JP2014149993A - Zinc negative electrode, battery and electrode base layer - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a zinc negative electrode which allows for formation of a battery having sufficiently enhanced battery performance, by suppressing dissociation of an electrode base layer and a negative electrode active material layer containing zinc, even if it is used as a battery, after improving electrification sufficiently between a collector layer composing the electrode base layer and the active material layer containing a zinc species, and to provide a battery using the zinc negative electrode, and an electrode base layer used for formation of the zinc negative electrode.SOLUTION: In a zinc negative electrode including an electrode base layer, and an active material layer containing a zinc species and being bound to the electrode base layer, the electrode base layer includes a collector layer, and a layer containing carbon. The layer containing carbon is a zinc negative electrode covering the surface of the collector layer on the active material layer side partially or entirely.

Description

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

The negative electrode is a negative electrode of a battery composed of a negative electrode active material. Among them, a zinc negative electrode using zinc as a negative electrode active material has been studied for a long time with the spread of batteries. Examples of batteries 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 the positive electrode active material, and silver / zinc batteries that use silver oxide as the positive electrode active material 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, a metal core is subjected to galvanization, and a part of the plated zinc has a higher redox potential than zinc and a hydrogen overvoltage. An alkaline zinc storage battery in which a current collector partially ion-substituted with a large metal is used for a zinc electrode is disclosed (for example, see Patent Document 1). A nickel-zinc battery cell, (a) a cathode layer having a current collector underlayer based on zinc metal in correspondence with an electrochemically active layer based on zinc oxide; and (b) nickel There is disclosed a nickel / zinc battery cell comprising: an anode layer comprising: (c) an isolation layer that separates the cathode layer from the anode layer; and (d) an electrolyte (see, for example, Patent Document 2).

JP-A-01-319261 Special table 2010-518585

As described above, various types of batteries using zinc as a negative electrode have been studied. However, as new batteries using other elements as negative electrodes have been developed, they have ceased to be the mainstream of battery development. However, the present inventors, when using zinc for the negative electrode in this way, the zinc negative electrode is inexpensive and a water-containing electrolyte can be used. In that case, in addition to high safety, the energy density is also high. From such a viewpoint, attention was paid to the possibility of being able to be suitably used in various applications. And when the performance aspect of the battery which uses zinc for a negative electrode was examined, in order to satisfy | fill the performance requested | required of the battery used in recent years, in the process of use as a battery, an electrode base layer and the negative electrode active material layer containing zinc When the battery performance is reduced and the battery is a secondary battery, it has been found that there is still a problem that this becomes remarkable by repeated charge and discharge.

The present invention has been made in view of the above-mentioned present situation, and as a battery after sufficiently improving the electrical conductivity between the current collector layer constituting the electrode base layer and the active material layer containing zinc species. Even when used, dissociation between the electrode base layer and the negative electrode active material layer containing zinc is suppressed, and a zinc negative electrode capable of forming a battery with sufficiently improved battery performance, a battery using the zinc negative electrode, and An object of the present invention is to provide an electrode underlayer used for forming the zinc negative electrode.

The present inventors have made various studies on zinc negative electrodes, and various zinc negative electrodes that can suppress dissociation between the electrode base layer and the active material layer containing zinc species in the process of use as the negative electrode of the battery. investigated. Here, in the conventional zinc negative electrode, the current collector layer and the active material layer are bound via the binder component, and in the process of use as the negative electrode of the battery, it is a solvent for the electrolytic solution. It is considered that water may permeate into the active material layer and water may act on the binder component, so that the current collector layer constituting the electrode base layer and the binder component may be dissociated. Furthermore, the present inventors have a phenomenon that dendritic zinc species precipitate on the current collector layer when the charge / discharge test is continued even after the active material layer containing zinc species and the current collector layer are dissociated. We have also found that it may occur. This is due to further dissociation of the current collector layer and active material layer, hydrogen generation due to water decomposition, participation and passivation of the dendritic zinc species in self-discharge, and further growth of the dendritic zinc species. This means that a short circuit or the like can occur sufficiently, and it is considered that the battery performance is adversely affected. Accordingly, the inventors of the present invention do not impair the above-described conductivity and sufficiently suppress dissociation between the electrode underlayer and the active material layer containing zinc species on the surface of the current collector layer on the active material layer side. We considered placing new members. Then, the electrode underlayer is provided with a layer containing carbon together with the current collector layer, and a part or all of the surface of the current collector layer on the active material layer side is covered with the material containing carbon. Thus, the conductivity can be improved sufficiently, and the adhesion between the carbon-containing layer and the active material layer can be improved. In the process of use as the negative electrode of the battery, carbon is included. It has been found that dissociation between the electrode base layer including the material and the active material layer containing zinc species can be sufficiently 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. As described above, the inventors of the present invention provide a zinc negative electrode including an electrode base layer and an active material layer bound to the electrode base layer and containing a zinc species. A body layer and a carbon-containing layer, and the carbon-containing layer covers a part or all of the surface of the current collector layer on the active material layer side, so that the above problem can be achieved. I came up with a solution. Here, according to the configuration of the present invention, the binding property between the binder component and the carbon-containing layer is excellent, and also the penetration of water into the carbon-containing layer can be prevented, and the carbon is contained. It is considered that the binding property (adhesiveness) between the conducting layer and the current collector layer can be made sufficiently excellent.

The battery disclosed in the above-mentioned patent document has no description or suggestion about the technical idea of coating the current collector layer with a material containing carbon, and dissociates the electrode underlayer from the negative electrode active material layer containing zinc. It was not intended to suppress and improve battery performance, and there was room for improvement in order to sufficiently solve this problem.

The present invention is used for a storage battery (secondary battery) in that the electrode base layer and the active material layer containing zinc species are likely to be dissociated due to repetition of charge and discharge. Is particularly preferred. The present invention can be used not only for storage batteries (secondary batteries) but also for other electrochemical devices such as primary batteries, capacitors, and hybrid capacitors.

