JP6306914B2 - Electrode and battery - Google Patents

Description

The present invention relates to an electrode and a battery. More specifically, the present invention relates to an electrode and a battery that are excellent in economy and safety and can be suitably used for a battery having high performance.

In recent years, the importance of development and improvement of batteries has increased in many industries from portable devices to automobiles, etc., and new battery systems that are superior mainly in terms of battery performance and conversion to secondary batteries have been developed. Various developments and improvements have been made.

For example, a zinc negative electrode using a zinc species as a negative electrode active material has been studied for a long time with the spread of batteries. In the zinc negative electrode, it is necessary to suppress the self-discharge reaction accompanied with hydrogen generation, and various studies have been made so far. A zinc negative electrode or an electrolyte that suppresses hydrogen generation by introducing an inorganic or organic additive into the electrolyte has a positive electrode made of nickel oxide as an active material, a negative electrode, and an alkaline electrolyte. Disclosed is a nickel-zinc storage battery characterized in that the active material is a zinc alloy containing one element selected from the group consisting of indium, lead, tin, cadmium, thallium, silver, gallium, tellurium and lanthanum. (For example, refer to Patent Document 1). Further, with respect to the improvement of the separator, a battery separator made of a nonwoven fabric or a woven fabric of a fiber mainly composed of a polyolefin resin, wherein the polyolefin resin particles are fixed on the surface of the fiber, and is resistant to resistance. A battery separator is disclosed in which a hydrophilic organic substance having electrolyte properties is dispersed on the surfaces of the fibers and particles, or covers the surfaces thereof (see, for example, Patent Document 2).

JP-A-53-85349 Japanese Patent No. 2734523

The batteries described in Patent Documents 1 and 2 using zinc as a negative electrode are no longer mainstream in battery development as new batteries using other elements as negative electrodes are developed. However, when zinc is used 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, and economical and safe As a battery that can achieve both performance and performance, there is a possibility that it can be used in many industrial fields from small devices to large devices such as cars. However, the inventions of the batteries described in Patent Documents 1 and 2 have room for improvement in terms of suppressing self-discharge reactions. Battery self-discharge is a problem common to all batteries, not limited to batteries using zinc as a negative electrode, and development of a method for further suppressing battery self-discharge and further improving battery performance is required. Furthermore, the electrode using the zinc negative electrode has a problem of short circuit due to zinc dendrite growth, and the invention of the battery described in Patent Documents 1 and 2 sufficiently prevents the short circuit due to dendrite even after repeated charge / discharge cycles. There was room for innovation.

This invention is made | formed in view of the said present condition, and aims at providing the electrode and battery which can suppress the self-discharge reaction and the growth of a dendrite.

As a result of various studies on methods for suppressing the self-discharge of the battery, the present inventors have found that the voids in the active material layer of the negative electrode affect the self-discharge reaction, and that the larger the void, the more the self-discharge reaction is suppressed. . And this inventor discovered that self-discharge could fully be suppressed, fully exhibiting the performance as a battery, when the porosity of the active material layer (inner) of an electrode shall be 30 to 79%.

Furthermore, the present inventors have studied various methods for suppressing the growth of dendrite.
A dendrite is formed when a metal such as zinc is deposited on the electrode during charging. In a battery comprising a zinc negative electrode, the dendrite formed by the precipitation of zinc is derived from the high crystallinity of zinc, which makes it easy to form crystals even when a uniform current flows in the electrode surface. Very easy to form. In order to suppress this, it is necessary to reduce the surface energy of zinc as much as possible. As an example so far, a second component such as indium or titanium is added to the electrode, and those films are formed on the zinc surface during charging. Some have controlled the crystalline state. However, in these cases, the dendrite growth was not sufficiently suppressed.
In the process of repeating the charge / discharge cycle, metal ions such as Zn (OH) ₄ ²⁻ move to a location where current easily flows in the electrode surface, so the charge / discharge cycle is repeated, and in the electrode surface where metal zinc is deposited and exposed. When the current easily flows in a part of the metal, the concentration of metal ions such as Zn (OH) ₄ ²⁻ increases around the part in the electrode surface. As described above, when the second component is added to the electrode to suppress the dendrite, the component for suppressing the dendrite is depleted at the portion where the zinc concentration is high, and the dendrite growth cannot be sufficiently suppressed. there is a possibility. That is, essential dendrite suppression requires a mechanism for suppressing the movement (diffusion) of metal ions such as Zn (OH) ₄ ^{2− in} addition to the device for reducing the surface energy of zinc.

From such an idea, the present inventors have a configuration that can reduce the surface energy of the active material, suppress dendrite growth, and short circuit caused by this, and include Zn (OH) ₄ ^{2- and the} like. Various electrodes have been studied which can sufficiently prevent the diffusion of metal ions, suppress the uneven concentration of metal ions, maintain the above-mentioned configuration even after repeating the charge / discharge cycle, and suppress short circuit due to dendrite.

Here, the present inventors paid attention to the active material layer contained in the electrode and studied various methods for controlling the diffusion of metal ions such as Zn (OH) ₄ ²⁻ from the active material layer. The inventors of the present invention have a selective ionic conductivity in the zinc negative electrode of a nickel / zinc battery that has conductivity of ions involved in the battery reaction but does not have conductivity of ions constituting the active material. By covering the active material and / or the active material layer with the ion conductive layer, the diffusion of metal ions such as Zn (OH) ₄ ²⁻ is sufficiently prevented, the concentration deviation of the metal ions is suppressed, the growth of dendrites and It discovered that the short circuit by this can be suppressed. Furthermore, the present inventors have also found that if the porosity in the active material layer of the electrode is in the above range, the growth of dendrites is suppressed by the voids, and short-circuiting is less likely to occur. The present inventors have arrived at the present invention.

That is, the present invention provides an electrode comprising an active material layer containing an active material and a current collector, wherein the active material and / or active material layer is covered with an ion conductive layer, and the ion conductive layer is involved in a battery reaction. The active material layer has a selective ion conductivity that does not have conductivity of ions constituting the active material but has the following formula (1):
Porosity = V '/ V (1)
(In the formula, V represents the volume of the active material layer. V ′ represents the volume of the voids in the active material layer.)
Is an electrode having a porosity of 30 to 79%.
The present invention is described in detail below.
A combination of two or more preferred embodiments of the present invention described below is also a preferred embodiment of the present invention.

<Porosity in the active material layer>
The electrode of the present invention is characterized in that the porosity in the active material layer represented by the above formula (1) is 30 to 79%, whereby a battery using this electrode has performance as a battery. While exhibiting sufficiently, self-discharge can be sufficiently suppressed, and the coulomb efficiency is good. The relationship between the porosity in the active material layer of the electrode and suppression of self-discharge is considered as follows.
When the active material layer is densely filled with active material particles, the porosity is small, and when the active material layer is loosely filled with active material particles, the porosity is large. When the porosity is large, the distance between the individual active materials in the active material layer becomes large, and thus the self-discharge reaction is suppressed by preventing the electron conductivity of the self-discharge reaction site in the charged state. it is conceivable that. On the other hand, when the porosity in the active material layer is small and the individual active materials are in close contact with each other, the electron conductivity at the self-discharge reaction site is high and the self-discharge reaction is likely to occur. If it is larger, it is considered that such a problem can be sufficiently suppressed.
Moreover, if the porosity in the active material layer of the said electrode is the said range, the growth in a dendrite will be suppressed by the space | gap in an active material layer, and it will become difficult to produce a short circuit.

The active material layer includes an active material, and is a layer formed by applying an electrode mixture composition, which will be described later, onto a current collector. The active material layer may be one type or two or more types. The number of active material layers may be one or two or more.
The void means a volume obtained by subtracting the volume of the active material contained in the active material layer from the volume of the active material layer. The volume of the active material layer means the total volume of two or more active material layers when there are two or more active material layers.
The volume of the active material layer can be determined from the product of the film thickness and the electrode geometric area.

The porosity is 30 to 79%, preferably 50 to 79%, more preferably 65% to 75%.
When the porosity exceeds 79%, the amount of the active material is reduced, so that the battery capacity is reduced and the strength of the electrode may be reduced. Furthermore, it becomes difficult to form a conductive matrix, and it is difficult to efficiently take a discharge capacity. However, such a problem can be suppressed if the porosity is 79% or less.
Moreover, it is difficult to produce an electrode having a porosity of 30%.
The void volume V ′ of the active material layer can be measured by a mercury porosimeter described later. In addition, when forming an active material layer using an active material covered with an ion conductive layer, which will be described later, the mercury porosimeter measures the volume of the voids including the voids in the ion conductive layer. The porosity of the active material layer is calculated from the measurement result of the void volume using the active material layer formed under the same conditions except that the active material not covered with the ion conductive layer is used.

The voids can be increased by increasing the volume V of the active material layer and / or decreasing the volume of the active material. Although the method of changing these volumes is not limited, the volume V of the active material layer is formed by, for example, applying, pressing, or adhering an electrode mixture composition described later to the current collector to form the active material layer. It can be changed by adjusting the pressing pressure. Moreover, the void volume V ′ of the active material layer can be varied by increasing or decreasing the amount of the active material in the electrode mixture composition, for example. When the volume V of the active material layer is increased by adjusting the press pressure at the time of forming the active material layer, the gap is increased without reducing the amount of the active material contained in the active material layer. This is preferable.

