discharge suppression. The same applies to the case of using the zinc negative electrode mixture of the invention. 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 (15)

A zinc negative electrode mixture used in a secondary battery having a water-containing electrolyte,
The zinc negative electrode mixture includes a zinc-containing compound and conductive carbon as a conductive auxiliary agent,
The zinc-containing compound is zinc oxide and has a true density value of 5.50 to 6.50 g / cm ³ .
Particles having an average particle diameter of 10 μm to 300 nm, mode diameters of 5 μm to 100 nm, median diameters of 5 μm to 500 nm, and / or particles having an aspect ratio (vertical / horizontal) of 5 or more And a specific surface area of 0.1 m ² / g or more and 50 m ² / g or less, a zinc negative electrode mixture for a secondary battery having a water-containing electrolyte. The zinc negative electrode mixture further contains other components,
The other component is at least one selected from the group consisting of a compound having at least one element selected from the group consisting of elements belonging to Groups 1 to 17 of the periodic table, an organic compound, and an organic compound salt. The zinc negative electrode mixture for secondary batteries which has the water-containing electrolyte solution of Claim 1 characterized by the above-mentioned. It said zinc negative electrode mixture, the amount of other components, in mass ratio, relative to the zinc-containing compound 100 in the zinc anode mixture, according to claim 2, characterized in that 0.01 to 100 A zinc negative electrode mixture for secondary batteries having a water-containing electrolyte. The other components to claim 2 or 3, characterized in that it comprises an oxide and / or hydroxide of at least one element selected from the group consisting of elements belonging to 1-17 of the periodic table The zinc negative electrode mixture for secondary batteries which has the water-containing electrolyte solution of description. The element belonging to Group 1 to 17 of the periodic table is at least one element selected from the group consisting of Al, Ca, Ce, La, Nb, Nd, P, Sc, Y, and Zr. rechargeable battery zinc anode mixture having a water content electrolyte according to any of claims 2-4 for. The conductive additive, a secondary battery for zinc anode mixture having a water content electrolyte solution according to any one of claims 1-5 in which the average particle size, characterized in that it comprises particles is 500Myuemu～1nm. The conductive additive, a specific surface area of 0.1 m 2 / ^g or more, having a water content electrolyte solution according to any one of claims 1 to 6, characterized in that it comprises particles is less than 1500 m 2 / ^g Zinc negative electrode mixture for secondary batteries. Said zinc negative electrode mixture, the amount of conductive additive is in a mass ratio, claim 1-7 which respect the zinc-containing compound 100 in the zinc anode mixture, characterized in that it is a 0.0001 A zinc negative electrode mixture for a secondary battery comprising the water-containing electrolytic solution according to any one of the above. A zinc electrode for a secondary battery having a water-containing electrolyte, wherein the zinc electrode is formed using the zinc negative electrode mixture according to any one of claims 1 to 8. The said zinc electrode is used as a negative electrode, The zinc electrode for secondary batteries which has a water-containing electrolyte solution of Claim 9 characterized by the above-mentioned. A secondary battery comprising the zinc electrode according to claim 9 or 10 and a water-containing electrolyte. A secondary battery comprising the zinc electrode according to claim 9 or 10, a positive electrode active material, a separator, and a water-containing electrolyte. The secondary battery according to claim 12 , wherein the positive electrode active material is a nickel-containing compound. The secondary battery according to claim 12 , wherein the positive electrode active material is oxygen. The water-containing electrolyte has a dissolved oxygen concentration value (mg / L) (at 25 ° C.) of α = −0.26375 × β + 8.11 (β is a hydroxide ion concentration in the aqueous electrolyte to be used <mol / L> secondary battery according to any one of claims 11 to 14, characterized in that is less than α value calculated by the equation).