JP6397646B2 - Zinc electrode mixture - Google Patents

Description

The present invention relates to a mixture for a zinc electrode. More specifically, the present invention relates to a zinc electrode mixture that is excellent in economic efficiency, safety, and high performance and can be suitably used for forming a negative electrode of a battery, a zinc electrode formed using the same, and a battery.

In recent years, (storage) batteries have been applied in various industrial fields such as portable devices and automobiles, and the demand for such batteries has increased. Among these, from the viewpoint of safety, low cost, high performance, and elemental strategic advantage, the importance of development and improvement of a mixture for zinc electrodes, a zinc electrode, and a battery using the electrode is increasing. A zinc electrode mixture is a material that includes a zinc species as an electrode active material, and forms a battery electrode. A zinc electrode formed using a zinc electrode mixture is suitable for various applications. A battery that can be used will be provided.

As a conventional mixture for a zinc electrode, a mixture obtained by mixing and preparing a zinc-containing compound and other electrode material constituent components by a wet method is disclosed (for example, see Non-Patent Documents 1 to 3). .)

Electrochimica Acta 56 (2011) 4378-4383 Electrochimica Acta 54 (2009) 6617-6621 Journal of Power Sources 165 (2007) 905-910

Various methods for mixing zinc-containing compounds such as zinc oxide and other electrode material constituents have been studied as preparation methods for zinc electrode mixtures, but mixing by a wet method such as a conventional coprecipitation method requires time and time. There were problems such as labor, cost, solvent selection, and waste liquid treatment. In addition, there has been room for further improvement in the performance of the electrode obtained by using a mixture obtained by mixing by a conventional wet method. On the other hand, in the dry method, there is a method using a ball mill, a raiki machine, etc., but when mixing by these methods, depending on the mixing conditions, the average particle size of the zinc-containing compound particles as the mother particles is too small. There is a problem that the performance of the obtained electrode is deteriorated.

The present invention has been made in view of the above situation, and it is possible to improve the rate characteristics by suitably dispersing the electrode material constituents in the mixture, and to improve the charge / discharge cycle characteristics in the secondary battery. An object of the present invention is to provide a zinc electrode mixture that can be produced, and a zinc electrode and a battery that are configured using the zinc electrode mixture.

The present inventors have intensively studied in order to obtain a zinc electrode mixture capable of exhibiting excellent performance, and a zinc-containing compound and an electrode material component other than the zinc-containing compound are made into nanoparticles. The dispersed zinc electrode mixture was considered to have a high possibility of exhibiting excellent performance. In order to obtain such a mixture for zinc electrodes, the present inventors first made nano-particles of electrode material components containing specific elements other than zinc as electrode materials, and obtained nano-sized electrode material components. When mixed with zinc-containing compound particles, the nanoparticles are likely to aggregate at the time of mixing, and it is difficult to uniformly disperse the electrode material constituents in the zinc electrode mixture and the electrode obtained from the mixture. I found the problem that the performance of the electrode was inferior. The inventors of the present invention have further studied earnestly, and by mixing the zinc-containing compound and the nanoparticles by dry stirring, the nanoparticles can be uniformly dispersed in the mixture, and zinc is contained before and after stirring. It has been found that it is possible to suppress changes in the average particle size of the compound. And the present inventors can make the average particle diameter of the zinc-containing compound particles in the mixture 0.6 μm or more by the dry stirring and mixing, and if the average particle diameter, the electrode active material is suitable. It has been found that it can be used, and nanoparticles can be uniformly dispersed in the mixture, and a zinc electrode with very good performance can be suitably produced. In addition, the present inventors have an average particle size of a zinc-containing compound in a mixture obtained by mixing by a conventional wet method, which is smaller than 0.6 μm, which can be suitably used as a zinc electrode mixture. In fact, the inventors have also found that the electrode and battery obtained from the mixture are not sufficiently satisfactory in performance. The present inventors further improved the rate characteristics of the battery, even when the amount of nanoparticles added as an electrode material component is small, and the electrode formed using the above-mentioned zinc electrode mixture improves the secondary characteristics of the battery. It has been found that an effect of improving charge / discharge cycle characteristics can be exhibited in a battery. The present inventors are not limited to the zinc electrode mixture obtained by the dry stirring and mixing, but for zinc electrodes in which a zinc-containing compound having an average particle size of 0.6 μm or more and the nanoparticles are uniformly dispersed. It was conceived that the above problem could be solved satisfactorily with a mixture, and the present invention has been achieved.

That is, the present invention is selected from the group consisting of a zinc-containing compound having an average particle diameter of 0.6 μm or more, and Groups 1 to 5, 11 and 13 to 17 of the periodic table. The zinc electrode mixture is characterized in that the nanoparticles containing the element are uniformly dispersed.

This invention is also a zinc electrode comprised using the mixture for zinc electrodes of this invention.
The present invention is also a battery configured using the zinc electrode of the present invention and an electrolytic solution.
The present invention is a method for producing a mixture for a zinc electrode, wherein the production method comprises a zinc-containing compound, a group 1 to a group 5, a group 11 and a group 13 to a group of the periodic table. A step of dry mixing a nanoparticle containing an element selected from the group consisting of group 17 to obtain a zinc electrode mixture in which a zinc-containing compound having an average particle size of 0.6 μm or more and nanoparticles are uniformly dispersed It is also a manufacturing method of the mixture for zinc electrodes containing.
The present invention is described in detail below.
In addition, the form which combined two or more each preferable structure of this invention described below is also a preferable form of this invention.

The zinc negative electrode mixture of the present invention is a group consisting of a zinc-containing compound having an average particle size of 0.6 μm or more, and Groups 1 to 5, 11 and 13 to 17 of the periodic table. What is necessary is just to uniformly disperse nanoparticles containing an element selected from more. In the present specification, uniform dispersion may be any material that is recognized in the technical field of the present invention as being substantially dispersed as a primary particle in a zinc-containing compound of 0.6 μm or more. Nanoparticles are substantially dispersed as primary particles as long as the nanoparticles cannot be clearly recognized as aggregated or unevenly distributed as a whole, and some nanoparticles are in one place. It may be aggregated or unevenly distributed. The determination of uniform dispersion can be performed by confirming with a scanning electron microscope (SEM), for example.
Due to the uniform dispersion, in the electrode active material layer obtained from the mixture, there is no significant bias in the electrochemical reaction during charge and discharge, in other words, the electrochemical reaction proceeds uniformly throughout the active material layer. Thus, the effect of improving the battery performance is exhibited.
In the present invention, a zinc-containing compound having an average particle size of 0.6 μm or more and the above nanoparticles are mixed so as to suppress a change in the average particle size of the zinc-containing compound before and after stirring, for example, by dry stirring and mixing. It is preferable. For example, it is more preferable that the change rate of the average particle diameter of the zinc-containing compound before and after dry stirring and mixing is within ± 30%. The change ratio is more preferably within ± 25%, and particularly preferably within ± 20%.
Dry stirring and mixing refers to stirring with substantially solid components without adding liquid components.