<Ion conductive layer>
The active material and / or active material layer of the electrode of the present invention is covered with an ion conductive layer, and the ion conductive layer has conductivity of ions involved in the battery reaction, but the conductivity of ions constituting the active material is It has no selective ionic conductivity.

The ion conductive layer can selectively transmit ions by the following mechanism or the like.
(1) When the ion conductive layer contains a layered substance, the ions are transmitted by ion exchange with ions existing between layers of the layered substance.
(2) When the ion conductive layer includes an ionic crystal, the ion is transmitted through the site in the crystal that can be occupied by the ion.
(3) When the ion conductive layer includes an ionic crystal having ion vacancies (lattice defects), the vacancies are permeated by movement of ions.
(4) An ion conductive layer is formed in the vicinity of the particle surface between particles constituting the ion conductive layer, and the ions are transmitted by moving between the particles.
In the mechanisms (1) to (4) described above, the ion charge density greatly influences the permeability in addition to the ion radius to be transmitted, and the ion conductive layer of the present invention has the ion permeability depending on the charge density of the ions to be transmitted. And can selectively permeate either a cation or an anion.
For this reason, the ion conductive layer of the present invention has high selective permeability, and a precise battery design is possible.

In the battery, an electrode reaction involving ions proceeds in each of the positive electrode and the negative electrode. The type of ions involved in the electrode reaction varies depending on the battery, and the active material may be an ion or an ion other than the active material.
Ions having conductivity in the battery reaction but having no conductivity of ions constituting the active material are ions other than ions constituting the active material among the ions involved in the electrode reaction of the battery. Means that the ions constituting the active material are not allowed to pass through.
Among the ions involved in the battery electrode reaction, ions other than the ions constituting the active material include, for example, hydroxide ions in nickel-zinc batteries and sulfate ions in lead-acid batteries.

Examples of ions constituting the active material include Zn (OH) ₄ ²⁻ in a nickel zinc battery, [Zn (NH ₃ ) ₄ ] ²⁺ in a manganese dry battery, and Pb ²⁺ in a lead storage battery.

The ion conductive layer is particularly limited as long as it has the conductivity of ions involved in the battery reaction but does not have the conductivity of ions constituting the active material to the extent that it can suppress the growth of dendrites. However, it is preferably formed using an anion conductive material described later.

Covering the active material and / or the active material layer means covering at least a part of the active material and the active material layer so that the active material and the electrolyte are not in direct contact when a battery is formed using an electrode. means. Here, when the battery is formed using the electrode, it is preferable to cover at least a part of the active material and the active material layer so that substantially all of the active material in the electrode of the present invention is not in direct contact with the electrolyte. . More preferably, the entire active material and active material layer are covered.
In the electrode of the present invention, since the active material and the electrolyte usually act via the ion conductive layer, when the battery is configured using the electrode of the present invention, an electrochemical reaction may occur as the battery. it can.
The ion conductive layer covering the active material means that the ion conductive layer covers each active material constituting the active material layer. Usually, the active material for forming the active material layer is previously covered with the ion conductive layer. Then, what is formed by forming an active material layer using an active material covered with an ion conductive layer. Here, the active material may be covered with the ion conductive layer only by the active material, and includes an active material and an active material layer constituent material other than the active material such as a conductive additive and other additives. It may be covered with an ion conductive layer.

Covering the active material layer means covering a part or the whole of the active material layer formed on the electrode, and usually using an active material and, if necessary, an active material layer constituent material other than the active material. It refers to what is formed by forming an active material layer and then covering the active material layer with an ion conductive layer. In addition, it is one preferable form to cover the entire active material layer formed on the electrode.

The ion conductive layer covers each active material particle constituting the active material layer, covers a part or the whole of the active material layer, or covers each unit in which the active material layer is divided. May be. In addition, when the active material layer is divided into several units in the electrode, the ion conductive layer covers one or more units for each unit, and forms other units for the other units. The active material particles to be covered may be covered.

When the ion conductive layer covers the active material layer of the electrode, if at least one surface of the active material layer constituting the electrode is bound to the current collector layer, the ion conductive layer is bonded to the current collector of the active material layer. It is only necessary that the remaining surface not covered is covered with the ion conductive layer. In other words, if the surface of the active material layer facing the electrolyte is covered with the ion conductive layer, the portion bound to the current collector layer of the active material layer is not covered with the ion conductive layer. Also good. In addition, when the active material layer has only one surface facing the electrolyte, it is sufficient that this one surface is covered with an ion conductive layer. However, the active material is advantageous in that the effect of the present invention becomes remarkable. It is preferable that there are a plurality of surfaces facing the electrolyte in the layer, and these surfaces are covered with the ion conductive layer.

When the ion conductive layer covers the active material layer of the electrode, the thickness of the ion conductive layer covering the active material layer can be appropriately selected, but is preferably 0.1 μm or more. More preferably, it is 0.5 μm or more. More preferably, it is 1 μm or more. Moreover, it is preferable that this thickness is 50 mm or less, for example. More preferably, it is 5 mm or less. More preferably, it is 1 mm or less.
The thickness of the ion conductive layer can be measured by measuring with a micrometer or the like, or observing a cross section of the electrode with a sharp instrument with an electron microscope.

That the active material particles are covered with the ion conductive layer means that the active material particles in the active material layer are respectively covered with the ion conductive layer. For example, the active material particles may be separated from each other in the active material layer and bound via the ion conductive layer. Although all of the active material particles contained in the active material layer may not be covered with the ion conductive layer, it is preferable that substantially all of the active material particles are covered with the ion conductive layer.
Examples of the shape of the active material particles include fine powders, powders, granules, granules, scales, polyhedrons, rods, curved surfaces, and the like. The active material particles may be not only primary particles but also secondary particles in which primary particles are aggregated.

The thickness of the electrode of the present invention is preferably 1 nm or more and 2000 μm or less 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 or more, More preferably, it is 20 nm or more. More preferably, it is 1500 micrometers or less, More preferably, it is 1000 micrometers or less.
The thickness of the electrode can be measured by a micrometer, a step meter, a contour shape measuring instrument, or the like.

The electrode of the present invention may be a positive electrode or a negative electrode, but is preferably a negative electrode. Moreover, the electrode of this invention may be comprised further including the general member used for an electrode besides having mentioned above.

(Anion conductive material of electrode)
The ion conductive layer of the present invention is preferably formed using an anion conductive material. The anion conductive material includes a polymer and a compound containing at least one element selected from Group 1 to Group 17 of the periodic table, and the compound includes an oxide, a hydroxide, and layered double water. What is necessary is just at least 1 compound chosen from the group which consists of an oxide, a sulfuric acid compound, and a phosphoric acid compound, and may further contain the other component mentioned later.

The anion conductive material according to the present invention is easy to permeate anions such as hydroxide ions involved in the battery reaction, and sufficiently prevents the diffusion of metal ions having a large ionic radius even if they are anions. Can do. In this specification, the anion conductivity means that an anion having a small ion radius such as a hydroxide ion is sufficiently transmitted, or the permeation performance of the anion. Anions having a large ion radius, such as metal ions, are more difficult to permeate and may not permeate at all. Such an anion-conducting material according to the present invention can selectively permeate the anion involved in the battery reaction, and can make it difficult to selectively permeate metal ions having a large ion radius. For example, when used for a zinc negative electrode, anions such as hydroxide ions involved in the battery reaction are easily transmitted, and metal ions such as Zn (OH) ₄ ²⁻ are not easily transmitted. In addition, the effect of preventing a short circuit caused by dendrite and prolonging the cycle life can be remarkably exhibited. Further, in some cases, the anion conductive material can transmit Li, Na, Mg, and Zn ions having a relatively small ionic radius.

The anion conductive material may be a gel having a three-dimensional structure. Moreover, as long as the effect of this invention can be exhibited, the said anion conductive material may have a void | hole in the surface and inside, and may not have a void | hole. For example, it may be preferable to have pores from the viewpoint of improving anion conductivity. Moreover, it may be preferable not to have a void | hole from a viewpoint of suppressing the spreading | diffusion of a metal ion more.

Hereinafter, an inorganic compound, a polymer, and other components will be described in order as included in the anion conductive material according to the present invention.

[Inorganic compounds]
Examples of the oxide include alkali metal, Be, Ca, Sr, Ba, Ra, Sc, Y, lanthanoid, Ti, Zr, Hf, V, Nb, Ta, Cr, Mo, W, Mn, Fe, Ru, Co Ni, Pd, Cu, Ag, Au, Zn, Cd, B, Al, Ga, In, Tl, C, Si, Ge, Sn, N, P, Sb, Bi, S, Se, Te, F, Cl And an oxide containing at least one element selected from the group consisting of Br. Among them, a compound containing at least one element selected from Group 1 to Group 15 of the periodic table is preferable, and Li, Na, K, Cs, Ca, Ba, Sc, Y, lanthanoid, Ti, Zr, Nb, Cr, Mn, Fe, Ru, Co, Ni, Pd, Cu, Ag, Au, Zn, Cd, B, Al, Ga, In, Tl, C, Si, Ge, Sn, Pb, N, P, An oxide containing at least one element selected from the group consisting of Sb and Bi is preferable. More preferably, Li, Ca, Ba, Sc, Y, lanthanoid, Ti, Zr, Nb, Cr, Mn, Fe, Ru, Co, Ni, Pd, Cu, Zn, Cd, B, Al, Ga, In, It is an oxide containing at least one element selected from the group consisting of Tl, Si, Sn, Pb, and Bi. More preferred are cerium oxide and zirconium oxide, and particularly preferred is cerium oxide. In addition, the cerium oxide may be, for example, a material doped with a metal oxide such as samarium oxide, gadolinium oxide, or bismuth oxide, or a solid solution with a metal oxide such as zirconium oxide. The oxide may have an oxygen defect.
As the hydroxide, for example, cerium hydroxide and zirconium hydroxide are preferable. In the present specification, the hydroxide refers to a hydroxide other than the layered double hydroxide.
As the layered double hydroxide, for example, hydrotalcite is preferable. Thereby, the anion conductivity of the anion conductive material can be remarkably improved.