That is, the present invention is a zinc negative electrode comprising an electrode base layer and an active material layer bound to the electrode base layer and containing a zinc species, wherein the electrode base layer includes a current collector layer, The carbon-containing layer is a zinc negative electrode that covers part or all of the surface of the current collector layer on the active material layer side. In addition, in this specification, a zinc negative electrode means the zinc electrode used as a negative electrode.
Moreover, this invention is also a battery comprised using the zinc negative electrode of this invention, a positive electrode, and electrolyte.
Furthermore, the present invention is an electrode underlayer used for a zinc negative electrode, wherein the electrode underlayer includes a current collector layer and a carbon-containing layer, and the carbon-containing layer is a current collector. It is also an electrode base layer that covers part or all of the surface of the layer.
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 layer containing carbon preferably contains, for example, conductive carbon. Examples of the conductive carbon include graphite such as natural graphite and artificial graphite, glassy carbon, amorphous carbon, graphitizable carbon, non-graphitizable carbon, carbon nanofoam, activated carbon, graphene, nanographene, graphene nanoribbon, fullerene, carbon Black, graphitized 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, Multi-wall / single-walled carbon nanotubes, carbon nanohorns, vulcan, acetylene black, carbon treated with hydrophilicity by introducing oxygen-containing functional groups, SiC-coated carbon, by dispersion / emulsion / suspension / microsuspension polymerization, etc. Surface-treated carbon, microcapsules carbon and the like as preferred. Among them, natural graphite, graphite such as artificial graphite, amorphous carbon, graphitizable carbon, non-graphitizable carbon, activated carbon, graphene, fullerene, carbon black, graphitized carbon black, ketjen black, vapor grown carbon fiber, pitch system Hydrophilic treatment by introducing carbon fiber, carbon coated with metal, carbon coated metal, fibrous carbon, boron-containing carbon, nitrogen-containing carbon, multi-wall / single-walled carbon nanotube, vulcan, acetylene black, oxygen-containing functional group Carbon that has been surface-treated by dispersion, emulsification, suspension, microsuspension polymerization or the like is preferred.

In addition, the carbon-containing layer is preferably formed of a compound having an aromatic ring in that the effect of the present invention can be further exhibited. Furthermore, it is preferable that the aromatic rings have a laminated shape or a bead shape due to π-π interaction or the like. The carbon-containing layer can also have an effect of roughening the current collector surface.

The average thickness of the carbon-containing layer is preferably 0.01 μm or more, for example. More preferably, it is 0.1 μm or more. More preferably, it is 0.5 μm or more. Moreover, it is preferable that this average thickness is 1000 micrometers or less, for example. More preferably, it is 500 μm or less. More preferably, it is 300 μm or less.
The average thickness of the carbon-containing layer refers to an average value of the thickness of the entire layer in which the carbon-containing layer is formed.

The carbon-containing layer preferably covers 10% or more of the surface area of the current collector layer on the active material layer side. More preferably, it is 40% or more, and still more preferably 80% or more. Particularly preferably, the layer containing carbon covers substantially the entire surface of the current collector layer on the active material layer side.
The carbon-containing layer of the present invention contains a simple substance or compound of carbon, and the blending amount of the simple substance or compound of carbon is 0.01% by mass with respect to 100% by mass of the layer containing carbon. The above is preferable. More preferably, it is 0.1 mass% or more, More preferably, it is 0.5 mass% or more. Moreover, it is preferable that this compounding quantity is 99.99 mass% or less with respect to 100 mass% of layers containing carbon. More preferably, it is 99.95 mass% or less, More preferably, it is 99.9 mass% or less.

The layer containing carbon preferably further contains a simple substance or a compound of at least one element selected from the group consisting of elements belonging to Groups 1 to 17 of the periodic table. Thereby, the effect of this invention which suppresses dissociation with an electrode base layer and a negative electrode active material layer can be exhibited more notably. Note that elements other than carbon are used as at least one element selected from the group consisting of elements belonging to Groups 1 to 17 of the periodic table.

Here, in the case of a battery configured using a water-containing electrolytic solution as an electrolytic solution, it is preferable to an organic solvent-based electrolytic solution from the viewpoint of safety. However, water decomposition proceeds to generate hydrogen. The side reaction of can occur. However, when the carbon-containing layer further contains a simple substance or a compound of at least one element selected from the group consisting of elements belonging to Groups 1 to 17 of the periodic table, Even when the battery is configured, it is possible to effectively suppress the generation of hydrogen due to the decomposition of water in the process of using the battery, and to change the shape of the active material and form the passive state. It can be sufficiently suppressed. That is, the effect of suppressing the dissociation between the electrode base layer and the negative electrode active material layer is remarkably exhibited, and the effect is compatible with the effect of suppressing the generation of hydrogen due to the decomposition of water during the use of the battery. Furthermore, it is possible to sufficiently suppress the morphological change of the active material and the formation of passive state.

When the layer containing carbon of the present invention contains a simple substance or a compound of at least one element selected from the group consisting of elements belonging to Groups 1 to 17 of the periodic table, the blending amount contains carbon. It is preferable that it is 0.01 mass% or more with respect to 100 mass% of layers. More preferably, it is 0.05 mass% or more, More preferably, it is 0.1 mass% or more. Moreover, it is preferable that this compounding quantity is 99.99 mass% or less with respect to 100 mass% of layers containing carbon. More preferably, it is 99.95 mass% or less, More preferably, it is 99.9 mass% or less.

