JP6190101B2 - Gel electrolyte or negative electrode mixture, and battery using the gel electrolyte or negative electrode mixture - Google Patents

Description

The present invention relates to a gel electrolyte or negative electrode mixture, and a battery using the gel electrolyte or negative electrode mixture. More specifically, the present invention relates to a gel electrolyte that can be suitably used as a battery electrolyte or a negative electrode mixture that can be preferably used to form a negative electrode of a battery, and a battery that uses the gel electrolyte or negative electrode mixture.

Conventionally, a battery has a configuration of a positive electrode, a negative electrode, and an electrolytic solution sandwiched between the electrodes. Batteries often have liquid electrolytes, and particularly storage batteries have problems that may be difficult to use safely and stably over the long term, such as expansion of the storage battery due to decomposition of the electrolyte. In particular, storage batteries that use zinc-containing compounds (aqueous electrolytes), metallic lithium (organic solvent electrolytes), etc. as negative electrodes are nickel metal hydride batteries (aqueous electrolytes) and lithium that are widely used as storage batteries. When ion batteries (organic solvent electrolytes) and electrolytes are compared in a unified manner, charging / discharging for a long period of time despite the fact that the operating voltage, energy density, etc. are substantially superior to these. If the process is repeated, the dissolution and precipitation reaction of the metal occurs at the local part of the electrode, and the change in the shape of the electrode active material such as shape change and dendrite occurs and grows. Also had.

As a general method for solving the safety and stability problems of storage batteries, a gel electrolyte (gel electrolyte) with high ionic conductivity and excellent safety and mechanical properties is used instead of the electrolyte. The method has been used as the main approach. As a gel electrolyte for such an approach, for example, an inorganic hydrogel electrolyte for an all-solid alkaline secondary battery in which an aqueous alkali hydroxide solution is held in a hydrotalcite having a layered structure (see, for example, Patent Document 1). Alternatively, a polymer hydrogel electrolyte for an alkaline battery in which an alkali hydroxide is contained in a polymer composition comprising polyvinyl alcohol and an anionic crosslinked (co) polymer is disclosed (for example, see Patent Document 2). Yes. Further, it is a copolymer comprising a hydrophobic monomer having a hydrophobic group that generates a carboxyl group by saponification, and a hydrophobic polyfunctional monomer, and the saponification product of the copolymer has a property of gelling an electrolyte solution. There is disclosed a polymer gelling agent for electrolyte obtained by saponifying a polymer gelling agent precursor for electrolyte (see, for example, Patent Document 3). As other gel electrolytes, alkali polymer gel electrolytes prepared by solution polymerization using acrylate, potassium hydroxide, and water as raw materials (see, for example, Non-Patent Document 1), hydrotalcite is hydroxylated. Inorganic hydrogel electrolyte holding an aqueous potassium solution (for example, see Non-patent Document 2), alkaline polyethylene oxide solid polymer electrolyte (for example, see Non-Patent Document 3), polyethylene oxide, polyvinyl alcohol, potassium hydroxide, water Polymer electrolyte prepared from (for example, Non-Patent Document 4), polyvinyl alcohol, nanoparticulate zirconium oxide, potassium hydroxide, and alkali polymer electrolyte nanocomposite prepared from water (for example, Non-Patent Document 4) 5, etc.). Also disclosed is a solid electrolyte (see, for example, Patent Document 4), which is a viscoelastic material containing a non-aqueous electrolyte in a high molecular weight polymer in an amount of 200% by weight or more based on the high molecular weight polymer.