When hydrotalcite is used as the anion conductive material, since it is a layered compound, anion can be transmitted by the selective permeation mechanism (1) of ions described above, and hydrotalcite- Since the anion conducting layer is formed in the vicinity of the particle surface between the hydrotalcite particles, the anion can be transmitted by the selective permeation mechanism (4) of ions described above.

The hydrotalcite is represented by the following formula (2);
[M ¹ _1-x M ² _x (OH) ₂ ] (A ⁿ⁻ ) _{x / n} · mH ₂ O (2)
(Wherein M ¹ = Mg, Fe, Zn, Ca, Li, Ni, Co, Cu, etc .; M ² = Al, Fe, Mn, etc .; A = CO ₃ ²⁻ etc., m is a positive number of 0 or more, x is preferably about 0.20 ≦ x ≦ 0.40, and n is preferably a compound represented by 1-2). This compound is a compound dehydrated by firing at 150 ° C. to 900 ° C., a compound obtained by decomposing an anion in the interlayer, a compound obtained by exchanging the anion in the interlayer with a hydroxide ion, or a natural mineral. Mg ₆ Al ₂ (OH) ₁₆ CO ₃ .mH ₂ O or the like may be used as the inorganic compound. The hydrotalcite may be coordinated with a compound having a functional group such as a hydroxyl group, an amino group, a carboxyl group, or a silanol group.
As the sulfate, for example, ettringite is preferable.

The inorganic compound may be in a dissolved state, a dispersed state of a colloid, or an insoluble state when it is introduced into an electrolytic solution raw material, an electrolytic solution, a gel electrolyte, etc., and a part of its surface is a plus. Or a negative charge is preferable, and the charged state of the particles can be inferred by measuring the zeta potential. As described later, these inorganic compounds interact with each other by non-covalent bonds such as covalent bonds, coordinate bonds, ionic bonds, hydrogen bonds, π bonds, van der Waals bonds, and agostic interactions with functional groups of polymers. It can also act. Moreover, when using layered compounds, such as a hydrotalcite, the polymer may be formed in the layer. The inorganic compound is used in a state where a part of its surface is not charged with a positive or negative charge (corresponding to an isoelectric point) when it is introduced into an electrolytic solution raw material, electrolytic solution, gel electrolyte, or the like. May be.

The anion conductive material is preferably one that becomes a hydrate when introduced into an electrolyte solution raw material, an electrolyte solution, a gel electrolyte, or the like. By being a hydrate, the conductivity of hydroxide ions and the like involved in the battery reaction can be further increased.

The inorganic compound preferably contains particles satisfying the following average particle diameter and / or the following specific surface area. More preferably, the inorganic compound satisfies the following average particle diameter and / or the following specific surface area.

The inorganic compound preferably has an average particle size of 1000 μm or less. The average particle diameter is more preferably 200 μm or less, still more preferably 100 μm or less, particularly preferably 75 μm or less, and most preferably 20 μm or less. On the other hand, the average particle size is preferably 5 nm or more. More preferably, it is 10 nm or more.
The average particle diameter can be measured with a scanning electron microscope (SEM).

Examples of the shape of the inorganic compound particles include fine powder, powder, granules, granules, scales, polyhedrons, rods, and curved surfaces. 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 inorganic compound preferably has a specific surface area of 0.01 m ² / g or more. The specific surface area is more preferably 0.1 m ² / g or more, and still more preferably 0.5 m ² / g or more. On the other hand, the specific surface area is preferably 500 m ² / g or less.
The specific surface area can be measured by a specific surface area measuring apparatus or the like by a nitrogen adsorption BET method.

The mass ratio of the inorganic compound is preferably 0.1% by mass or more with respect to 100% by mass of the anion conductive material. More preferably, it is 0.5 mass% or more, More preferably, it is 1 mass% or more, Most preferably, it is 3 mass% or more. Moreover, it is preferable that it is 99.9 mass% or less. More preferably, it is 99 mass% or less, More preferably, it is 75 mass% or less, Most preferably, it is less than 55 mass%.
By making the mass ratio of the inorganic compound within the above range, the effect of the present invention can be exhibited, and the effect of making it difficult to cause cracks in the anion conductive material can be exhibited. Among these, it is particularly preferable that the mass ratio of the layered double hydroxide is within the above range.

〔polymer〕
Examples of the polymer according to the present invention include hydrocarbon group-containing polymers such as polyethylene and polypropylene, aromatic group-containing polymers represented by polystyrene, etc .; ether group-containing polymers represented by alkylene glycol, etc .; polyvinyl alcohol and poly (α- Hydroxymethyl acrylate) and other hydroxyl group-containing polymers; polyamides, nylon, polyacrylamide, polyvinylpyrrolidone, N-substituted polyacrylamides and other amide group-containing polymers; polymaleimides and other imide group-containing Polymer; carboxyl group-containing polymer represented by poly (meth) acrylic acid, polymaleic acid, polyitaconic acid, polymethyleneglutaric acid, etc .; poly (meth) acrylate, polymaleate, polyitaconate, polymethyleneglutarate Carboxylate-containing polymers such as acid salts; halogen-containing polymers such as polyvinyl chloride, polyvinylidene fluoride, and polytetrafluoroethylene; polymers bonded by opening of epoxy groups such as epoxy resins; sulfonates AR ¹ R ² R ³ B (A represents N or P. B represents an anion such as a halogen anion or OH ^−. R ¹ , R ² and R ³ may be the same or different. Represents an alkyl group having 1 to 7 carbon atoms, a hydroxyalkyl group, an alkyl carboxyl group, or an aromatic ring group, and R ¹ , R ² , and R ³ may be bonded to form a ring structure. Quaternary ammonium salts and quaternary phosphonium salt-containing polymers represented by polymers with attached groups; ion-exchangeable heavys used for cation / anion exchange membranes, etc. Body; natural rubber; artificial rubber typified by styrene butadiene rubber (SBR), etc .; typified by cellulose, cellulose acetate, hydroxyalkylcellulose (eg, hydroxyethylcellulose), carboxymethylcellulose, chitin, chitosan, alginic acid (salt), etc. Amino group-containing polymer represented by polyethyleneimine; Carbamate group site-containing polymer; Carbamide group site-containing polymer; Epoxy group site-containing polymer; Heterocyclic and / or ionized heterocyclic site-containing polymer; Polymer alloy; Atom-containing polymers; low molecular weight surfactants and the like. Of these, carboxyl group-containing polymers and / or halogen-containing polymers are preferred. In the electrode of the present invention, the polymer preferably contains at least one selected from the group consisting of a halogen atom, a carboxyl group, a hydroxyl group, and an ether group. Among these, the above polymer is comprehensively considered in terms of (1) being an insulator, (2) being able to bind an anion conductive material powder, and (3) being excellent in physical strength. From such a viewpoint, a fluororesin, a carboxyl group-containing polymer, and a carboxylate salt-containing polymer are preferable. Examples of the fluororesin include a fully fluorinated resin in which all hydrogen atoms are substituted with fluorine atoms in the hydrocarbon moiety-containing polymer, and a partially fluorinated resin in which some hydrogen atoms are substituted with fluorine atoms in the hydrocarbon moiety-containing polymer. However, it is more preferably a fully fluorinated resin. A homopolymer or a copolymer may be used, but polytetrafluoroethylene is particularly preferable.

The above polymers are radical polymerization, radical (alternate) copolymerization, anionic polymerization, anionic (alternate) copolymerization, cationic polymerization, cationic (alternate) copolymerization, graft polymerization, graft (alternate), from the monomer corresponding to the constituent 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. Can do. When these polymers have a functional group, they may be present in the main chain and / or side chain, and may exist as a binding site with a crosslinking agent. These polymers may be used alone or in combination of two or more.
The polymer is composed of an ester bond, an amide bond, an ionic bond, a van der Waals bond, an agostic interaction, a hydrogen bond, an acetal bond, a ketal bond, an ether bond, a peroxide bond, and a carbon- It may be crosslinked via a carbon bond, carbon-nitrogen bond, carbon-oxygen bond, carbon-sulfur bond, carbamate bond, thiocarbamate bond, carbamide bond, thiocarbamide bond, oxazoline moiety-containing bond, triazine bond, etc. . However, when the crosslinked polymer has water absorption, the anion conductive material may be cracked. Therefore, the crosslinked polymer should not have water absorption.