The zinc electrode mixture of the present invention is preferably obtained by dry stirring and mixing the zinc-containing compound and the nanoparticles.
Dry stirring and mixing may be performed by using a ball mill ball, a ladle machine, or the like, without rubbing the inner wall of the container during mixing, and electrodes such as zinc-containing compound particles between the inner wall of the container A tool that does not grind the material constituent components may be used, but from the viewpoint of suppressing a change in the average particle size of the zinc-containing compound, a tool that uses the tool is preferable. Examples of the instrument include a stirrer, a mixer, a blender, and a kneader. In addition, the container should just partition the place where mixing is performed appropriately. An instrument generally called a stirrer can also be used. Examples of the stirrer include Nobilta cyclomix (product name, manufactured by Hosokawa Micron Corporation), Henschel mixer, and the like.
Moreover, it is one preferable form of this invention to perform the said dry stirring mixing using a stirring bar.

As described above, the stirring is preferably performed by appropriately setting the position of the rotating shaft, the shape and length of the stirring blade, etc. so as not to rub the inner wall of the container. For example, it is preferable that the longest distance from the rotating shaft to the end of the stirring blade is set to be less than the shortest length from the rotating shaft to the inner wall of the container.

Various shapes can be used for the stirring blade, and examples thereof include a propeller type, a paddle type, a turbine type, a cone type, a ribbon type, and a screw type.

In the dry stirring, the peripheral speed is preferably 0.01 m / S to 150 m / S. The peripheral speed is more preferably 0.015 m / S or more, still more preferably 0.02 m / S or more, and particularly preferably 1 m / S or more. Further, the peripheral speed is more preferably 130 m / S or less, still more preferably 120 m / S or less, and particularly preferably 110 m / S or less.

The dry stirring time is preferably 5 seconds to 8 hours. By stirring for 5 seconds or more, the nanoparticles can be dispersed more uniformly in the mixture. Moreover, the effect which suppresses that the average particle diameter of a zinc containing compound changes before and behind stirring becomes larger by stirring for 8 hours or less. The time for the dry stirring is more preferably 20 seconds or more, still more preferably 30 seconds or more, and particularly preferably 50 seconds or more. Further, the dry stirring time is more preferably 6 hours or less, still more preferably 4 hours or less, and particularly preferably 2 hours or less. What is necessary is just to set the time of the said dry stirring suitably with peripheral speed.

After the dry stirring and mixing step of the zinc-containing compound and the nanoparticles, water or an organic solvent may be added to produce a mixture. Moreover, operations such as sieving may be performed in order to align the zinc-containing compound particles and the like with a desired particle diameter. Furthermore, as long as the effect of the present invention is exhibited by dry stirring and mixing the zinc-containing compound and the nanoparticles, the wet electrode method and the dry method may be combined to prepare a zinc electrode mixture. For example, after the nanoparticles are mixed by a wet method, a solid mixture obtained by removing liquid components by drying and a zinc-containing compound are stirred and mixed by a dry method to obtain the zinc electrode mixture of the present invention. It may be prepared. Alternatively, the zinc-containing compound and the nanoparticles may be stirred and mixed by a dry method, and then an organic compound or the like may be further stirred and mixed by a wet method.

Examples of the zinc-containing compound include zinc oxide, zinc metal, zinc powder, zinc fiber, zinc hydroxide, zinc sulfide, tetrahydroxy zinc alkali metal salt, tetrahydroxy zinc alkaline earth metal salt, zinc fluoride, and the like. Periodic table represented by halides, zinc carboxylate compounds, zinc alloys, zinc borate, zinc phosphate, zinc hydrogen phosphate, zinc silicate, zinc aluminate, carbonate, bicarbonate, nitrate, sulfate, etc. Zinc (alloy) compounds, organic zinc compounds, zinc compound salts and the like having at least one element selected from the group consisting of elements belonging to Groups 1 to 17 of the above. Among these, zinc oxide, zinc metal, zinc powder, zinc fiber, zinc hydroxide, tetrahydroxy zinc alkali metal salt, tetrahydroxy zinc alkaline earth metal salt, zinc fluoride such as zinc fluoride, zinc carboxylate compound, Zinc alloys, zinc borate, zinc phosphate, zinc silicate, zinc aluminate, and zinc carbonate are more preferred. More preferred is zinc oxide.

Examples of the shape of the particles of the zinc-containing compound include powder, granules, scales, fibers, granules, polyhedrons, rods, rectangular parallelepipeds, cylinders, and the like.

The average particle size of the zinc-containing compound in the zinc electrode mixture of the present invention is 0.6 μm or more. The average particle diameter of the zinc-containing compound is more preferably 0.61 μm or more, and still more preferably 0.62 μm or more. The average particle size of the zinc-containing compound is preferably 100 μm or less, more preferably 10 μm or less, still more preferably 5 μm or less, and even more preferably 3 μm or less, particularly preferably. Is 2.5 μm or less.
The average particle size of the zinc-containing compound is any zinc at 10 different locations in the zinc electrode mixture using JSM-7600FA (product name: scanning electron microscope manufactured by JEOL Ltd.). A total of 20 contained compound particles can be selected, and the particle diameter can be measured and averaged. In addition, the average particle diameter is determined from the shape of the particles observed with the microscope (SEM), in the case of a rectangular parallelepiped, the length of the longest side is the particle diameter, and other cylindrical, spherical, and curved surfaces In the case of inclusions, polyhedra, scales, rods, etc., a two-dimensional shape created when one part of the particles is placed on the bottom and projected from the direction that maximizes the aspect ratio In this form, the length of the side connecting the longest point from one point to the other point is defined as the particle diameter.