As at least one element selected from the group consisting of elements belonging to Groups 1 to 17 of the periodic table, Li, Na, K, Rb, Cs, Mg, Ca, Sr, Ba, Sc, Y, lanthanoid, Ti, Zr, Hf, V, Nb, Ta, Mo, W, Mn, Fe, Ru, Co, Ni, Pd, Cu, Ag, Au, Zn, Cd, belonging to Groups 13 to 15 of the periodic table It is preferably at least one element selected from the group consisting of the element, S, Se, Te, F, Cl, and Br. Among them, Li, Na, K, Cs, Mg, Ca, Ba, Sc, Y, lanthanoid, Ti, Zr, V, Nb, Mo, W, Mn, Fe, Co, Ni, Pd, Cu, Zn, Cd, Particularly preferred is at least one element selected from the group consisting of B, Al, Ga, In, Si, Ge, Sn, Pb, N, P, Sb, Bi, S, and F. Thereby, in the zinc negative electrode of the present invention, the effect of suppressing the dissociation between the electrode base layer and the negative electrode active material layer can be further exerted, the generation of hydrogen due to the decomposition of water in the process of using the battery is suppressed, and The effect of suppressing the change in the shape of the active material and the formation of the passive state can be brought about more remarkably.

The compound of at least one element selected from the group consisting of elements belonging to Groups 1 to 17 of the periodic table includes oxides of the elements; complex oxides; layered double hydroxides; hydroxides; clay compounds Solid solution; Alloy; Halide; Carboxylate compound; Carbonate compound; Hydrogen carbonate compound; Nitric acid compound; Sulfuric acid compound; Silicic acid compound; Aluminate compound; Compound; boric acid compound; ammonium compound; sulfide; onium compound; hydrogen storage compound. In the present specification, the hydroxide refers to a hydroxide other than the layered double hydroxide.

The compound of at least one element selected from the group consisting of elements belonging to Groups 1 to 17 of the periodic table includes oxides of the elements; complex oxides; layered double hydroxides; hydroxides; clay compounds A solid solution; an alloy; a fluoride; a carboxylate compound; a carbonic acid compound; a nitric acid compound; a sulfuric acid compound; a silicic acid compound; an aluminate compound; a boric acid compound; Thereby, dissociation between the electrode base layer and the active material layer containing zinc species can be further sufficiently suppressed. Specifically, for example, lithium oxide, lithium hydroxide, lithium fluoride, lithium carbonate, lithium nitrate, lithium sulfate, lithium silicate, lithium aluminate, lithium phosphate, lithium borate, sodium oxide, sodium hydroxide, Sodium fluoride, sodium carbonate, sodium nitrate, sodium sulfate, sodium silicate, sodium aluminate, sodium phosphate, sodium borate, potassium oxide, potassium hydroxide, potassium fluoride, potassium carbonate, potassium nitrate, potassium sulfate, silicic acid Potassium, potassium aluminate, potassium phosphate, potassium borate, cesium oxide, cesium hydroxide, cesium fluoride, cesium carbonate, cesium nitrate, cesium sulfate, cesium silicate, cesium aluminate, cesium phosphate, cesium borate, acid Magnesium, magnesium hydroxide, magnesium fluoride, magnesium carbonate, magnesium nitrate, magnesium sulfate, magnesium silicate, magnesium aluminate, magnesium phosphate, magnesium borate, calcium oxide, calcium hydroxide, calcium fluoride, calcium carbonate, nitric acid Calcium, calcium sulfate, calcium silicate, calcium aluminate, calcium phosphate, calcium borate, barium oxide, barium hydroxide, barium fluoride, barium carbonate, barium nitrate, barium sulfate, barium silicate, barium aluminate, barium phosphate , Barium borate, scandium oxide, scandium hydroxide, scandium fluoride, scandium carbonate, scandium nitrate, scandium sulfate, scandium silicate, aluminum Scandium, scandium phosphate, scandium borate, yttrium oxide, yttrium hydroxide, yttrium fluoride, yttrium carbonate, yttrium nitrate, yttrium sulfate, yttrium silicate, yttrium aluminate, yttrium phosphate, yttrium borate, lanthanum oxide, water Lanthanum oxide, lanthanum fluoride, lanthanum carbonate, lanthanum nitrate, lanthanum sulfate, lanthanum silicate, lanthanum aluminate, lanthanum phosphate, lanthanum borate, cerium oxide, cerium hydroxide, cerium fluoride, cerium carbonate, cerium nitrate, sulfuric acid Cerium, cerium silicate, cerium aluminate, cerium phosphate, cerium borate, neodymium oxide, neodymium hydroxide, neodymium fluoride, neodymium carbonate, neodymium nitrate, neodymium sulfate, neodymium silicate, Neodymium aluminate, neodymium phosphate, neodymium borate, samarium oxide, samarium hydroxide, samarium fluoride, samarium carbonate, samarium nitrate, samarium sulfate, samarium silicate, samarium aluminate, samarium phosphate, samarium borate, europium oxide , Europium hydroxide, europium fluoride, europium carbonate, europium nitrate, europium sulfate, europium silicate, europium aluminate, europium phosphate, europium borate, gadolinium oxide, gadolinium hydroxide, gadolinium fluoride, gadolinium carbonate, gadolinium nitrate Gadolinium sulfate, gadolinium silicate, gadolinium aluminate, gadolinium phosphate, gadolinium borate, dysprosium oxide, dysprosium hydroxide, fluorine Dysprosium, dysprosium carbonate, dysprosium nitrate, dysprosium sulfate, dysprosium silicate, dysprosium aluminate, dysprosium phosphate, dysprosium borate, ytterbium oxide, ytterbium hydroxide, ytterbium fluoride, ytterbium carbonate, ytterbium nitrate, ytterbium nitrate Ytterbium aluminate, ytterbium phosphate, ytterbium borate, titanium oxide, titanium hydroxide, titanium fluoride, titanium carbonate, titanium nitrate, titanium sulfate, titanium silicate, titanium aluminate, titanium phosphate, titanium borate, oxidation Zirconium, zirconium hydroxide, zirconium fluoride, zirconium carbonate, zirconium nitrate, zirconium sulfate, zirconium silicate, dialuminate Conium, zirconium phosphate, zirconium borate, vanadium oxide, vanadium phosphate, vanadium pyrophosphate, niobium oxide, molybdenum oxide, tungsten oxide, manganese oxide, iron oxide, cobalt oxide, nickel oxide, palladium oxide, copper oxide, cadmium oxide , Boric acid, aluminum oxide, gallium oxide, indium oxide, indium hydroxide, zinc oxide, zinc hydroxide, metal zinc, silicon oxide, germanium oxide, tin oxide, tin hydroxide, lead oxide, carbon nitride, phosphoric acid, oxidation Antimony, bismuth oxide, bismuth hydroxide and the like can be mentioned. The compound may be stabilized by coordination of an organic compound (organic chain) such as a carboxylic acid, a nitrogen-containing compound, a phosphorus-containing compound, a carbene-containing compound, or a sulfur-containing compound.