On the other hand, although it is not intended to suppress changes in the shape of electrode active materials such as shape change and dendrite, an additive (binder / binder) is added to the electrode mixture to form the electrode, and the active material (metal) A method is known in which the active material is held on an electrode by restraining the active material. For example, after impregnating a monomer or lower polymer compound that can be polymerized or copolymerized into the pores of an active material particle group or a particle group mainly composed of an active material, A method for obtaining a battery electrode by polymerizing or copolymerizing a polymer compound (for example, see Patent Document 5) is disclosed. In addition, an additive (thickening agent) made of a water-insoluble water-absorbent resin used in an electrode paste manufacturing process for an alkaline storage battery (for example, see Patent Document 6) is disclosed as a polymer to be added to the electrode mixture. An electrochemistry comprising a vinyl polymer-based thermoreversible thickener that reversibly changes hydrophilicity and hydrophobicity at a certain transition temperature, a water-dispersible binder resin, and a metal salt of Group I to VII of the element periodic table A binder for an electrode of an element (see, for example, Patent Document 7) and an aqueous dispersion composed of an aqueous phase and a binder for an electrode dispersed in an aqueous phase, the binder having a glass transition temperature of − An aqueous dispersion made of a synthetic resin having a temperature of less than 40 ° C. (for example, see Patent Document 8) is disclosed.

JP 2007-227032 A JP 2005-322635 A JP 2003-1778797 A JP-A-5-205515 JP-A-60-37655 JP-A-8-222225 JP 2003-331848 A JP 2006-172992 A

Xiaoming Zhu, three others, “Electrochimica Acta”, 2004, 49, 16, p. 2533-2539 Hiroshi Inoue, 4 others, “Electrochemical and Solid-State Letters”, 2009, Vol. 12, No. 3, p. A58-A60 J. et al. F. J. F. Fauvarque, four others, “Electrochimica Acta”, 1995, 40, 13-14, p. 2449-2453 Chun-Chen Yang, “Journal of Power Sources”, 2002, 109, p. 22-31 Chun-Chen Yang, “Materials Science and Engineering B”, 2006, vol. 131, p. 256-262

As described above, various gel electrolytes and additives for electrode mixtures have been studied in order to solve the problems of storage batteries and improve their performance. However, from the viewpoint of the superiority of storage battery performance such as operating voltage and energy density, it satisfies the performance required for storage batteries using zinc-containing compounds and metallic lithium instead of hydrogen storage alloy and graphite as the negative electrode active material of the electrode. In order to achieve this, battery performance such as cycle characteristics, rate characteristics, and coulomb efficiency is achieved after suppressing the formation of the electrode active material such as shape change and dendrite, dissolution, corrosion, and the formation of passives that contribute to them. In addition, there is room for improvement in order to realize a storage battery that balances these. Even in the above-mentioned storage battery, as reported in Non-Patent Document 1 and Non-Patent Document 3, gel electrolyte has often been used, but the present situation is that the above problem has not been solved. Also in Non-Patent Documents 2, 4, and 5, only the characteristics of whether or not the gel electrolyte can be used as an electrolyte of a battery are observed, and the above problem has not been solved. That is, the gel electrolytes disclosed in these non-patent documents are not used for the purpose of suppressing the change in form of the electrode active material and improving battery performance such as cycle characteristics, rate characteristics, and Coulomb efficiency. In order to sufficiently solve these problems, there is room for further ingenuity.
In any of the methods disclosed in Patent Documents 5 to 8, the additive polymer is only positioned as a thickener for paste-type electrodes such as alkaline storage batteries, and changes in the shape and passivation of the electrode active material Is not used for the purpose of suppressing battery performance and improving battery performance such as cycle characteristics, rate characteristics, and coulomb efficiency, and there is room for further improvement in order to sufficiently solve these problems. It was a thing.