In the zinc electrode mixture of the present invention, the proportion of particles having a particle diameter of less than 0.6 μm is preferably 60% by mass or less in the total amount of 100% by mass of the zinc-containing compound and nanoparticles described later. . The ratio of the particles is more preferably 55% by mass or less, and still more preferably 50% by mass or less.
The ratio of the above particles was determined by adding the zinc-containing compound and other particles in the zinc electrode mixture to ion-exchanged water to which 0.1% of sodium hexametaphosphate as a dispersant was added and ultrasonically irradiating and dispersing for 5 minutes. It can be measured by a laser diffraction / scattering type particle size distribution measuring apparatus LA-950 manufactured by HORIBA.
By appropriately setting the average particle size of the raw material zinc-containing compound before mixing, the ratio of the nanoparticles, and the mixing conditions of the zinc-containing compound and the nanoparticles, the average particles of the zinc-containing compound in the mixture It is possible to adjust the diameter and the proportion of particles having a particle diameter of less than 0.6 μm within a desired range.

The zinc-containing compound particles 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 0.2 m < ² > / g or more. Moreover, it is preferable that this specific surface area is 20 m < ² > / g or less.
The specific surface area can be measured by a specific surface area measuring device.

The aspect ratio (vertical / horizontal) of the particles of the zinc-containing compound can be measured, for example, when the particles of the zinc-containing compound are rectangular, columnar, spherical, curved surface-containing, polyhedral, scaly or rod-like. In some cases, it is preferably 1.1 to 100,000, more preferably 1.2 to 50,000, and still more preferably 1.5 to 10,000. When particles that satisfy the above average particle diameter and aspect ratio are not included, the charge / discharge cycle characteristics deteriorate due to the shape change and passivation formation of the negative electrode active material, and self-discharge during charging and storage in the charged state May be likely to occur.
The aspect ratio (vertical / horizontal) is determined from the shape of particles observed by TEM or SEM. In the case of a rectangular shape, the longest side is vertical, the second longest side is horizontal, and the vertical length is horizontal. It can be obtained by dividing by the length. In the case of a cylinder, sphere, curved surface, polyhedron, etc., when a certain part is placed on the bottom so that the aspect ratio is maximized, it is projected from the direction that maximizes the aspect ratio. Measure the length of a point farthest away from a point in a two-dimensional shape that can be made, with the longest side as the vertical, the shortest side of the straight line passing through the vertical center point as the horizontal, and the vertical length as the horizontal It can be obtained by dividing by the length of.

It is preferable that content of a zinc containing compound is 30 mass% or more with respect to 100 mass% of the mixture for zinc electrodes of this invention. More preferably, it is 40 mass% or more, More preferably, it is 50 mass% or more, More preferably, it is 70 mass% or more, Most preferably, it is 80 mass% or more. Moreover, it is preferable that content of a zinc containing compound is 99 mass% or less. More preferably, it is 98 mass% or less, More preferably, it is 97 mass% or less. Here, the mass of the zinc electrode mixture in the calculation of the content of the zinc-containing compound is the mass of the solid content of the mixture, and does not include the amount of the solvent in the mixture.
In addition, the mixture for zinc electrodes of this invention may contain the component which acts as another active material, as long as it contains a zinc containing compound.

The nanoparticles include an element selected from the group consisting of Group 1 to Group 5, Group 11 and Group 13 to Group 17 of the periodic table. The above nanoparticles enable effective suppression of battery performance deterioration due to active material shape change / passive formation, self-discharge during charging, hydrogen generation due to water decomposition, etc. In the characteristics and secondary battery, Coulomb efficiency and charge / discharge cycle characteristics are further improved. It also serves to significantly improve the storage stability of the battery.

As a simple substance and / or a compound having at least one element selected from the group consisting of elements belonging to Groups 1 to 5, 11 and 13 to 17 of the periodic table, Ag is used. Al, Au, Ba, B, Be, Bi, Ca, Ce, Cs, Cu, F, Ga, Ge, Hf, In, K, Li, Mg, Na, Nb, Pb, Rb, Sc, Si, P , S, Se, Sn, Sr, Sb, Ta, Te, Ti, Tl, V, Y, Zr, Group 1 to Group 5, Group 11 to Group 13 of the Periodic Table An oxide of at least one element selected from the group consisting of elements belonging to Group 17; hydroxide; layered double hydroxide; sulfide; halogen compound; carboxylate compound; carbonate compound; Sulfurous acid compound; Sulfuric acid compound; Sulfonic acid compound Silicate compounds; aluminate compounds; phosphoric acid compounds; hydrogen phosphate compound; boric acid compound; onium salts; ammonium salts; solid solution; simple metal; alloys. These elements may be doped in zinc oxide, or may be contained in a zinc-containing compound or a conductive additive.
Among these, oxides, hydroxides of at least one element selected from the group consisting of elements belonging to Group 1 to Group 5, Group 11 and Group 13 to Group 17 of the Periodic Table, Layered double hydroxide, halogen compound, carboxylate compound, carbonic acid compound, sulfuric acid compound, sulfonic acid compound, silicic acid compound, phosphoric acid compound, boric acid compound, onium salt, ammonium salt, solid solution, simple metal, alloy, nitride Ceramic is preferred. More preferably, it is an oxide of at least one element selected from the group consisting of elements belonging to Group 1 to Group 5, Group 11 and Group 13 to Group 17 of the periodic table. More preferably, it is an oxide of at least one element selected from the group consisting of elements belonging to Groups 3 to 5 and Groups 13 to 15 of the periodic table.

As an element in a simple substance and / or a compound having at least one element selected from the group consisting of elements belonging to Group 1 to Group 5, Group 11 and Group 13 to Group 17 of the periodic table , Ag, Al, Au, Ba, B, Be, Bi, Ca, Ce, Cs, Cu, F, Ga, Ge, Hf, In, K, Li, Mg, Na, Nb, Pb, Rb, Sc, Si P, S, Se, Sn, Sr, Sb, Ta, Te, Ti, Tl, V, Y, Zr, and at least one element selected from the group consisting of lanthanoids are preferred. More preferable elements are Ag, Al, Au, Ba, B, Bi, Ca, Ce, Cs, Cu, F, Ga, Ge, In, K, Li, Mg, Na, Nb, Pb, Sc, Si, P , S, Sn, Sr, Sb, Ta, Te, Ti, Tl, Y, Zr, and at least one element selected from the group consisting of lanthanoids.