The simple substance or compound of at least one element selected from the group consisting of elements belonging to Groups 1 to 17 in the periodic table preferably has an average particle diameter of 1000 μm or less. Moreover, it is preferable that this average particle diameter is 5 nm or more. 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, rod, and curved surface. 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, and drying to solidify, 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 simple substance or compound of 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. .1m and ² / g or more, further 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 by a specific surface area measuring apparatus or the like by a nitrogen adsorption BET method.

The carbon-containing layer described above may be a single layer or a laminate of two or more different layers.
The carbon-containing layer described above may contain other components as long as the effects of the present invention can be exhibited. Further, the other members may be one type or two or more types.

Examples of the method for preparing the carbon-containing layer include the following methods.
The carbon-containing material for forming the carbon-containing layer is obtained as a slurry or paste mixture. Next, the obtained slurry or paste mixture is applied, 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 foil, copper foil added with Ni, Zn, Sn, Pb, Hg, Bi, In, Tl, etc., Ni, Zn, Sn, Pb, Hg, Bi, In, Copper foil plated with Tl, copper mesh (expanded metal), copper mesh (expanded metal) with added Ni, Zn, Sn, Pb, Hg, Bi, In, Tl, Ni, Zn, Sn, Pb, Copper mesh plated with Hg / Bi / In / Tl (expanded metal), expanded copper, expanded copper added with Ni / Zn / Sn / Pb / Hg / Bi / In / Tl, Ni / Zn / Sn / Pb・ Foamed copper plated with Hg, Bi, In, Tl, etc., copper alloys such as brass, brass foil, brass foil with addition of Ni, Zn, Sn, Pb, Hg, Bi, In, Tl, etc., Ni, Zn・ Sn ・ Pb ・ Hg ・ B -Brass foil plated with In, Tl, etc., brass mesh (expanded metal), brass mesh (expanded metal) with added Ni, Zn, Sn, Pb, Hg, Bi, In, Tl, etc., Ni, Zn, Sn・ Brass mesh (expanded metal) plated with Pb, Hg, Bi, In, Tl, expanded brass, expanded brass with Ni, Zn, Sn, Pb, Hg, Bi, In, Tl, etc., Ni, Zn, Expanded brass plated with Sn, Pb, Hg, Bi, In, Tl, nickel foil, nickel mesh, corrosion resistant nickel, nickel mesh with added Zn, Sn, Pb, Hg, Bi, In, Tl, etc. (expanded metal) ), Nickel mesh (expanded metal) plated with Zn, Sn, Pb, Hg, Bi, In, Tl, etc. Metal, corrosion-resistant zinc metal, zinc metal added with Ni, Sn, Pb, Hg, Bi, In, Tl, etc., zinc metal plated with Ni, Sn, Pb, Hg, Bi, In, Tl, etc., zinc foil, Zinc foil added with Ni, Sn, Pb, Hg, Bi, In, Tl, etc., zinc foil plated with Ni, Sn, Pb, Hg, Bi, In, Tl, etc., zinc mesh (expanded metal), Ni Zinc mesh (expanded metal) added with Sn, Pb, Hg, Bi, In, Tl, etc., zinc mesh plated with Ni, Sn, Pb, Hg, Bi, In, Tl, etc. (expanded metal), silver, alkali Examples thereof include materials used as current collectors and containers for batteries and zinc-air batteries.

The slurry or paste mixture is usually applied, pressure-bonded, or adhered to one side, both sides, or the entire surface of the current collector. Then, it is preferable to dry at 0-250 degreeC. 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. The steps of coating, pressure bonding, adhesion, etc. and drying may be repeated. Moreover, it is preferable to press with a roll press etc. at the pressure of 0.00001-20t after drying. The pressure for pressing is more preferably 0.0001 to 15 t. You may apply the temperature of 10-500 degreeC at the time of a press. The pressing may be performed after an active material layer containing zinc species is formed on the electrode base layer.

A simple substance or a compound of at least one element selected from the group consisting of elements belonging to Groups 1 to 17 of the periodic table is mixed with the slurry or paste mixture for forming the carbon-containing layer described above. The carbon-containing layer may be included. 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 of the simple substance or the compound with a desired particle diameter. 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. In addition, when using zinc or an element whose reduction potential is nobler than zinc as at least one element selected from the group consisting of elements belonging to Groups 1 to 17 of the periodic table, charging / discharging It is also possible to introduce the element into the electrode underlayer by a process.

Moreover, the following is mentioned as another preparation method of the said layer containing carbon. That is, an emulsion composition composed of the above simple substance or compound particles having an organic chain is applied onto a current collector and fired in an inert gas such as nitrogen. Thereby, a layer containing at least one element or a compound of at least one element selected from the group consisting of elements belonging to Groups 1 to 17 of the periodic table and containing carbon can be obtained.