The polymer preferably has a weight average molecular weight of 200 to 7000000. Thereby, the ion conductivity, flexibility, etc. of an anion conductive material can be adjusted. The weight average molecular weight is more preferably 400 to 6500000, and still more preferably 500 to 5000000.
The weight average molecular weight can be measured by gel permeation chromatography (GPC) or a UV detector.

The mass ratio of the polymer is preferably 0.1% by mass or more with respect to 100% by mass of the anion conductive material. More preferably, it is 1 mass% or more, More preferably, it is 25 mass% or more. Especially preferably, it is 40 mass% or more. Moreover, it is preferable that it is 99.9 mass% or less. More preferably, it is 99.5 mass% or less, More preferably, it is 99 mass% or less. Especially preferably, it is 80 mass% or less. Thereby, the effect which makes it hard to produce the crack of an anion conductive material is exhibited, and the effect of this invention can be made remarkable.

In the anion conductive material of the present invention, the mass ratio between the polymer and the inorganic compound is preferably 5000000/1 to 1/100000. More preferably, it is 2000000/1-1 / 50,000, More preferably, it is 1000000/1-1/10000. Particularly preferred is 100/3 to 82/100. In particular, when the inorganic compound contained in the anion conductive material according to the present invention is hydrotalcite, by satisfying the above mass ratio, the effect of improving the anion conductivity in the anion conductive material and cracks are produced. Both of the effects of making it difficult can be remarkably improved.

[Other ingredients]
The anion conductive material of the present invention may further contain other components as long as it contains a polymer and an inorganic compound.

The other components are not particularly limited. For example, clay compound; solid solution; alloy; zeolite; halide; carboxylate compound; carbonate compound; hydrogencarbonate compound; nitrate compound; Acid compound, boric acid compound; silicic acid compound; aluminate compound; sulfide; onium compound; The other components are compounds different from the inorganic compound and the polymer. The above-mentioned other components function to assist ion conductivity or form pores in the anion conductive material described later by being removed using a method such as solvent, heat, baking, electricity, etc. Is also possible.

The other components preferably include particles satisfying at least one selected from the group consisting of the following average particle diameter, the following specific surface area, and the following aspect ratio (length / width). More preferably, the other component satisfies at least one selected from the group consisting of the following average particle diameter, the following specific surface area, and the following aspect ratio (length / width).

The average particle size of the other components is preferably 1000 μm or less. The average particle diameter is more preferably 500 μm or less, still more preferably 200 μm or less, still more preferably 100 μm or less, particularly preferably 75 μm or less, and most preferably 20 μm or less. is there. On the other hand, the average particle size is preferably 5 nm or more. The average particle diameter is more preferably 10 nm or more, and still more preferably 20 nm or more.
The average particle size of the other components can be measured by the same method as the average particle size of the inorganic compound described above.

Examples of the shape of the particles of the other components 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 other components preferably have a specific surface area of 0.01 m ² / g or more. The specific surface area is more preferably 0.1 m ² / g or more, and still more preferably 0.5 m ² / g or more. Moreover, it is preferable that this specific surface area is 1500 m < ² > / g or less. The specific surface area is more preferably 500 m ² / g or less, still more preferably 450 m ² / g or less, and particularly preferably 400 m ² / g or less.
The specific surface area can be measured by the same method as the specific surface area of the inorganic compound described above.
The particles having a specific surface area as described above can be produced, for example, by making the particles into nanoparticles or by making the particle surface uneven by selecting the preparation conditions for particle production. is there.

The other components preferably have an aspect ratio (vertical / horizontal) of 1.1 or more. The aspect ratio (vertical / horizontal) is more preferably 2 or more, and further preferably 3 or more. The aspect ratio (vertical / horizontal) is preferably 100,000 or less. The aspect ratio (vertical / horizontal) is more preferably 50000 or less.
The aspect ratio (vertical / horizontal) can be determined from the shape of particles observed with a transmission electron microscope (TEM) or a scanning electron microscope (SEM). For example, when the particles of the other components are rectangular parallelepiped, the longest side can be obtained by dividing the vertical length by the horizontal length with the longest side being the vertical length and the second longest side being the horizontal direction. In the case of other shapes, a point is placed in the two-dimensional shape that is created when one part is placed on the bottom so that the aspect ratio is maximized and projected from the direction that maximizes the aspect ratio. Is measured by measuring the length of one point farthest from the vertical axis and dividing the vertical length by the horizontal length with the longest side as the vertical, the longest side of the straight line passing through the vertical center point as the horizontal. be able to.
In addition, particles having an aspect ratio (vertical / horizontal) in the above-described range are, for example, a method for selecting particles having such an aspect ratio, and optimization of preparation conditions at the stage of manufacturing the particles. It can be obtained by a method of obtaining selectively.

When other components are used, the mass ratio of the other components is preferably 0.001% by mass or more with respect to 100% by mass of the anion conductive material. More preferably, it is 0.01 mass% or more, More preferably, it is 0.05 mass% or more. Moreover, it is preferable that it is 90 mass% or less. More preferably, it is 80 mass% or less, More preferably, it is 70 mass% or less.

The anion conductive material according to the present invention may contain only one kind or two or more kinds of the above-mentioned polymer, inorganic compound and other components. In addition, when two or more types of polymers are included, the mass of the polymer means the total mass of the two or more types of polymers unless otherwise specified. The same applies to the case where two or more inorganic compounds and other components are contained.

The active material layer according to the present invention contains an active material, but may further contain a conductive additive and other additives described later. In addition, a conductive additive and other additives may be present in the voids. Hereinafter, the active material, the conductive additive, and other additives contained in the active material layer according to the present invention will be described in order.

[Active material]
The content ratio of the active material in the active material layer is preferably 50 to 99.9% by mass with respect to 100% by mass of the total amount of the active material layer. When the blending amount of the active material is in such a range, the volume of the active material in the active material layer is preferable, which contributes to setting the porosity to a preferable range. Therefore, when an electrode including such an active material layer is used for a battery, better battery performance is exhibited. More preferably, it is 55-99.5 mass%, More preferably, it is 70-99 mass%. The mass ratio of the active material contained in the active material layer can be calculated as the mass of the active material relative to the mass of solids other than the solvent contained in the electrode mixture composition.

The active material contained in the active material layer of the present invention may be a positive electrode active material or a negative electrode active material, but is preferably a negative electrode active material.

When the electrode of the present invention is a negative electrode, the active material of the negative electrode includes carbon species, lithium species, sodium species, magnesium species, zinc species, tin species, lead species, silicon-containing materials, hydrogen storage alloy materials, etc. What is normally used as a negative electrode active material of a battery can be used. Among these, it is one of the preferred embodiments of the present invention that the active material in the electrode of the present invention contains a zinc species.
When a zinc species is used as the active material, electrons pass through the zinc atom to move to a site where hydrogen is likely to be generated, and hydrogen is generated by the decomposition reaction of water, so that self-discharge accompanied with hydrogen generation occurs. . By using zinc species as the active material of the electrode of the present invention, hydrogen generation is suppressed by introducing inorganic or organic additives into the conventional zinc negative electrode or electrolyte as described in Patent Documents 1 and 2 above. As compared with the method of suppressing self-discharge accompanied with hydrogen generation by improving the separator and the method of improving the separator, the self-discharge accompanied with hydrogen generation can be more sufficiently suppressed.
Here, the zinc species refers to a zinc-containing compound. The zinc species may be repeatedly oxidized and reduced by driving the battery as long as it contains zinc.

The zinc-containing compound is not particularly limited as long as it can be used as an active material. For example, zinc oxide (1 type / 2 types / 3 specified in JIS K1410 (2006)), zinc hydroxide and zinc sulfide・ Tetrahydroxy zinc alkali metal salt ・ Tetrahydroxy zinc alkaline earth metal salt ・ Zinc halogen compound ・ Zinc carboxylate compound ・ Zinc alloy ・ Zinc solid solution ・ Zinc borate ・ Zinc phosphate ・ Zinc hydrogen phosphate ・ Zinc silicate ・ Alumine Zinc (alloy) compounds typified by zinc acid, carbonic acid compound, hydrogen carbonate compound, nitric acid compound, sulfuric acid compound, etc., organic zinc compounds, zinc compound salts, groups consisting of elements belonging to Groups 1 to 17 of the periodic table And zinc (alloy) compounds having at least one element selected from the above. Among these, zinc oxide (1 type / 2 types / 3 specified in JIS K1410 (2006)), zinc hydroxide, tetrahydroxy zinc alkali metal salt, tetrahydroxy zinc alkaline earth metal salt, zinc halogen compound, Zinc carboxylate compound, zinc alloy, zinc solid solution, zinc borate, zinc phosphate, zinc silicate, zinc aluminate, zinc carbonate, selected from the group consisting of elements belonging to groups 1 to 17 of the periodic table More preferred are zinc (alloy) compounds having at least one element. The zinc alloy may be a zinc alloy used in an (alkali) dry battery or an air battery. The zinc-containing compound can be used alone or in combination of two or more.