As a simple substance and / or compound having at least one element selected from the group consisting of elements belonging to Groups 1 to 5, Group 11, and Groups 13 to 17 of the periodic table, for example, Specifically, silver oxide, aluminum oxide, barium oxide, bismuth oxide, bismuth-containing composite oxide, calcium oxide, calcium-containing composite oxide, lanthanum oxide, cerium oxide, cerium-containing composite oxide, cerium-containing solid solution, ytterbium oxide Lanthanoid oxides such as cesium oxide, gallium oxide, indium oxide, indium-containing composite oxide, potassium oxide, lithium oxide, magnesium oxide, magnesium-containing composite oxide, sodium oxide, niobium oxide, lead oxide, phosphorus oxide, tin oxide, Scandium oxide, antimony oxide, titanium oxide, yttrium oxide Zirconium oxide, zirconium oxide stabilized with scandium oxide, zirconium oxide stabilized with yttrium oxide, zirconium-containing composite oxide, germanium oxide, rubidium oxide, silicon oxide, strontium oxide, tellurium oxide, vanadium oxide, thallium oxide, Lanthanoid hydroxides such as gold, silver, copper, copper oxide, aluminum hydroxide, barium hydroxide, bismuth hydroxide, calcium hydroxide, cerium hydroxide, cesium hydroxide, indium hydroxide, potassium hydroxide, lanthanum hydroxide, Magnesium hydroxide, lithium hydroxide, sodium hydroxide, rubidium hydroxide, tin hydroxide, strontium hydroxide, antimony hydroxide, titanium hydroxide, zirconium hydroxide, thallium hydroxide, lithium fluoride, sodium fluoride, fluoride potassium Magnesium fluoride, calcium fluoride, barium fluoride, scandium fluoride, yttrium fluoride, lanthanoid fluoride, titanium fluoride, silver chloride, lithium chloride, magnesium chloride, sodium chloride, rubidium chloride, tin chloride, silver acetate, acetic acid Barium, bismuth acetate, calcium acetate, calcium tartrate, calcium glutamate, cerium acetate, cesium acetate, gallium acetate, indium acetate, potassium acetate, lanthanum acetate, lithium acetate, magnesium 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, cesium carbonate Gallium carbonate, indium carbonate, potassium carbonate, lanthanum carbonate, lithium carbonate, magnesium carbonate, sodium carbonate, lead carbonate, rubidium carbonate, tin carbonate, strontium carbonate, 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, aluminum nitrate, barium nitrate, bismuth nitrate, calcium nitrate, cerium nitrate, cesium nitrate, gallium nitrate, indium nitrate, potassium nitrate, glass Lanthanum, lithium nitrate, magnesium nitrate, sodium nitrate, lead nitrate, rubidium nitrate, tin nitrate, strontium nitrate, antimony nitrate, titanium nitrate, tellurium nitrate, vanadium nitrate, zirconium nitrate, potassium silicate, calcium silicate, magnesium silicate, Barium silicate, potassium phosphate, calcium phosphate, magnesium phosphate, barium phosphate, calcium borate, barium borate, layered double hydroxide (hydrotalcite etc.), clay compound, laponite, hydroxyapatite, cerium oxide-oxidation Solid solutions such as zirconium, ettringite, cement, and titanium nitride.

The said nanoparticle should just contain a particle | grain with a particle diameter of 100 nm or less. Thereby, performances such as rate characteristics and charge / discharge cycle characteristics can be improved.
In the present invention, the average particle size of the nanoparticles is preferably 100 nm or less. More preferably, it is 90 nm or less, More preferably, it is 80 nm or less, Most preferably, it is 70 nm or less. Moreover, it is preferable that the average particle diameter of the said nanoparticle is 1 nm or more. More preferably, it is 5 nm or more, More preferably, it is 7 nm or more, Especially preferably, it is 10 nm or more.
The average particle diameter can be measured using a particle size distribution measuring device.

The nanoparticles preferably have a specific surface area of 0.01 m ² / g or more. More preferably, it is not 0.1 m ² / g or more, further preferably not ^{1 m} 2 / g or more, and particularly preferably ^2m 2 / g or more. Moreover, it is preferable that this specific surface area is 500 m < ² > / g or less. More preferably, it is 300 m < ² > / g or less, More preferably, it is 200 m < ² > / g or less, Most preferably, it is 100 m < ² > / g or less.
The specific surface area can be measured by a specific surface area measuring device.

In addition, it is preferable that the ratio of the said nanoparticle is 0.01-60 mass% with respect to 100 mass% of mixture for zinc electrodes. By being 0.01 mass% or more, the rate characteristic of a battery can be improved and the effect of improving charge / discharge cycle characteristics can be more sufficiently exhibited in a secondary battery. The proportion of the nanoparticles is more preferably 0.05% by mass or more, still more preferably 0.1% by mass or more, still more preferably 1% by mass or more, and particularly preferably 2% by mass. % Or more. Further, the ratio of the nanoparticles is more preferably 40% by mass or less, still more preferably 25% by mass or less, still more preferably 15% by mass or less, and particularly preferably 10% by mass or less. It is.

The zinc electrode mixture of the present invention may further contain a conductive additive in addition to the above-described zinc-containing compound and nanoparticles.
Examples of the conductive auxiliary agent include conductive carbon, metallic zinc, and conductive ceramic. Conductive carbon includes graphite, glassy carbon, amorphous carbon, graphitizable carbon, non-graphitizable carbon, carbon nanofoam, activated carbon, graphene, nanographene, graphene nanoribbon, fullerene, carbon black, carbon fiber, fibrous carbon, carbon Nanotubes, carbon nanohorns, Vulcan, ketjen black, acetylene black and the like can be mentioned. Among these, graphite, graphitizable carbon, non-graphitizable carbon, graphene, carbon black, carbon fiber, fibrous carbon, carbon nanotube, Vulcan, Ketjen black, and acetylene black are preferable. In addition, the metal zinc may be the same as that used in an actual battery such as an alkaline battery or an air battery, or may have a surface treated with other elements or carbon, or an alloy. It may be made. Moreover, a solid solution may be sufficient. The said conductive support agent can be used by 1 type, or 2 or more types. The metallic zinc can also act as an active material. In other words, in the process of using the battery, metallic zinc, which is a conductive additive, performs a redox reaction and functions as an active material. Similarly, in the process of using the battery, metallic zinc produced from a zinc-containing compound as an active material also functions as a conductive additive. Metal zinc and a zinc-containing compound added as a mixture in the preparation stage of an electrode such as a negative electrode substantially function as an active material and a conductive aid in the process of using the battery.