The firing temperature is preferably 100 ° C. or higher, for example. Moreover, it is preferable that this calcination temperature is 1000 degrees C or less. More preferably, it is 200 degreeC or more and 800 degrees C or less. Moreover, it is preferable that the said baking time is 0.1 hour or more, for example. Moreover, it is preferable that this baking time is 72 hours or less.

In the zinc negative electrode of the present invention, it is usually preferable that the electrode base layer and the active material layer containing zinc species are usually bound via a binder component. The binder may be the same as or different from the binder used for the electrode underlayer and / or the active material layer containing zinc species. The following binders can also be used for binding between the electrode underlayer and the active material layer containing zinc species, and within the electrode underlayer or the active material layer containing zinc species, It can also be contained as a binder of the above components. In addition, 1 type or 2 types or more can be used for a binder.
The binder component may be formed by applying a commonly used binder, for example, a poly (meth) acrylic acid moiety-containing polymer, a poly (meth) acrylate moiety-containing polymer , Poly (meth) acrylate moiety-containing polymer, poly (α-hydroxymethyl acrylate) moiety-containing polymer, poly (α-hydroxymethyl acrylate) moiety-containing polymer, polyacrylonitrile moiety-containing polymer, polyacrylamide moiety-containing Polymer, Polyvinyl alcohol moiety-containing polymer, Polyethylene oxide moiety-containing polymer, etc., Epoxy ring-opening moiety-containing polymer, Polyethylene moiety-containing polymer, Polypropylene moiety-containing polymer, Polybutene moiety-containing polymer, Polyisoprenol moiety-containing polymer, Poly (meth) allylamine Lucol moiety-containing polymer, polyisoprene moiety-containing polymer, aromatic ring moiety-containing polymer represented by polystyrene, polymaleimide moiety-containing polymer, polyvinylpyrrolidone moiety-containing polymer, polyacetylene moiety-containing polymer, polycarbonate moiety-containing polymer, thiopolycarbonate moiety-containing polymer, Artificial rubber typified by ketone group site-containing polymer, ether group site-containing polymer, ester group site-containing polymer, carbonate group site-containing polymer, thiocarbonate group-containing polymer, cyclopolymerization site-containing polymer, styrene butadiene rubber (SBR), etc. , Cellulose, cellulose acetate, hydroxyalkyl cellulose (for example, hydroxyethyl cellulose), carboxymethylcellulose, chitin, chitosan, alginic acid (salt) Amino group-containing polymer, amide group-containing polymer, polytetrafluoroethylene-containing polymer, polyvinylidene fluoride-containing polymer, poly (anhydride) maleic acid-containing polymer, polymaleate-containing polymer , Poly (anhydride) itaconic acid moiety-containing polymer, polyitaconate moiety-containing polymer, poly (anhydrous) methylene glutarate moiety-containing polymer, polymethylene glutarate moiety-containing polymer, cation / anion exchange membrane Ion exchange polymer, sulfonate moiety-containing polymer, quaternary ammonium salt moiety-containing polymer, quaternary phosphonium salt moiety-containing polymer, imide group moiety-containing polymer, hydroxyl group moiety-containing polymer, urethane group moiety-containing polymer, conductive polymer The Maaroi, heteroatom-containing polymers, low molecular weight surfactants. The functional group may be in the main chain or in the side chain, and the main chain may be partially crosslinked.
The polymer contains a specific site as long as the polymer includes a monomer unit having the site in part, and may include a monomer unit that does not have the site. Good. In other words, the polymer may be a copolymer.

The above polymers are radical polymerization, radical (alternate) copolymerization, anionic polymerization, anion (alternate) copolymerization, cationic polymerization, cationic (alternate) copolymerization, graft polymerization, graft (alternate), from monomers corresponding to the polymer structural unit. ) Copolymerization, living polymerization, living (alternate) copolymerization, dispersion polymerization, emulsion polymerization, suspension polymerization, ring-opening polymerization, cyclization polymerization, polymerization by light, ultraviolet ray or electron beam irradiation, metathesis polymerization, electrolytic polymerization, etc. be able to. At this time, a compound containing at least one element selected from the group consisting of zinc-containing compound particles such as zinc oxide particles, conductive auxiliary agent particles, and elements belonging to Groups 1 to 17 of the periodic table, in the polymer, and / or Alternatively, it can be incorporated on the surface to form a single particle. The polymer may cause a reaction such as hydrolysis in the electrolytic solution. Moreover, a monomer may be used at the time of electrode preparation, and it may be polymerized at the time of charging / discharging.

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

As a compounding quantity in the zinc negative electrode mixture of the said zinc containing compound, it is preferable that it is 50-99.9 mass% with respect to 100 mass% of whole quantity of a zinc negative electrode mixture. When the amount of the zinc-containing compound is in such a range, better battery performance is exhibited when a zinc negative electrode formed from a zinc negative electrode mixture is used as the negative electrode of the battery. More preferably, it is 55-99.5 mass%, More preferably, it is 60-99 mass%.

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.
The average particle diameter can be measured by the same method as the above-described average particle diameter measuring method.
Examples of the shape of the zinc-containing compound particles include fine powder, powder, granule, fine granule, scaly, fiber, granule, polyhedron, rod, rectangular, cylindrical, curved surface, and the like. .

The specific surface area of the zinc-containing compound is preferably 0.01 m ² / g or more and 60 m ² / g or less, and more preferably 0.1 m ² / g or more and 50 m ² / g or less.
The specific surface area can be measured by the same method as the method for measuring the specific surface area described above.

It is preferable that the said zinc negative electrode mixture contains a conductive support agent with a zinc containing compound.
Examples of the conductive aid include conductive carbon, conductive ceramics, zinc / zinc powder / zinc alloy / zinc used in (alkaline) dry batteries and air batteries (hereinafter also referred to as metal zinc). be able to.
The conductive carbon is the same as that described above as the conductive carbon in the carbon-containing layer.
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 metallic zinc may be one whose surface is coated with another element, carbon or the like, or may be alloyed. It may be a solid solution. The said conductive support agent can be used by 1 type, or 2 or more types.