When the electrode of the present invention is a positive electrode, as the positive electrode active material, those normally used as the positive electrode active material of a primary battery or a secondary battery can be used. Examples include nickel-containing compounds such as nickel oxyhydroxide, nickel hydroxide, and cobalt-containing nickel hydroxide; manganese-containing compounds such as manganese dioxide; silver oxide; lithium-containing compounds such as lithium cobaltate; iron-containing compounds.
Among these, it is one of the preferred embodiments of the present invention that the positive electrode active material contains a nickel species.
In the case where the electrode of the present invention is a negative electrode, the active material can be used as a positive electrode in a battery configured using the negative electrode. Also, oxygen as the positive electrode active material (when oxygen is the positive electrode active material, the positive electrode is a perovskite type compound, cobalt-containing compound, iron-containing compound, copper-containing compound, manganese-containing compound capable of reducing oxygen and oxidizing water) , A vanadium-containing compound, a nickel-containing compound, an iridium-containing compound, a platinum-containing compound, a palladium-containing compound, a gold-containing compound, a silver-containing compound, a carbon-containing compound, etc.).

In the case of using a water-containing electrolyte when producing a storage battery using the active material, the active material may cause a water decomposition side reaction in the process of using the battery, thereby suppressing the side reaction. Therefore, a specific element may be introduced into the active material. Specific elements include Al, B, Ba, Bi, Br, C, Ca, Cd, Ce, Cl, Cu, F, Ga, Hg, In, La, Mg, Mn, N, Nb, Nd, Ni, P, Pb, S, Sb, Sc, Si, Sn, Sr, Ti, Tl, Y, Zr, etc. are mentioned.
Here, introducing a specific element into an active material means that the active material is a compound having these elements as constituent elements.

[Conductive aid]
The active material layer may include a conductive additive together with an electrode active material (referred to as a positive electrode active material or a negative electrode active material).
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.

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 microbead, carbon coated with metal, carbon coated metal, fibrous carbon, boron-containing carbon, nitrogen-containing carbon, multilayer / Single-walled carbon nanotubes, carbon nanohorns, Vulcan, acetylene black, carbon treated by introducing oxygen-containing functional groups, SiC-coated carbon, expressed by dispersion / emulsion / suspension / microsuspension polymerization, etc. Treated carbon, microcapsules carbon.

Examples of the conductive ceramic include a compound containing at least one selected from Bi, Co, Nb, and Y fired with zinc oxide.

Among the above conductive aids, graphite such as natural graphite and artificial graphite, graphitizable carbon, non-graphitizable carbon, graphene, carbon black, graphitized carbon black, ketjen black, vapor-grown carbon fiber, pitch-based carbon fiber Preferred are mesocarbon microbeads, fibrous carbon, multi-wall / single-wall carbon nanotubes, vulcan, acetylene black, carbon treated with a hydrophilic treatment by introducing an oxygen-containing functional group, and metallic zinc. In addition, the metallic zinc may be used for an actual battery such as an alkaline battery or an air battery, or may have a surface coated with another element or carbon, or may be alloyed. Also good. It may be a solid solution. 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.

In the case of using a water-containing electrolyte when producing a storage battery using this conductive auxiliary agent, there may be a case where a side reaction of water proceeds in the process of using the battery, and this side reaction is suppressed. In order to do this, a specific element may be introduced into the conductive additive. Specific elements include Al, B, Ba, Bi, Br, C, Ca, Cd, Ce, Cl, Cu, F, Ga, Hg, In, La, Mg, Mn, N, Nb, Nd, Ni, P, Pb, S, Sb, Sc, Si, Sn, Sr, Ti, Tl, Y, Zr, etc. are mentioned. When conductive carbon is used as one of the conductive assistants, specific elements include Al, B, Ba, Bi, C, Ca, Cd, Ce, Cu, F, Ga, In, La, and Mg. Mn, N, Nb, Nd, Ni, P, Pb, S, Sb, Sc, Si, Sn, Ti, Tl, Y, Zr are preferable.
Here, the introduction of a specific element into a conductive assistant means that the conductive assistant is a compound having these elements as constituent elements.

When the active material layer contains a conductive additive, the content of the conductive additive in the active material layer is 0.001 to 100% by mass with respect to 100% by mass of the active material in the active material layer. preferable. When the content ratio of the conductive auxiliary is in such a range, better battery performance is exhibited when an electrode including an active material layer is used for a battery. More preferably, it is 0.01-60 mass%, More preferably, it is 0.1-20 mass%. The mass ratio of the conductive auxiliary agent contained in the active material layer can be calculated as the mass of the conductive auxiliary agent relative to the mass of solids other than the solvent contained in the electrode mixture composition.
In addition, when using metallic zinc at the time of electrode mixture preparation, metallic zinc is considered not as an active material but as a conductive support agent. In addition, zinc metal produced in the process of battery use, such as zinc oxide and zinc hydroxide, which are zinc-containing compounds, will also function as a conductive aid in the system. Since it is not zero-valent metal zinc at the time of preparation, it is calculated here assuming that it is an active material, not a conductive aid. That is, the preferable content ratio of the active material and the conductive auxiliary agent is calculated by considering the zinc-containing compound at the time of preparing the zinc negative electrode mixture or the zinc negative electrode as the active material and metal zinc as the conductive auxiliary agent.

The conductive auxiliary agent preferably has an average particle size of 1 nm to 500 μm. More preferably, it is 5 nm-200 micrometers, More preferably, it is 10 nm-100 micrometers, Most preferably, it is 10 nm-60 micrometers.
In addition, the average particle diameter of the conductive auxiliary agent is determined by the transmission electron microscope (TEM) when the particle material included in the conductive auxiliary agent is a carbon material, or the scanning electron microscope when the material is a metal material. (SEM).

It is preferable that the specific surface area of the said conductive support agent is 0.1 m < ² > / g or more. More preferably, it is 1 m ² / g or more. Moreover, it is preferable that it is 1500 m < ² > / g or less. More preferably, it is 1200 m < ² > / g or less, More preferably, it is 900 m < ² > / g or less, More preferably, it is 250 m < ² > / g or less, Most preferably, it is 150 m < ² > / g or less.
By making the specific surface area of the conductive aid within the above range, it is possible to suppress the change in the shape of the active material and the formation of passive state in the process of using the battery, and to improve the utilization rate of the active material. effective.
In addition, the said specific surface area can be measured with a specific surface area measuring apparatus etc. by nitrogen adsorption BET method.

The zinc negative electrode mixture of the present invention may contain components other than the zinc-containing compound and the conductive additive, but when the zinc negative electrode mixture of the present invention further contains other components, the blending amount thereof is zinc. It is preferable that it is 0.01-100 mass% with respect to 100 mass% of zinc containing compounds in a negative mix. More preferably, it is 0.01-50 mass%, More preferably, it is 0.1-20 mass%. As described above, the zinc negative electrode mixture of the present invention is 0.01 to 100% by mass with respect to 100% by mass of the zinc-containing compound in the zinc negative electrode mixture. It is one of the preferred embodiments of the invention.

[Other additives]
The active material layer according to the present invention further comprises a compound comprising at least one element selected from the group consisting of elements belonging to Group 1 to Group 17 of the periodic table, an organic compound, and an organic compound salt It may contain at least one selected from more.

The compound having at least one element selected from the group consisting of elements belonging to Group 1 to 17 of the periodic table is at least one selected from the group consisting of elements belonging to Group 1 to 17 of the periodic table. Elemental oxides; hydroxides; layered double hydroxides; sulfides; halogen compounds; carboxylate compounds; carbonate compounds; hydrogen carbonate compounds; nitric acid compounds; sulfite compounds; Acid compounds; Phosphoric acid compounds; Hydrogen phosphate compounds; Boric acid compounds; Onium salts; Ammonium salts; Solid solutions; These elements may be doped in zinc oxide, or may be contained in a zinc-containing compound or a conductive additive.

Among the elements belonging to Group 1 to 17 of the periodic table, compounds having at least one element selected from the group consisting of elements belonging to Groups 1 to 5, 8, 9, and 11 to 17 of the periodic table are preferable. .

Here, in the case of a battery configured using an aqueous electrolytic solution as an electrolytic solution, it is preferable to an organic solvent based electrolytic solution from the viewpoint of safety. A side reaction that a decomposition reaction of water proceeds and hydrogen is generated may occur due to a chemical reaction. However, the zinc negative electrode mixture of the present invention contains, as another component, a compound having at least one element selected from the group consisting of elements belonging to Groups 1 to 5, 8, 9, and 11 to 17 of the periodic table. Assuming that an organic compound and an organic compound salt are included, even when a zinc negative electrode formed from the zinc negative electrode mixture of the present invention is used as a negative electrode and a battery is formed using an aqueous electrolyte, hydrogen generated by the decomposition of water It is possible to effectively suppress the occurrence of charge, and charge / discharge characteristics and coulomb efficiency are improved. In addition, when using conductive carbon as one of the conductive assistants, it is difficult to suppress the side reaction of hydrogen generation due to decomposition of water from proceeding completely thermodynamically. When conductive carbon is used as a component of the zinc negative electrode mixture as a conductive aid in the present invention, the other component is composed of elements belonging to Groups 1 to 3, 5, 8, 9, 11 to 17 of the periodic table. Combining with a compound, an organic compound or an organic compound salt having at least one element selected from the group has a particularly great technical significance. The zinc negative electrode mixture of the present invention further contains other components, and the other components are selected from the group consisting of elements belonging to Groups 1-3, 5, 8, 9, 11-17 of the periodic table. It is also one of the preferred embodiments of the present invention to include a compound having at least one element, an organic compound, and / or an organic compound salt.