When blending the conductive auxiliary, the blending amount is preferably 0.0001 to 40% by mass with respect to 100% by mass of the zinc electrode mixture. When the blending amount of the conductive auxiliary is within such a range, better battery performance is exhibited when the zinc electrode formed from the zinc electrode mixture is used as the negative electrode of the battery. More preferably, it is 0.0005-20 mass%, More preferably, it is 0.001-15 mass%.

The mixture for a zinc electrode of the present invention may be obtained by further mixing other components other than an active material such as a zinc-containing compound, nanoparticles, and a conductive additive.
For example, the zinc electrode mixture of the present invention may be obtained by further mixing an organic compound and / or an organic compound salt with an active material such as a zinc-containing compound and a uniform dispersion of nanoparticles. Good. The organic compound and / or the organic compound salt improves the dispersibility of the nanoparticle and the like according to the present invention, and also efficiently binds the zinc-containing compound particles to each other and to the current collector. It works as a material that exhibits effects such as adhesives, suppression of active material shape change and passive formation of zinc electrode, suppression of active material dissolution, improvement of hydrophilicity / hydrophobicity balance, improvement of anion conductivity, and improvement of electron conductivity. Expected, and when water-containing electrolyte is used, side reactions during charge and discharge when water decomposition reaction proceeds and hydrogen is generated, which can usually occur thermodynamically, change in form of zinc electrode active material In addition, it suppresses self-discharge during charge formation and corrosion reaction and during storage in a charged state or in a charged state, thereby significantly improving charge / discharge characteristics, coulomb efficiency, and storage stability of the battery. One of the factors of this effect is that the organic compound or organic compound salt suitably covers or adsorbs the surface of the zinc-containing compound such as zinc oxide, or chemically interacts with the zinc-containing compound such as zinc oxide. It is thought to be derived from the fact that the action is manifested. That is, it is also one of preferred embodiments of the present invention that the zinc electrode mixture of the present invention further contains an organic compound and / or an organic compound salt.

Examples of the organic compound and organic compound salt include hydrocarbon moiety-containing polymer; aromatic group-containing polymer; ether group-containing polymer; hydroxyl group-containing polymer; amide group-containing polymer; imide group-containing polymer; carboxyl group-containing polymer; Salt-containing polymers; Halogen-containing polymers; Polymers bonded by ring opening of epoxy groups such as epoxy resins; Sulfonate moiety-containing polymers; Quaternary ammonium salt and quaternary phosphonium salt-containing polymers; Cations and anions Ion exchange polymers used for exchange membranes, etc .; natural rubber; artificial rubber; sugars; amine group-containing polymers; carbamate group site-containing polymers; carbamide group site-containing polymers; epoxy group site-containing polymers; , Ionized heterocyclic moiety-containing polymer; polymer Alloy; heteroatom-containing polymer; low molecular weight surfactants, and the like.

When the zinc electrode mixture of the present invention further contains other components, the blending amount thereof is 0.01 to 100% by mass with respect to 100% by mass of the zinc-containing compound in the zinc electrode mixture. Is preferred. More preferably, it is 0.05-80 mass%, More preferably, it is 0.1-60 mass%.
In addition, the ratio of the total amount of the organic compound or the organic compound salt contained in the other component is 0.1% by mass or more with respect to 100% by mass of the total amount of the other components. More preferably, it is 0.5 mass% or more, More preferably, it is 1.0 mass% or more. The upper limit is preferably 100% by mass.

The method for producing a zinc electrode mixture for obtaining the zinc electrode mixture of the present invention is also one aspect of the present invention. Unlike the mixing by the conventional wet method, the dry stirring and mixing in the production method of the present invention has a small change in the size and shape of the particles due to the mixing. In addition, the preferable structure of the manufacturing method of the mixture for zinc electrodes of this invention and the mixture for zinc electrodes obtained by the said manufacturing method is the same as the preferable structure mentioned above regarding the mixture for zinc electrodes of this invention.

A zinc electrode constructed using the zinc electrode mixture of the present invention is also one aspect of the present invention. In addition, this zinc electrode is normally comprised including the electrical power collector and the active material layer formed on this electrical power collector using the mixture for zinc electrodes. A solid electrolyte or an anion conductive material may be introduced on and / or into the active material layer. The zinc electrode of the present invention is preferably a zinc negative electrode.

Examples of the method for preparing the zinc electrode include the following methods. The zinc electrode mixture (mixture) of the present invention obtained by the above-described method is prepared by using at least one compound selected from the group consisting of the above organic compounds and organic compound salts, and / or water and N-methylpyrrolidone. Kneading with a solvent such as an organic solvent using a kneader or the like. Next, the obtained slurry or paste mixture is coated, pressed, bonded, melted, rolled, stretched, etc. on the current collector so that the film thickness is as constant as possible. Examples of the current collector include (electrolytic) copper foil; copper mesh (expanded metal); foamed copper; punched copper; copper alloy such as brass; brass foil; brass mesh (expanded metal); Nickel foil; Corrosion-resistant nickel; Nickel mesh (expanded metal); Punching nickel; Metal zinc; Corrosion-resistant metal zinc; Zinc foil; Zinc mesh (expanded metal); (Punching) steel plate; Ni, Zn, Sn, Pb, Hg, Bi -Copper foil, copper mesh (expanded metal) with added or plated with In, Tl, brass, etc.-Copper alloy such as foamed copper, punched copper, brass, brass foil, brass mesh (expanded metal) ) ・ Foamed brass ・ Punching brass ・ Nickel foil ・ Corrosion resistant nickel ・ Nickel mesh (Expa Metal), punched nickel, metal zinc, corrosion resistant metal zinc, zinc foil, zinc mesh (expanded metal), (punched) steel sheet, non-woven fabric; silver; materials used as current collectors and containers for alkaline batteries and air zinc batteries, etc. Is mentioned. The slurry or paste mixture may be coated, pressed, bonded, melted, rolled or stretched on one side of the current collector, or coated, pressed, bonded, melted, rolled or stretched on both sides or the entire surface. May be. After coating, it is dried at 0 to 400 ° C. More preferably, it is 15-380 degreeC as drying temperature. The drying time is preferably 4 to 48 hours. Drying may be performed by vacuum drying or drying under reduced pressure. Moreover, it is preferable to press with a roll press machine etc. at the pressure of normal pressure-20t after drying. The pressure for pressing is more preferably a pressure of normal pressure to 15 t. You may apply the temperature of 10-400 degreeC at the time of a press. The pressing process may be performed once or a plurality of times. When performing the pressing, the adhesion between the active materials and / or the active material and the binder can be improved, and the amount of the active material and the thickness of the active material layer can be adjusted. In addition, when the zinc negative electrode of the present invention contains a solid electrolyte or an anion conductive material on the active material layer, the zinc negative electrode mixture is applied onto the current collector, crimped, bonded, melted, rolled, stretched, etc. Thus, a solid electrolyte or an anion conductive material can be formed on the active material layer during or before the preparation of the active material layer. Thus, the obtained zinc electrode (zinc mixture electrode) can improve a rate characteristic, and when using as a negative electrode for secondary batteries especially, can improve charging / discharging cycling characteristics. The film thickness of the zinc electrode is preferably 1 nm to 10000 μm. More preferably, it is 10 nm-9000 micrometers, More preferably, it is 20 nm-8000 micrometers.