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

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

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

The specific surface area of the conductive aid 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, and still more preferably. 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. .
By setting the specific surface area of the conductive additive to the above value, there are effects such as the ability to suppress the shape change of the zinc-containing compound which is the active material and the formation of the passive state in the process of using the battery.
The average particle diameter and specific surface area can be measured by the same method as described above.

The zinc negative electrode mixture 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, the above-described simple substance or compound of at least one element selected from the group consisting of elements belonging to Groups 1 to 17 of the periodic table is added to a slurry or paste mixture for forming a carbon-containing layer. A method similar to the method of mixing can be performed. 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. 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 may be alloyed. It is also possible to introduce an element having a reduction potential more noble than zinc into the zinc-containing compound by a charge / discharge process.

The zinc negative electrode of the present invention is preferably formed using the zinc negative electrode mixture.

The active material layer containing the zinc species can be prepared by coating, pressure bonding, or bonding a zinc negative electrode mixture containing a zinc-containing compound. Examples of the method for preparing the active material layer of 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 applied, pressure-bonded, or bonded on a current collector and / or a layer containing carbon (electrode underlayer) so that the film thickness is as constant as possible. . It is also possible to add the carbon to the slurry or paste mixture of the zinc negative electrode mixture, and form the active material layer of the zinc negative electrode and the layer containing carbon on the current collector by one liquid.

The slurry or paste mixture may be applied, pressure-bonded, or adhered to one surface of the electrode base layer, or may be coated, pressure-bonded, or adhered to both surfaces or the entire surface. 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 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 10-500 degreeC at the time of a press. When performing the pressing, it is possible to improve the adhesion between the active materials and / or between the active material and the binder, and to adjust the thickness of the active material layer.

The zinc negative electrode (zinc mixture electrode) thus obtained suppresses the decomposition of water in the zinc negative electrode, particularly when used as a negative electrode for a secondary battery. Deformation such as dendrite, deterioration due to passive formation, and generation of hydrogen in the process of use as a negative electrode of a battery can be suppressed to the maximum.
The film thickness of the zinc negative electrode is preferably 1 nm to 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-600 micrometers, More preferably, it is 20 nm-500 micrometers.
In addition, as long as the zinc negative electrode of this invention is equipped with the layer containing carbon mentioned above, you may be equipped with the other member. Moreover, this other member may contain 1 type, and may contain 2 or more types.

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

The battery of the present invention can include a positive electrode, an electrolyte, and the like in addition to the zinc negative electrode. Further, as the electrolyte, a water-containing electrolytic solution is preferable as described later.
Therefore, a battery comprising the zinc negative electrode, the positive electrode, 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.

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

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

The concentration of the electrolytic solution is preferably 0.01 to 50 mol / L of an electrolyte (for example, potassium hydroxide). By using an electrolytic solution having such a concentration, good battery performance can be exhibited. More preferably, it is 1-20 mol / L, More preferably, it is 3-18 mol / L. In addition, when the following water-containing electrolyte is used for a primary battery or a secondary battery using a water-containing electrolyte having a zinc-containing compound as a negative electrode, zinc oxide, zinc hydroxide, phosphorous is further added to the electrolyte. It is preferable to add at least one zinc compound selected from zinc acid, zinc pyrophosphate, zinc borate, zinc silicate, zinc aluminate, zinc metal, and tetrahydroxy zinc ion salt. Thereby, generation | occurrence | production of the shape change of electrode active materials, such as a shape change and a dendrite accompanying the melt | dissolution of a zinc electrode active material in the process of use of a battery, growth, and formation of a passive state can further be suppressed. The zinc compound in the electrolytic solution is preferably from 0.0001 mol / L to a saturated concentration. Note that the electrolytic solution may or may not be circulated.