A compound having at least one element selected from the group consisting of elements belonging to Groups 1 to 5, 8, 9, 11, and 11 in the periodic table, an organic compound, and / or included in the other components In addition, as a ratio of the organic compound salt, a compound having at least one element selected from the group consisting of elements belonging to Groups 1 to 5, 8, 9, and 11 to 17 of the periodic table, contained in other components, And the ratio of the total amount of what corresponds to either an organic compound or an organic compound salt is preferably 0.1% by mass or more, more preferably, 0.1% by mass or more with respect to 100% by mass of the total amount of other components. It is 5 mass% or more, More preferably, it is 1.0 mass% or more. The upper limit is preferably 100% by mass.

Examples of the compound having at least one element selected from the group consisting of elements belonging to Groups 1 to 5, 8, 9, and 11 to 17 in the periodic table include Ag, Al, Ba, Be, Bi, Ca, and Cd. , Ce, Co, Cs, Cu, Fe, Ga, Hg, In, K, La, Li, Mg, Na, Pb, Rb, Si, P, Sn, Sr, Sb, Ti, Tl, V, Zr, Nb An oxide of at least one element selected from the group consisting of elements belonging to Groups 1 to 5, 8 to 9, and 11 to 17 of the periodic table; a hydroxide; a halide; a carboxylate compound; a carbonate; Examples thereof include bicarbonates; nitrates; sulfates; sulfonates; silicates; The compound having at least one element selected from the group consisting of elements belonging to Groups 1 to 5, 8, 9, 11 and 17 of the periodic table does not participate in the charge / discharge reaction and is not reduced to metal. preferable. Among these, oxides, hydroxides, halides, carboxylate compounds, carbonic acids of at least one element selected from the group consisting of elements belonging to Groups 1 to 5, 8, 9, 11 and 17 of the periodic table Salts, sulfates, sulfonates, silicates and phosphates are preferred. More preferably, it is an oxide of at least one element selected from the group consisting of elements belonging to Groups 1 to 5, 8, 9, and 11 to 17 of the periodic table. That is, it is also preferable that the other component contains an oxide of at least one element selected from the group consisting of elements belonging to Groups 1 to 5, 8 to 9, and 11 to 17 of the periodic table. It is one of the embodiments.

Examples of the element in the compound having at least one element selected from the group consisting of elements belonging to Groups 1 to 5, 8, 9, and 11 to 17 in the periodic table include 1 to 5, 8 to 9 in the periodic table. 11, 13 to 17 elements are preferable, that is, Ag, Al, Ba, Bi, Ca, Ce, Co, Cs, Cu, Fe, Ga, In, K, La, Li, Mg, Na, Pb At least one element selected from the group consisting of Rb, Si, P, Sn, Sr, Sb, Ti, Tl, V, Zr and Nb is preferred. More preferable elements are elements belonging to Groups 1 to 5, 9, 11, 13 to 17 of the periodic table, that is, Ag, Al, Ba, Bi, Ca, Ce, Co, Cs, Ga, In, K, La , Li, Mg, Na, Pb, Rb, Si, P, Sn, Sr, Sb, Ti, Tl, V, Zr and at least one element selected from the group consisting of Nb.

Specific examples of the compound having at least one element selected from the group consisting of elements belonging to Groups 1 to 5, 8, 9, and 11 to 17 in the periodic table include silver oxide, aluminum oxide, and barium oxide. , Bismuth oxide, calcium oxide, cerium oxide, cobalt oxide, cesium oxide, gallium oxide, indium oxide, potassium oxide, lanthanum oxide, lithium oxide, magnesium oxide, sodium oxide, lead oxide, rubidium oxide, tin oxide, silicon oxide, oxide Phosphorus, strontium oxide, antimony oxide, titanium oxide, tellurium oxide, vanadium oxide, zirconium oxide, niobium oxide, aluminum hydroxide, barium hydroxide, calcium hydroxide, cesium hydroxide, potassium hydroxide, lanthanum hydroxide, lithium hydroxide , Magnesium hydroxide, sodium hydroxide Rubidium hydroxide, tin hydroxide, strontium hydroxide, antimony hydroxide, titanium hydroxide, zirconium hydroxide, silver chloride, lithium chloride, magnesium chloride, sodium chloride, rubidium chloride, tin chloride, potassium fluoride, 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, lead acetate, Rubidium acetate, tin acetate, strontium acetate, antimony acetate, tellurium acetate, silver carbonate, aluminum carbonate, barium carbonate, bismuth carbonate, calcium carbonate, cerium carbonate, cobalt carbonate, cesium carbonate, carbonic acid Lithium, 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, sodium lignin sulfonate, aluminum nitrate, barium nitrate, bismuth nitrate, calcium nitrate, cerium nitrate, cesium nitrate, gallium nitrate, indium nitrate Potassium nitrate, lanthanum nitrate, 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, and barium phosphate are particularly preferable.

Most preferably, the compound having at least one element selected from the group consisting of elements belonging to Groups 1 to 5, 8, 9, 11 and 17 of the periodic table is silver oxide, aluminum oxide, barium oxide, bismuth oxide. , Calcium oxide, cerium oxide, cobalt oxide, cesium oxide, gallium oxide, indium oxide, lanthanum oxide, lead oxide, rubidium oxide, silicon oxide, phosphorus oxide, tin oxide, antimony oxide, titanium oxide, tellurium oxide, vanadium oxide, oxidation Zirconium, aluminum hydroxide, barium hydroxide, calcium hydroxide, cesium hydroxide, potassium hydroxide, cerium hydroxide, lanthanum hydroxide, lithium hydroxide, magnesium hydroxide, sodium hydroxide, rubidium hydroxide, tin hydroxide, Strontium hydroxide, antimony hydroxide, titanium hydroxide , Zirconium hydroxide, silver chloride, lithium chloride, magnesium chloride, sodium chloride, rubidium chloride, tin chloride, potassium fluoride, silver acetate, barium acetate, bismuth acetate, calcium acetate, cesium acetate, cerium acetate, gallium acetate, acetic acid Indium, potassium acetate, lanthanum acetate, lithium acetate, magnesium acetate, sodium acetate, lead acetate, rubidium acetate, tin acetate, strontium acetate, antimony acetate, tellurium acetate, silver carbonate, barium carbonate, bismuth carbonate, calcium carbonate, cerium carbonate, Cobalt carbonate, cesium carbonate, gallium carbonate, indium carbonate, lead carbonate, tin carbonate, strontium carbonate, antimony carbonate, bismuth sulfate, calcium sulfate, cerium sulfate, cesium sulfate, gallium sulfate, indium sulfate, lead sulfate, tin sulfate Antimony sulfate, titanium sulfate, tellurium sulfate, vanadium sulfate, zirconium sulfate, calcium lignin sulfonate, sodium lignin sulfonate, bismuth nitrate, calcium nitrate, gallium nitrate, indium nitrate, lead nitrate, tin nitrate, antimony nitrate, titanium nitrate, nitric acid Tellurium, potassium silicate, calcium silicate, magnesium silicate, barium silicate, potassium phosphate, calcium phosphate, magnesium phosphate and barium phosphate.

Examples of the organic compound and organic compound salt include poly (meth) acrylic acid moiety-containing polymer, poly (meth) acrylate moiety-containing polymer, poly (meth) acrylic ester moiety-containing polymer, poly (α-hydroxymethyl) (Acrylate) site-containing polymer, poly (α-hydroxymethyl acrylate) site-containing polymer, polyacrylonitrile site-containing polymer, polyacrylamide site-containing polymer, polyvinyl alcohol site-containing polymer, polyethylene oxide site-containing polymer, etc. Site-containing polymer, epoxy ring-opening site-containing polymer, polyalkylene site-containing polymer such as polyethylene site-containing polymer, polyisoprenol site-containing polymer, poly (meth) allyl alcohol site-containing polymer, Riisoprene 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, ketone group moiety-containing polymer , Ether group site-containing polymer, sulfide group-containing polymer, sulfone group-containing polymer, carbamate group-containing polymer, thiocarbamate group-containing polymer, carbamide group-containing polymer, thiocarbamide group-containing polymer, thiocarboxylic acid (salt) group-containing polymer, ester group -Containing polymer, carbonate group site-containing polymer, thiocarbonate group-containing polymer, cyclopolymerization site-containing polymer, lignin, styrene butadiene rubber (SBR), etc. Representative artificial rubber, agar, betaine site-containing compounds, sugars such as cellulose, chitin, chitosan, alginic acid (salt), polyalkylene glycol chain-containing compounds such as ethylene glycol and polyethylene glycol chain-containing compounds, amino groups such as polyethyleneimine -Containing polymer, amide group site-containing polymer, polypeptide site-containing polymer, polytetrafluoroethylene site-containing polymer, polyvinylidene fluoride site-containing polymer, poly (anhydride) maleic acid (salt) site-containing polymer, poly (anhydride) itaconic acid ( Salt) site-containing polymer, poly (anhydrous) methylene glutaric acid (salt) site-containing polymer, ion-exchange polymer used for cation / anion exchange membrane, sulfonate, sulfonate site-containing polymer, Quaternary ammonium salt, quaternary anne Nium salt moiety-containing polymer, quaternary phosphonium salt, quaternary phosphonium salt moiety-containing polymer, isocyanate group-containing polymer, isocyanate group-containing polymer, thioisocyanate group-containing polymer, imide group moiety-containing polymer, oxetane group moiety-containing polymer, Examples thereof include a hydroxyl group-containing polymer, a heterocyclic ring, and / or an ionized heterocyclic moiety-containing polymer, a polymer alloy, a heteroatom-containing polymer, and a low molecular weight surfactant. The organic compound and the organic compound salt are preferably polytetrafluoroethylene. The above organic compounds and organic compound salts can be used alone or in combination of two or more. When the organic compound and the organic compound salt are polymers, the functional group may be in the main chain or in the side chain, and the main chain may be partially crosslinked.