A battery comprising the zinc electrode of the present invention and an electrolytic solution (electrolyte) is also one aspect of the present invention. When the zinc electrode of this invention is a zinc negative electrode, the battery of this invention is comprised using the zinc negative electrode of this invention, a positive electrode, and electrolyte.

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. The separator is not particularly limited, but non-woven fabric, polyethylene, polypropylene, polytetrafluoroethylene, polyvinylidene fluoride, cellulose, cellulose acetate, hydroxyalkyl cellulose, carboxymethyl cellulose, polyvinyl alcohol, cellophane, polystyrene, polyacrylonitrile, polyacrylamide, polychlorinated High molecular weight polymers having micropores such as vinyl, polyamide, vinylon, and poly (meth) acrylic acid, copolymers thereof, gel compounds, ion-exchange membrane polymers, copolymers thereof, cyclized polymers, and copolymers thereof Polymers, poly (meth) acrylate-containing polymers and their copolymers, sulfonate-containing polymers and their copolymers, quaternary ammonium salt-containing polymers and their copolymers, quaternary phosphonium salt polymers and their Et copolymer, anion conducting material, and the like.
The separator can be used alone or in combination of two or more.

Furthermore, since a water-containing electrolyte can be used as the electrolyte in the battery using the zinc electrode of the present invention, a highly safe battery can be obtained. Thus, the battery comprised using the zinc electrode of this invention, a separator, and aqueous electrolyte solution is also one of this invention. The battery of the present invention may contain one of these essential components, or may contain two or more.

The positive electrode is formed using a positive electrode mixture. The positive electrode mixture includes a positive electrode active material. As the positive electrode active material, a material normally used as a positive electrode active material of a primary battery or a secondary battery can be used. For example, oxygen (when oxygen is a positive electrode active material, the positive electrode is reduced with oxygen or water). A perovskite compound that can be oxidized, a cobalt-containing compound, an iron-containing compound, a copper-containing compound, a manganese-containing compound, a platinum-containing compound, a gold-containing compound, a carbon-containing compound, etc.); nickel oxyhydroxide Nickel compounds such as nickel hydroxide and cobalt-containing nickel hydroxide; manganese compounds such as manganese dioxide; silver oxide; iron-containing compounds. Among these, oxygen, a nickel compound, or a manganese compound is preferable.
The positive electrode mixture may further contain the nanoparticles, a conductive additive, an organic compound, an organic compound salt, and the like.

The electrolyte is not particularly limited as long as it is usually used as a battery electrolyte, and examples thereof include water-containing electrolytes and organic solvent-based electrolytes, and water-containing electrolytes are preferred. The water-containing electrolytic solution refers to an electrolytic solution using only water as an electrolytic solution raw material (aqueous electrolytic solution) or an electrolytic solution using a solution obtained by adding an organic solvent to water as an electrolytic solution raw material. Examples of the aqueous electrolyte include potassium hydroxide aqueous solution, sodium hydroxide aqueous solution, lithium hydroxide aqueous solution, zinc sulfate aqueous solution, zinc nitrate aqueous solution, zinc phosphate aqueous solution, and zinc acetate aqueous solution. Although it does not restrict | limit especially as electrolyte, When using aqueous electrolyte solution, the compound which generate | occur | produces the hydroxide ion which bears ion conduction in a system is preferable. In particular, an aqueous potassium hydroxide solution is preferable from the viewpoint of ion conductivity. The aqueous electrolyte solution can be used alone or in combination of two or more. Moreover, the said water containing electrolyte solution may contain the organic solvent used for an organic solvent type electrolyte solution. Examples of the organic solvent include ethylene carbonate, propylene carbonate, dimethyl carbonate, diethyl carbonate, γ-butyrolactone, dimethoxymethane, diethoxymethane, dimethoxyethane, tetrahydrofuran, methyltetrahydrofuran, diethoxyethane, dimethyl sulfoxide, sulfolane, acetonitrile, and benzonitrile. Ionic liquid, fluorine-containing carbonates, fluorine-containing ethers, polyethylene glycols, fluorine-containing polyethylene glycols and the like. The electrolytic solution can be used alone or in combination of two or more.

The concentration of the electrolyte is preferably 0.01 to 20 mol / L. By using the electrolytic solution having such a concentration, good battery performance can be exhibited. Moreover, More preferably, it is 0.1-18 mol / L. Further, the electrolytic solution may contain an additive. Examples of the additive include simple substances and / or compounds having at least one element selected from the group consisting of elements belonging to Groups 1 to 17 of the periodic table other than zinc. One or more additives can be used.