The electrolytic solution may contain, as an additive, a compound containing at least one element selected from the group consisting of elements belonging to Groups 1 to 17 of the periodic table other than zinc. In the case of using an aqueous electrolyte, side reactions in the process of using a battery in which hydrogen is generated by the progress of a water decomposition reaction, which usually occurs thermodynamically, the shape change of the zinc electrode active material, the Dynamic formation can be suppressed. It is considered that this is because the additive suitably interacts with the surface on the zinc oxide to suppress side reactions, morphological change of the zinc electrode active material, and passive formation.
As an additive, for example, in the case of an aqueous electrolyte using potassium hydroxide as an electrolyte, magnesium hydroxide, barium hydroxide, calcium hydroxide, magnesium chloride, barium chloride, calcium chloride, potassium fluoride, potassium borate Potassium hydrogen borate, sodium borate, sodium hydrogen borate, potassium phosphate, potassium hydrogen phosphate, sodium phosphate, sodium hydrogen phosphate, potassium arsenate, lithium carbonate, potassium carbonate, sodium carbonate, magnesium carbonate, carbonic acid Calcium, barium carbonate, indium hydroxide, potassium silicate, sodium silicate, lithium hydroxide, sodium sulfide, potassium sulfate, sodium sulfate, potassium thiosulfate, sodium thiosulfate, cadmium oxide, cobalt hydroxide, titanium oxide, zirconium oxide , Aluminum fluoride, lithium oxide, sodium oxide, lithium hydroxide, sodium hydroxide, magnesium oxide, calcium oxide, barium oxide, bismuth oxide, bismuth hydroxide, zinc hydroxide, lead oxide, lead acetate, tellurium oxide, iron oxide, oxidation Germanium, tin oxide, tin hydroxide, tin chloride, indium oxide, lanthanoid oxide, niobium oxide, chromium oxide, copper oxide, gallium oxide, thallium oxide, antimony oxide, sorbitol and other sugars, quaternary ammonium salts, quaternary Phosphonium salt, caprolactam compound, chelating agent, methanol, ethanol, butanol, carboxylic acid, carboxylate, sulfonic acid, sulfonate, sulfonamide, sulfone, sulfoxide, polymer, gel compound, carboxylate group, and / or sulfonate Group and / or They are quaternary ammonium salts, and / or a polymer or gel compound having a quaternary phosphonium salt.
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 the battery of the present invention, the electrolyte may be a gel 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, filter paper, polymer containing hydrocarbon moiety such as polyethylene and polypropylene, polymer containing polytetrafluoroethylene moiety, polymer containing polyvinylidene fluoride, cellulose, fibrillated cellulose, viscose rayon. , Cellulose acetate, hydroxyalkyl cellulose, carboxymethyl cellulose, polyvinyl alcohol-containing polymer, cellophane, polystyrene-containing aromatic ring moiety-containing polymer, polyacrylonitrile moiety-containing polymer, polyacrylamide moiety-containing polymer, polyhalogenated vinyl moiety-containing polymer, polyamide moiety-containing Polymers, polyimide site-containing polymers, ester site-containing polymers such as nylon, poly (meth) acrylic acid site-containing polymers, poly ( T) Acrylate moiety-containing polymers, hydroxyl group-containing polymers such as polyisoprenol and poly (meth) allyl alcohol, carbonate group-containing polymers such as polycarbonate, ester group-containing polymers such as polyester, carbamate and carbamide group moieties such as polyurethane Polymer, agar, gel compound, organic-inorganic hybrid (composite) compound, ion exchange membrane polymer, cyclized polymer, sulfonate-containing polymer, quaternary ammonium salt-containing polymer, quaternary phosphonium salt polymer, cyclic hydrocarbon group Inorganic substances such as containing polymers, ether group-containing polymers, ceramics and the like. In the case where the separator is composed of the polymer, the polymer contains a specific site / functional group if the polymer includes a monomer unit having the site / functional group in part. What is necessary is just to include the monomer unit which does not have the said site | part and functional group. In other words, the polymer may be a copolymer.
The separator may include a compound having at least one element selected from the group consisting of elements belonging to Groups 1 to 17 of the periodic table. When the separator is composed of a polymer, when the polymer has a functional group, the functional group may be in the main chain or in the side chain. The main chain is ester bond, amide bond, ionic bond, van der Waals bond, agostic interaction, hydrogen bond, acetal bond, ketal bond, ether bond, peroxide bond, carbon-carbon bond, carbon-nitrogen bond, carbamate bond. , A thiocarbamate bond, a carbamide bond, a thiocarbamide bond, an oxazoline moiety-containing bond, a triazine bond, and 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. When using a water-containing electrolyte, it is preferable to perform a hydrophilic treatment on the separator by introducing a surfactant or the like. A water-containing electrolytic solution and a solid electrolyte may be used in combination.

As described above, a battery having a zinc negative electrode prepared from the zinc negative electrode mixture is also one aspect of the present invention. The positive electrode is more preferably a nickel electrode, a manganese electrode, or an air electrode. Here, taking the nickel electrode as an example, the configuration of the nickel / zinc storage battery will be described below.
The nickel-zinc 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 walls of the assembly and the holding container are made of a material that does not deteriorate due to corrosion or reaction in the process of using the battery. It is also possible to use a container used for an alkaline battery or a zinc-air battery. The storage battery is a single type, single type, single type, single type, single type, single type, single type, R123A type, cylindrical type such as R-1 / 3N type, etc .; square type such as 9V type, 006P type, etc. A button type; a coin type; a laminate type; a laminated type; a type in which positive and negative plates formed 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 in the process of using a battery.

The negative electrode mixture of the present invention may contain a negative electrode active material and a polymer. By adopting such a configuration for the negative electrode mixture, it is possible to effectively suppress the form change and the formation of passive state such as shape change and dendrite of the electrode active material.

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

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.

An electrode base layer used for a zinc negative electrode, wherein the electrode base layer includes a current collector layer and a layer containing carbon, and the carbon-containing layer is a part of a surface of the current collector layer. Or the electrode base layer which covers all is also one of this invention. When a battery is formed using a zinc negative electrode including such an electrode base layer, dissociation between the electrode base layer and the negative electrode active material layer containing zinc is suppressed, and the battery performance is sufficiently improved. Can do.
The layer containing carbon in the electrode underlayer of the present invention may be any one that covers a part or all of one of the main surfaces of the current collector layer.
The preferable structure in the electrode base layer of the present invention is the same as the preferable structure of the electrode negative layer in the zinc negative electrode and battery of the present invention described above.

The zinc negative electrode of the present invention has the above-described configuration. When a battery is formed using this, the dissociation between the electrode base layer and the negative electrode active material layer containing zinc is suppressed as compared with a conventional battery using a zinc negative electrode. In addition, battery performance can be sufficiently improved. In addition, when a water-containing electrolyte is used, the battery is highly safe.

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 present specification, the carbon-containing layer usually refers to a solid obtained after removing the solvent from the composition used to form the carbon-containing layer.
In addition, the adhesiveness between a certain member and a certain member may be through a binder component between both members.

Example 1
(Operation A)
Add natural graphite (1.0 g), 12% polyvinylidene fluoride / N-methylpyrrolidone solution (0.97 g), N-methylpyrrolidone (1.5 g) to a glass vial and use a stirrer bar with a stirrer overnight. Stir. The obtained slurry was coated on a copper foil using an automatic coating apparatus and dried at 80 ° C. for 12 hours to obtain a copper foil having a carbon-containing layer thereon.