The electrode of the present invention is preferably obtained by the electrode preparation method of the present invention described later. Especially, it is especially preferable that it is what is obtained by the preferable method of the preparation method of the electrode of this invention mentioned later.

<Method for Preparing Electrode of the Present Invention>
A method for preparing the electrode of the present invention will be described below.
The electrode of the present invention is an active material and / or an active material layer covered with an ion conductive layer. The active material covered with the ion conductive layer is an ion conductive compound such as a polymer or an anion conductive material. And, if necessary, a composition containing other components can be produced by coating, press-bonding, and adhering to the active material.
In addition, the active material layer is an electrode mixture composition (a positive electrode mixture composition or a positive electrode mixture composition or an electrode active material that may be covered with an anion conductive material) and, if necessary, a conductive additive and other additives. A negative electrode mixture composition) can be formed on the current collector by coating, pressure bonding, adhesion, or the like.
The ion conductive layer covering the active material layer is formed by coating, pressing, adhering, or the like, a composition containing an ion conductive compound such as a polymer or an anion conductive material, and other components as necessary. Can be manufactured.
The order of these steps is not particularly limited, and can be appropriately selected depending on the mode in which the anion conductive material covers the active material and / or the active material layer. In addition, the active material for forming the active material layer, the conductive auxiliary agent, and preferred types and blending ratios of other additives, polymers for forming the anion conductive material, inorganic compounds, and other Preferred types and blending ratios of the components are the same as those described above for the electrode of the present invention.

(Method of forming ion conductive layer)
Examples of the method for forming the ion conductive layer according to the present invention include the following methods.
When an anion conductive material is used as the material of the ion conductive layer, the other components are mixed with the polymer and the inorganic compound as necessary. For mixing, a mixer, blender, kneader, bead mill, ready mill, ball mill, or the like can be used. In mixing, water, an organic solvent such as methanol, ethanol, propanol, isopropanol, butanol, hexanol, 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 to a desired particle size. Mixing may be performed by either a wet method in which a liquid component such as water or an organic solvent is added to the solid component, or a dry method in which only the solid component is added without adding the liquid component. When mixing is performed by a wet method, after mixing, liquid components such as water and organic solvent may be removed by drying. Mixing can also be performed by combining a wet method and a dry method. Pressure or temperature may be applied during mixing.

By the preparation method described above, a slurry or paste mixture containing a polymer and an inorganic compound is obtained.

Next, in the electrode of the present invention, when the entire active material layer constituting the electrode is covered with an ion conductive layer, the active material layer is formed in advance by a method of forming an active material layer of the electrode described later, A slurry or paste mixture containing a polymer and an inorganic compound is applied, pressure-bonded, or pressure-applied on the surface of the active material layer that faces the electrolyte when the battery is configured, so that the film thickness is as constant as possible. Adhere. For example, the slurry or paste mixture is adhered to the active material layer by coating, pressure bonding, adhesion, piezoelectric, etc., or the slurry or paste mixture is applied to the active material layer and dried several times, and the ion conductive layer It is preferable to cover the active material layer. Thus, there is only one active material layer constituting the electrode, and the process of forming the ion conductive layer covering the entire active material layer is usually performed after the active material layer is formed on the current collector. . Note that as long as the active material layer is formed, the ion conductive layer forming step may be performed before the active material layer is disposed on the current collector. The layer may be a flat surface or a curved surface.

In the electrode of the present invention, when each active material particle is covered with an ion conductive layer, a slurry or paste mixture containing a polymer and an inorganic compound is applied to the active material particle, pressure bonded, stirred, or adhered to the active material. The particles are previously covered with an ion conductive layer. For example, the active material particles may be covered with the ion conductive layer by bonding the slurry or paste mixture to the active material particles by piezoelectric, or by repeating the application of the slurry or paste mixture to the active material particles and drying a plurality of times. it can. Using the active material particles covered with the ion conductive layer thus obtained as a raw material, an active material layer is formed by a method of forming an active material layer of an electrode to be described later. That is, an electrode mixture composition containing active material particles covered with an ion conductive layer is prepared, and the electrode mixture composition is applied to, bonded to, or bonded to a current collector. Thereby, the electrode of this invention covered with the ion conductive layer for every active material particle is producible. In addition, as long as it can be covered with the ion conductive layer for every active material particle, other methods can be employ | adopted, for example, the active material which is not covered with the ion conductive layer for every active material particle After forming the layer, a slurry or paste mixture containing a polymer and an inorganic compound or the like is applied / bonded / bonded onto the active material layer to obtain an ion conductive layer, and the obtained ion conductive layer is subjected to heat / pressure / It is also possible to adopt a method of introducing into the active material layer by using a solvent or the like. The layer may be a flat surface or a curved surface.

(Method of forming an active material layer of an electrode)
Examples of the method for forming the active material layer of the electrode include the following methods.
The electrode mixture composition used to prepare the active material layer may be mixed with an active material that may be covered with an ion conductive layer and, if necessary, a conductive additive and other additives. Can be prepared. For mixing, a mixer, blender, kneader, bead mill, ready mill, ball mill, or the like can be used. In mixing, water, an organic solvent such as methanol, ethanol, propanol, isopropanol, butanol, hexanol, 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 to a desired particle size. Mixing may be performed by either a wet method in which a liquid component such as water or an organic solvent is added to the solid component, or a dry method in which only the solid component is added without adding the liquid component. When mixing is performed by a wet method, after mixing, liquid components such as water and organic solvent may be removed by drying. Mixing can also be performed by combining a wet method and a dry method. Pressure or temperature may be applied during mixing. You may add the said polymer as a binder, a thickener, etc.

For example, an active material that may be covered with an ion conductive layer and, if necessary, other additives are mixed by a wet method, and then a liquid mixture is removed by drying, and a conductive mixture is obtained. An electrode mixture composition may be prepared by mixing an agent with a dry method. The active material and a compound having at least one element selected from the group consisting of elements belonging to Group 1 to Group 17 of the periodic table, which are other additives, may be alloyed. It is also possible to introduce the element into the zinc-containing compound by passing electricity through the electrode mixture composition.

By the preparation method described above, the electrode mixture composition is obtained as a slurry or a 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. The ion conductive layer may be applied, pressure-bonded or bonded after the electrode mixture composition is applied, pressure-bonded or bonded, and applied, pressure-bonded or bonded simultaneously with the application, pressure-bonding or bonding of the electrode mixture composition. Or you may adhere | attach. The ion conductive layer may be applied, pressure-bonded or bonded in advance on the electrode mixture composition. These may be layered or non-layered.

The slurry or paste mixture may be applied, pressure-bonded, or adhered to one surface of the current collector, 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 perform a press with a roll press machine etc. by the pressure of normal pressure-30 kN / m < ² > with a roll press machine etc. after drying the said slurry or paste mixture. The pressure for pressing is more preferably a pressure of normal pressure to 10 kN / m ² . Since the volume of the active material layer is preferable when the pressing pressure is in the above preferable range, the porosity in the active material layer can be set in the above preferable range. You may apply the temperature of 10-500 degreeC at the time of a press. The pressing process may be performed once or a plurality of times. When performing 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.

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

The electrode obtained by the above preferred adjustment method suppresses the decomposition of water in the negative electrode, particularly when used as a negative electrode for a secondary battery, and changes in shape such as shape change and dendrite of electrode active material, passivity Deterioration due to formation and generation of hydrogen during use as a negative electrode of a battery can be suppressed to the maximum.
The film thickness of the negative electrode is preferably 1 nm to 1000 μm from the viewpoints of battery configuration and suppression of peeling of the active material from the current collector. More preferably, it is 10 nm-900 micrometers, More preferably, it is 50 micrometers-900 micrometers.

<Battery of the present invention>
Moreover, this invention is also a battery comprised using the electrode of this invention.
The battery of the present invention includes a primary rechargeable battery; a dischargeable secondary battery (storage battery); a battery using mechanical charge (mechanical replacement of the negative electrode); a third electrode separate from the positive electrode and the negative electrode ( For example, any form such as a battery using an electrode that removes oxygen and hydrogen generated during charging and discharging may be used. For example, a secondary battery (storage battery) is preferable.
Since the battery using the electrode of the present invention can use a water-containing electrolytic solution as the electrolytic solution, a highly safe battery can be obtained.
The battery of the present invention can include an electrolyte sandwiched between the negative electrode and the positive electrode.
As the electrolytic solution, a water-containing electrolytic solution is preferable as described later.

The positive electrode can be formed using a material normally used as a positive electrode active material for a primary battery or a secondary battery, and is not particularly limited. For example, the positive electrode active material described above can be used.