Moreover, as a form of the battery using the mixture for zinc electrodes of the present invention, a primary battery, a secondary battery capable of charge / discharge, use of mechanical charge (mechanical replacement of the zinc electrode), a zinc electrode of the present invention Any form such as utilization of a third electrode different from the positive electrode composed of the positive electrode active material as described above may be used, but a secondary battery is particularly preferable. Thereby, the effect of improving the charge / discharge cycle characteristics can be remarkably exhibited.
Below, taking the nickel electrode as an example, the configuration of the nickel-zinc storage battery will be described. The nickel / zinc battery includes the zinc 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 into strips are alternately sandwiched between pleated separators, a sealed type, an open type, or a vent type Good. You may have the site | part which reserves the gas generated at the time of charging / discharging.

The battery manufacturing process of the present invention may be a wet process or a dry process. In the wet process, for example, the positive electrode current collector and the negative electrode current collector are coated with a paste or slurry of a positive electrode material and a paste or slurry of a negative electrode material, respectively, and the coated electrode is dried and compressed, and after cutting and cleaning Then, the cut electrodes and the separator are stacked in layers to form a battery assembly. The dry process is a process using, for example, electrode component powder or a granular dry mixture instead of slurry or paste. (1) The negative electrode material is applied to a current collector, and (2) the positive electrode material is collected in a dry state. (3) A separator is placed between the sheets of (1) and (2) to form a layered structure to form a battery assembly, and (4) the battery assembly of (3) is wound or folded. The three-dimensional structure is formed through the same process. 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. During the battery manufacturing process or storage, the battery may be in a charged state or a discharged state.

A battery using a zinc electrode formed using the zinc electrode mixture of the present invention can improve rate characteristics. Moreover, in a secondary battery, the charge / discharge cycle characteristics of the battery can be improved and the battery life can be extended.

1 is a photograph of a mixture of zinc oxide and bismuth oxide nanoparticles of Example 1 taken with an SEM. FIG. 2 is a photograph of a mixture of zinc oxide and cerium oxide nanoparticles of Example 2 taken with an SEM. FIG. 3 is a photograph of a mixture of zinc oxide and tin oxide nanoparticles of Example 3 taken with an SEM. FIG. 4 is a photograph of a mixture of zinc oxide and aluminum oxide nanoparticles of Example 4 taken with an SEM.

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.
The average particle diameter of zinc oxide before and after dry stirring and mixing in the examples was measured by the method described above.
The ratio of particles having a particle diameter of less than 0.6 μm was measured by the method described above.

Example 1
291 g of zinc oxide (average particle size: 0.66 μm) and 9 g of bismuth oxide nanoparticles (average particle size: 51 nm, manufactured by CII Kasei Co., Ltd.) were stirred using a stirring and mixing device (product name: Nobilta) manufactured by Hosokawa Micron Co., Ltd. The mixture was stirred at 20 m / S for 10 minutes. When the obtained mixture was observed by SEM, it was found that the bismuth oxide nanoparticles were uniformly dispersed in the zinc oxide (FIG. 1). Moreover, the average particle diameter of the zinc oxide after stirring was 0.63 μm. Further, the proportion of particles having a particle diameter of less than 0.6 μm among the stirred zinc oxide particles and bismuth oxide nanoparticles was 24%.

(Example 2)
291 g of zinc oxide and 9 g of cerium oxide nanoparticles (average particle size 14 nm, manufactured by C-I Kasei Co., Ltd.) were stirred for 10 minutes at a peripheral speed of 20 m / S using a stirring and mixing device (product name: Nobilta) manufactured by Hosokawa Micron Corporation. When the obtained mixture was observed by SEM, it was found that the cerium oxide nanoparticles were uniformly dispersed in the zinc oxide (FIG. 2). Moreover, the average particle diameter of the zinc oxide after stirring was 0.70 μm.

(Example 3)
291 g of zinc oxide and 9 g of tin oxide nanoparticles (average particle size 21 nm, manufactured by C-I Kasei Co., Ltd.) were stirred for 10 minutes at a peripheral speed of 20 m / S using a stirring and mixing device (product name: Nobilta) manufactured by Hosokawa Micron Corporation. . When the obtained mixture was observed by SEM, it was found that the tin oxide nanoparticles were uniformly dispersed in the zinc oxide (FIG. 3). Moreover, the average particle diameter of the zinc oxide after stirring was 0.71 μm.

(Example 4)
291 g of zinc oxide and 9 g of aluminum oxide nanoparticles (average particle size 31 nm, manufactured by CII Kasei Co., Ltd.) were stirred for 10 minutes at a peripheral speed of 20 m / S using a stirring and mixing device (product name: Nobilta) manufactured by Hosokawa Micron Corporation. . When the obtained mixture was observed by SEM, it was found that the aluminum oxide nanoparticles were uniformly dispersed in zinc oxide (FIG. 4). Moreover, the average particle diameter of the zinc oxide after stirring was 0.73 μm.

(Example 5)
Hydrotalcite [Mg _0.8 Al _0.2 (OH) ₂ ] (CO ₃ ²⁻ ) _0.1 mH ₂ O (25 g) was added with polytetrafluoroethylene (30 g) and water, and stirred with a spatula. The obtained solid was rolled with a drawing roll machine to produce a solid electrolyte.
A 60% aqueous polytetrafluoroethylene solution (15 g) and water (170 g) were added to the mixture (300 g) obtained in Example 1, and the mixture was stirred for 5 minutes at a peripheral speed of 0.04 m / S using a planetary mixer. Further, the mixture was stirred for 1 minute at a peripheral speed of 0.05 m / S to prepare a zinc negative electrode mixture. This zinc negative electrode mixture is pressure-bonded to a copper mesh as a current collector, and then a solid electrolyte is pressure-bonded onto the zinc negative electrode mixture, and then dried to obtain a zinc negative electrode, and the solid electrolyte is provided on the active material. The zinc mixture electrode was used so as to be a working electrode having an apparent area of 1 cm ² .
Furthermore, 8 mol / L potassium hydroxide aqueous solution in which zinc oxide is dissolved as an electrolyte solution until saturation, nonwoven fabric as separator, nickel electrode as counter electrode (active material: cobalt-coated nickel hydroxide, capacity is 0.7 times that of zinc electrode) And a charge / discharge test (charge / discharge test: 1 hour each) at a current value of 25 mA / cm ² using a three-electrode cell, using the same electrode as the positive electrode (counter electrode) as a reference electrode. ) And a cycle life of at least 200 cycles or more was observed (Coulomb efficiency of the 200th charge / discharge: 93.2%).