(Operation B)
Zinc oxide (1.84 g), acetylene black (0.21 g), cerium (IV) oxide (0.16 g), 12% polyvinylidene fluoride / N-methylpyrrolidone solution (2.42 g), N-methylpyrrolidone (3 g) ) Was added to a glass vial and stirred with a stirrer overnight using a stir bar. The obtained slurry was applied to a copper foil having a carbon-containing layer obtained in the above (Example 1, operation A) using an automatic coating apparatus, dried at 80 ° C. for 12 hours, and then 3 t. Pressed with pressing pressure. By punching this with a punching machine (diameter: 15.95 mm), a carbon-containing layer is used as a zinc mixture electrode covering the entire surface of the active material layer side of the copper foil, and 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 in which zinc oxide is dissolved to saturation is used for the electrolyte, and a current value of 0.96 mA using a triode cell. (Charge / discharge time: 1 hour each / -0.1V and 0.4V cut off). When the electrode after 60 cycles was observed with an SEM, almost no dendritic zinc species were observed on the current collector.

(Example 2)
(Operation A)
Acetylene black (0.3 g), an acrylic resin (copolymer of ethyl acrylate and lithium methacrylate) and an aqueous solution (0.97 g) containing 3% of styrene maleic acid polymer, water (1.5 g), ethanol (1.0 g) was added to a glass vial and stirred with a stirrer overnight using a stir bar. The obtained slurry was coated on a copper foil using an automatic coating apparatus and dried at 80 ° C. for 12 hours to obtain a copper foil having a carbon-containing layer thereon.

(Operation B)
Zinc oxide (1.84 g), acetylene black (0.21 g), cerium (IV) oxide (0.16 g), 12% polyvinylidene fluoride / N-methylpyrrolidone solution (2.42 g), N-methylpyrrolidone (3 g) ) Was added to a glass vial and stirred with a stirrer overnight using a stir bar. The obtained slurry was coated on the copper foil having the carbon-containing layer obtained in the above (Example 2, operation A) using an automatic coating apparatus and dried at 80 ° C. for 12 hours. Pressing was performed at a press pressure of 3 t. By punching this with a punching machine (diameter: 15.95 mm), a carbon-containing layer is used as a zinc mixture electrode covering the entire surface of the active material layer side of the copper foil, and a working electrode having an apparent area of 0.48 cm ² (Zinc mixture weight: 2.31 mg). A zinc electrode is used for the counter electrode, a zinc wire is used for the reference electrode, and a 4 mol / L aqueous potassium hydroxide solution in which zinc oxide is dissolved to saturation is used for the electrolyte, and a current value of 1.52 mA using a three-electrode cell. (Charge / discharge time: 1 hour each / -0.1V and 0.4V cut off). When the electrode after 60 cycles was observed with an SEM, the adhesion between the current collector layer and the carbon-containing layer was very high, and almost no dendritic zinc species were observed on the current collector.

(Comparative Example 1)
Zinc oxide (1.84 g), acetylene black (0.21 g), cerium (IV) oxide (0.16 g), 12% polyvinylidene fluoride / N-methylpyrrolidone solution (2.42 g), N-methylpyrrolidone (3 g) ) Was added to a glass vial and stirred with a stirrer overnight using a stir bar. The obtained slurry was coated on a copper foil using an automatic coating apparatus, dried at 80 ° C. for 12 hours, and then pressed with a 3 t press pressure. By punching this out with a punching machine (diameter: 15.95 mm), the electrode underlayer is a zinc mixture electrode not including a carbon-containing layer, and 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 in which zinc oxide is dissolved to saturation is used for the electrolyte, and a current value of 0.96 mA using a triode cell. (Charge / discharge time: 1 hour each / -0.1V and 0.4V cut off). When the electrode after 60 cycles was observed with an SEM, dendritic zinc species were observed on a part of the current collector.

The following was found from the results of the examples.
A zinc negative electrode comprising an electrode underlayer and an active material layer bound to the electrode underlayer and containing a zinc species, the electrode underlayer containing a current collector layer and carbon The zinc-containing negative electrode that covers a part or all of the surface of the current collector layer on the active material layer side of the current collector layer is an active material containing a current collector layer constituting the electrode base layer and a zinc species. In the process of use as the negative electrode of the battery, dissociation between the electrode underlayer and the negative electrode active material layer containing zinc is suppressed, and the battery performance is sufficiently improved. It was proved that it can be improved.
In the above embodiment, the carbon-containing layer is formed using specific conductive carbon. However, the zinc negative electrode of the present invention uses the current collector layer and the zinc species constituting the electrode base layer. In the process of use as the negative electrode of the battery, dissociation between the electrode base layer and the negative electrode active material layer containing zinc is suppressed after sufficiently improving the electrical conductivity between the active material layer including The battery performance can be sufficiently improved in the same manner when the carbon-containing layer is used.
Further, in the above embodiment, the carbon-containing layer covers the entire surface of the current collector layer on the active material layer side, but the carbon-containing layer is on the active material layer side of the current collector layer. If it covers a part of the surface of the battery, of course, the current-carrying property between the current collector layer constituting the electrode base layer and the active material layer containing zinc species is sufficiently excellent. It can be said that the effect of the present invention that improves the battery performance is suppressed by suppressing dissociation between the electrode base layer and the negative electrode active material layer containing zinc in the process of use as the negative electrode.
Therefore, it can be said from the results of the above-described embodiments that the present invention can be applied in the entire technical scope of the present invention and in various forms disclosed in this specification, and can exhibit advantageous effects.

Claims (3)

A zinc negative electrode comprising an electrode underlayer and an active material layer bound to the electrode underlayer and containing a zinc species,
The electrode underlayer includes a current collector layer and a layer containing carbon,
The zinc-containing negative electrode characterized in that the carbon-containing layer covers part or all of the surface of the current collector layer on the active material layer side. A battery comprising the zinc negative electrode according to claim 1, a positive electrode, and an electrolyte. An electrode underlayer used for a zinc negative electrode,
The electrode underlayer includes a current collector layer and a layer containing carbon,
The electrode-containing layer, wherein the carbon-containing layer covers part or all of the surface of the current collector layer.