The electrolytic solution sandwiched between the negative electrode and the positive electrode is not particularly limited as long as it is usually used as an electrolytic solution for a battery, and examples thereof include a water-containing electrolytic solution and an organic solvent-based electrolytic solution. A water-containing electrolyte is preferred. The water-containing electrolytic solution refers to an electrolytic solution using only water as an electrolytic solution raw material (aqueous electrolytic solution) or an electrolytic solution using a solution obtained by adding an organic solvent to water as an electrolytic solution raw material.

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. Of these, alkaline electrolytes such as an aqueous potassium hydroxide solution, an aqueous sodium hydroxide solution, and an aqueous lithium hydroxide solution are preferred. The aqueous electrolyte solution can be used alone or in combination of two or more.

The water-containing electrolytic solution may contain an organic solvent used for an organic solvent-based electrolytic solution. Examples of the organic solvent include ethylene carbonate, propylene carbonate, dimethyl carbonate, diethyl carbonate, γ-butyrolactone, dimethoxymethane, diethoxymethane, dimethoxyethane, tetrahydrofuran, methyltetrahydrofuran, diethoxyethane, dimethyl sulfoxide, sulfolane, acetonitrile, Examples include benzonitrile, ionic liquid, fluorine-containing carbonates, fluorine-containing ethers, polyethylene glycols, fluorine-containing polyethylene glycols and the like. The organic solvent electrolyte can be used alone or in combination of two or more. The electrolyte of the organic solvent-based electrolytic solution is not particularly limited, but LiPF ₆ , LiBF ₄ , LiB (CN) ₄ , lithium bis (fluorosulfonyl) imide (LiFSI), lithium bis (trifluoromethylsulfonyl) imide ( LiTFSI) and the like are preferable.

In the case of the water-containing electrolyte containing the organic solvent-based electrolyte, the content of the water-based electrolyte is 10 to 99.9% by mass with respect to a total of 100% by mass of the water-based electrolyte and the organic solvent-based electrolyte. It is preferable. More preferably, it is 20-99.9 mass%.

It is also possible to use a gel electrolyte as the electrolyte. The gel electrolyte is not particularly limited as long as it can be used as a battery electrolyte, and examples thereof include a solid electrolyte containing an inorganic compound and a gel electrolyte crosslinked by a crosslinking agent.

The concentration of the electrolytic solution is preferably 0.01 to 15 mol / L. By using the electrolytic solution having such a concentration, good battery performance can be exhibited. More preferably, it is 4-12 mol / L. Further, the electrolytic solution may contain an additive. As an additive, for example, in the case of potassium hydroxide electrolyte, magnesium hydroxide, barium hydroxide, calcium hydroxide, zinc oxide, zinc metal, tetrahydroxy zinc ion, magnesium chloride, barium chloride, calcium chloride, fluoride Potassium, potassium borate, potassium hydrogen borate, sodium borate, sodium hydrogen borate, potassium phosphate, potassium hydrogen phosphate, sodium phosphate, sodium hydrogen phosphate, potassium arsenate, potassium carbonate, sodium carbonate, hydroxylated Indium, 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 oxide, calcium oxide, water Calcium hydroxide, zinc hydroxide, lead oxide, lead acetate, tellurium oxide, iron oxide, germanium oxide, tin oxide, tin hydroxide, tin chloride, indium oxide, indium hydroxide, sorbitol and other sugars, quaternary ammonium salts, Quaternary phosphonium salt, caprolactam compound, chelating agent, methanol, ethanol, polymer, gel compound, carboxylate group, and / or sulfonate group, and / or quaternary ammonium salt, and / or quaternary phosphonium Examples thereof include a polymer having a salt and a gel compound.

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

The 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 Group 1 to Group 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 a separator, the said specific polyvalent cation and / or an inorganic compound, a nitrogen-containing organic compound, surfactant, electrolyte solution, etc. may be included in the separator.

The battery using the electrode of the present invention includes a primary battery; a chargeable / dischargeable secondary battery (storage battery); use of mechanical charge (mechanical replacement of the negative electrode); a third different from the positive electrode and the negative electrode. Any form such as utilization of an electrode (for example, an electrode for removing oxygen and hydrogen generated during charge and discharge) may be used. A secondary battery (storage battery) is preferable.

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.

The electrode of the present invention has the above-described configuration, can suppress dendrite growth and self-discharge reaction, and a battery configured using such an electrode has good coulomb efficiency. From these facts, the electrode of the present invention can be suitably used for forming a negative electrode of a battery excellent in battery performance.

It is the figure which showed the Coulomb efficiency of the electrode whose porosity of Example 1 is 52, 60, 71, 75, 79% and whose porosity of the comparative example 1 is 80%.

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. Unless otherwise specified, “part” means “part by weight” and “%” means “mass%”.

Example 1
Zinc oxide as a zinc-containing compound and a polytetrafluoroethylene dispersion as a binder were mixed and stirred using a planetary mixer to prepare a zinc negative electrode mixture. The zinc negative electrode mixture was pressure-bonded to a copper mesh as a current collector and dried to obtain a zinc negative electrode. When press-bonding, electrodes having a porosity of 52, 60, 71, 75, and 79% were prepared by changing the press thickness. A paste prepared by mixing hydrotalcite as an anion conductive material and a polytetrafluoroethylene dispersion as a binder was rolled into a sheet to form an ion conductive layer having a thickness of 300 μm. As an electrolytic solution, a solution in which zinc oxide was saturated in an 8 mol / L potassium hydroxide aqueous solution was used. For samples in which an ion conductive layer is pressure-bonded to these electrodes, after charging for 1 hour at a current value of 25 mA / cm ² in a constant temperature bath at 40 ° C., until the voltage reaches 1.2 V at a current value of 25 mA / cm ² Discharge for 10 cycles, then charge for 1 hour at a current value of 25 mA / cm ² , and after standing for 24 hours, discharge again until it reaches 1.2 V at a current value of 25 mA / cm ^2. The coulomb efficiency (= discharge capacity / charge capacity) was determined from the discharge capacity at that time.
From FIG. 1, it was revealed that self-discharge was suppressed most in the electrodes having porosity of 71 and 75%.

(Comparative Example 1)
An electrode was prepared in the same manner as in Example 1 except that the porosity of the electrode was 80%, and the same evaluation was performed.

(Comparative Example 2)
When an electrode was formed and charged / discharged in the same manner as in Example 1 except that the ion conductive layer was not formed, a short circuit due to dendrite occurred at the beginning of the cycle, and the electrical characteristics could not be evaluated.

(Example 2)
Zinc oxide is added as a zinc-containing compound, cerium oxide is added as an additive at a mass ratio of zinc oxide / cerium oxide = 97/3, mixed with a polytetrafluoroethylene dispersion as a binder, and a planetary mixer is used. The mixture was stirred to prepare a zinc negative electrode mixture. The zinc negative electrode mixture was pressure-bonded to a copper mesh as a current collector and dried to obtain a zinc negative electrode. The porosity of this electrode was 77%. A paste prepared by mixing hydrotalcite as an anion conductive material and a polytetrafluoroethylene dispersion as a binder was rolled into a sheet shape to prepare an ion conductive layer having a thickness of 300 μm. As an electrolytic solution, a solution in which zinc oxide was saturated in an 8 mol / L potassium hydroxide aqueous solution was used. For samples in which an ion conductive layer is pressure-bonded to these electrodes, after charging for 1 hour at a current value of 25 mA / cm ² in a constant temperature bath at 40 ° C., until the voltage reaches 1.2 V at a current value of 25 mA / cm ² Discharge for 10 cycles, then charge for 1 hour at a current value of 25 mA / cm ² , and after standing for 24 hours, discharge again until it reaches 1.2 V at a current value of 25 mA / cm ^2. The coulomb efficiency (= discharge capacity / charge capacity) was determined from the discharge capacity at that time.

(Example 3)
A zinc electrode was prepared and evaluated in the same manner as in Example 2. At that time, indium oxide was added as an additive instead of cerium oxide.

Example 4
A zinc electrode was prepared and evaluated in the same manner as in Example 2. At that time, gallium oxide was added instead of cerium oxide as an additive.

(Example 5)
A zinc electrode was prepared and evaluated in the same manner as in Example 2. At that time, potassium fluoride was added as an additive instead of cerium oxide.

(Example 6)
A zinc electrode was prepared and evaluated in the same manner as in Example 2. At that time, tin oxide was added instead of cerium oxide as an additive.

(Example 7)
A zinc electrode was prepared and evaluated in the same manner as in Example 2. At that time, niobium oxide was added as an additive instead of cerium oxide.

The results of Examples 2 to 7 are shown in Table 1. From Table 1, it was confirmed that, even when the additive was introduced into the electrode, high coulomb efficiency was exhibited and self-discharge was suppressed by setting the porosity to a predetermined range.

Claims (2)

In a negative electrode composed of an active material layer containing an active material and a current collector,
The active material is at least one selected from the group consisting of lithium, sodium, magnesium, zinc, tin, and lead,
The active material and / or active material layer is covered with an ion conductive layer,
The ion conductive layer has conductivity of ions involved in the battery reaction, but has selective ion conductivity that does not have conductivity of ions constituting the active material,
The active material layer has the following formula (1):
Porosity = V ′ / V (1)
(In the formula, V represents the volume of the active material layer. V ′ represents the volume of the voids in the active material layer.)
Anode porosity of in represented by the active material layer is characterized in that it is a 65-7 5%. A battery comprising the negative electrode according to claim 1.

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