(Example 6)
An electrode was prepared and a charge / discharge test was conducted in the same manner as in Example 5 except that the mixture obtained in Example 2 was used. At this time, a cycle life of at least 200 cycles or more was observed (Coulomb efficiency of the 200th charge / discharge: 92.3%).

(Example 7)
An electrode was prepared and a charge / discharge test was conducted in the same manner as in Example 5 except that the mixture obtained in Example 3 was used. At this time, a cycle life of at least 200 cycles or more was observed (Coulomb efficiency of 200th charge / discharge: 91.1%).

(Example 8)
An electrode was prepared and a charge / discharge test was conducted in the same manner as in Example 5 except that the mixture obtained in Example 4 was used. At this time, a cycle life of at least 200 cycles was observed (Coulomb efficiency of 200th charge / discharge: 92.2%).

From Examples 1 to 4 above, even when stirring and mixing by a dry method, the mother particles and the nanoparticles could be uniformly mixed without impairing the mother particles (zinc oxide particles). In addition, when adding water and mixing with a binder using a planetary mixer with respect to the mixture obtained by stirring and mixing by a dry method like Examples 5-8, it is 5 minutes at a peripheral speed of 0.04 m / S. After stirring, the mixture was further stirred for 1 minute at a peripheral speed of 0.05 m / S, but the mother particles, that is, the zinc-containing compound was not damaged, the average particle diameter did not change, and the rate characteristics and charge / discharge cycle characteristics were improved. The effect of the present invention was able to be exhibited.

In the above examples, zinc oxide is used as the zinc-containing compound, bismuth oxide nanoparticles, cerium oxide nanoparticles, tin oxide nanoparticles, and aluminum oxide nanoparticles are used as nanoparticles, and dry stirring and mixing are performed. Although a mixture in which the zinc-containing compound and the nanoparticles are uniformly dispersed is prepared, the rate characteristics can be improved and the charge / discharge cycle characteristics can be improved in the secondary battery. The same applies to a mixture in which a zinc-containing compound of 0.6 μm or more and nanoparticles containing a specific element that can be suitably used for an electrode are uniformly dispersed.

In addition, the above examples relate to a nickel-zinc battery including a zinc negative electrode prepared using the zinc electrode mixture of the present invention, and this is a preferred embodiment of the present invention. In addition, as long as a zinc electrode prepared using the zinc electrode mixture of the present invention is provided, the effects of the present invention can be exhibited. Therefore, from the results of the above examples, it is proved that the present invention can be applied in various technical forms of the present invention and in various forms disclosed in the present specification, and advantageous effects can be exhibited.

Example 9
Zinc oxide (average particle size 0.66 μm) and bismuth oxide nanoparticles (average particle size 51 nm, manufactured by C.I. For 5 minutes. It was confirmed that there was no change in the average particle diameter of zinc oxide before and after stirring.
The obtained mixture was mixed with a 60% polytetrafluoroethylene aqueous solution at a mass ratio of 100: 3, and a zinc negative electrode mixture was prepared using a rolling roller. This zinc negative electrode mixture is pressure-bonded to a copper mesh as a current collector, and then a solid electrolyte similar to that of Example 5 is pressure-bonded onto the zinc negative electrode mixture, and then dried to obtain a zinc negative electrode. A zinc mixture electrode having a solid electrolyte on it was used so as to be a working electrode having an apparent area of 1.948 cm ² .
A rate test was conducted by charging the battery at 0.25 C for 1 hour using a tripolar cell in the same manner as in Example 5 and discharging it to 1.2 V at 1 C. Coulomb efficiency was 79% (Note that 1 / n · C means a current value required for n hours for full charge).

( Reference Example 1 )
Zinc oxide (average particle size 0.66 μm) was mixed with a 60% polytetrafluoroethylene aqueous solution at a mass ratio of 100: 3 in the same manner as in Example 9, and the resulting mixture was subjected to the same steps as in Example 9. Electrode preparation and rate tests were performed. Coulomb efficiency was 72%.

(Example 11)
Zinc oxide (average particle size 0.66 μm) was mixed with bismuth oxide particles (average particle size 2.57 μm, Yasuda Pharmaceutical Co., Ltd.) at a mass ratio of 80:20 by hand shaking. At this time, it was confirmed by SEM that most of the bismuth oxide particles were aggregated without being uniformly dispersed as primary particles.
From the obtained mixture, an electrode was prepared and a rate test was performed in the same steps as in Example 9. Coulomb efficiency was 80%.

From Example 9 and Reference Example 1 , it was revealed that rate characteristics were improved by adding nanoparticles. Moreover, from Example 9 and Example 11, it became clear that a rate characteristic improves by addition of a small amount by mixing nanoparticle uniformly disperse | distributing.

Claims (7)

The average and particle size of 0.6μm or more zinc oxide Bisumasunano particles, cerium oxide particles, tin oxide nanoparticles, and at least one nanoparticle is homogeneously dispersed is selected from the group consisting of aluminum oxide nanoparticles A zinc electrode mixture,
The ratio of the nanoparticles is 1% by mass or more and 10% by mass or less with respect to 100% by mass of the zinc electrode mixture. The zinc electrode mixture according to claim 1, wherein the average particle diameter of the nanoparticles is 100 nm or less. 3. The zinc electrode mixture according to claim 1, wherein a ratio of particles having a particle diameter of less than 0.6 μm is 60% by mass or less in a total amount of 100% by mass of the zinc oxide and nanoparticles. A zinc electrode comprising the zinc electrode mixture according to any one of claims 1 to 3 . A battery comprising the zinc electrode according to claim 4 and an electrolytic solution. A method for producing a zinc electrode mixture,
The manufacturing method includes a zinc oxide Bisumasunano particles, cerium oxide particles, tin oxide nanoparticles, and at least one nanoparticle is selected from the group consisting of aluminum oxide nanoparticles, were dry stirred mixture, average particle size observed including the step of obtaining a zinc electrode mixture in which the above zinc oxide nanoparticles 0.6μm uniformly dispersed,
The method for producing a zinc electrode mixture, wherein the proportion of the nanoparticles is 1% by mass or more and 10% by mass or less with respect to 100% by mass of the zinc electrode mixture. The said dry-type stirring mixing is performed using a stirring bar, The manufacturing method of the mixture for zinc electrodes of Claim 6 characterized by the above-mentioned.