The present invention has been made in view of the above-described situation, and suppresses changes in the shape, dissolution, corrosion, and passive formation of the electrode active material such as electrode active material shape change and dendrite, and has high cycle characteristics and rate characteristics. An object of the present invention is to provide a gel electrolyte or a negative electrode mixture, and a storage battery using the gel electrolyte or negative electrode mixture, which can be suitably used to form a storage battery that exhibits battery performance such as Coulomb efficiency. And

The present inventor has made various studies on problems related to shape change, dissolution, corrosion, and passive formation of electrode active materials such as shape change and dendrite in batteries, and has focused on gel electrolytes. The conventional gel electrolytes still have insufficient performance as electrolytes, and in particular in the case of high-concentration alkaline aqueous solutions, the decomposition proceeds gradually, and for industrial and industrial secondary battery applications. I found out that I can't stand it. Here, when the gel electrolyte has a cross-linked structure with polyvalent ions and / or inorganic compounds, the storage battery formed using such a gel electrolyte has a shape change such as shape change or dendrite of the electrode active material. In addition, the gel electrolyte can exhibit high cycle characteristics, rate characteristics, and coulomb efficiency while maintaining high ionic conductivity, and is particularly resistant to highly concentrated aqueous alkali solutions. Found to improve. As described above, the present inventors have arrived at the present invention by conceiving that the gel electrolyte used in the storage battery has a cross-linked structure of polyvalent ions and / or inorganic compounds, so that the above problem can be solved brilliantly. Is.
In addition, the present inventor also paid attention to the negative electrode mixture for the problem of shape change such as shape change and dendrite of the electrode active material in the storage battery. And even if the negative electrode mixture includes a negative electrode active material and a polymer, a storage battery formed using such a negative electrode mixture can change the shape and passivity of the electrode active material such as shape change and dendrite. It has been found that high cycle characteristics, rate characteristics, and coulomb efficiency can be exhibited while effectively suppressing and maintaining high electrical conductivity. As described above, the inventors have arrived at the present invention by conceiving that the above problem can be solved brilliantly even when the negative electrode mixture used in the storage battery includes a negative electrode active material and a polymer. The present invention can be used not only for storage batteries (secondary batteries) but also for other electrochemical devices such as primary batteries, capacitors, and hybrid capacitors.

That is, the present invention is a gel electrolyte used in a battery, wherein the gel electrolyte has a cross-linked structure with multivalent ions and / or inorganic compounds.
The present invention is also a negative electrode mixture for use in a battery, wherein the negative electrode mixture includes a negative electrode active material and a polymer.
The present invention is described in detail below.
In addition, the form which combined two or more each preferable form of this invention described below is also a preferable form of this invention.
As described above, the present invention is an invention related to a gel electrolyte (also referred to as a first present invention) and an invention related to a negative electrode mixture (also referred to as a second present invention). Or the effect of this invention can be acquired by implementing either of 2nd this invention. Of course, the present invention includes a combination of the first invention and the second invention.
In the following, the first invention will be described first, and then the second invention will be described.

The gel electrolyte of the present invention has a cross-linked structure with polyvalent ions and / or inorganic compounds, that is, the gel electrolyte contains a cross-linked structure, and the cross-linked structure contains multivalent ions and / or inorganic compounds. It is what is bridge | crosslinked by. 1 type may be used for a multivalent ion and an inorganic compound, respectively, and 2 or more types may be used for them.
Examples of the element of the multivalent ion include alkaline earth metals, Sc, Y, lanthanoids, Ti, Zr, Hf, V, Nb, Ta, Cr, Mo, W, Mn, Re, Fe, Ru, Co, Rh, Ir, Ni, Pd, Pt, Cu, Ag, Au, Zn, Cd, B, Al, Ga, In, Tl, Si, Ge, Sn, Pb, P, As, Sb, Bi, S, Se, Te preferable. More preferably, Mg, Ca, Sr, Ba, Sc, Y, La, Ce, Yb, Ti, Zr, Nb, Nd, Cr, Mo, W, Mn, Co, Ni, Cu, Zn, Cd, B, Al, Ga, In, Tl, Si, Ge, Sn, Pb, P, Sb, Bi, and S.

The multivalent ion is an oxide containing an element of the multivalent ion; a composite oxide; a layered double hydroxide such as hydrotalcite; a hydroxide; a clay compound; a solid solution; a halide; a carboxylate compound; Hydrogen carbonate compound; nitric acid compound; sulfuric acid compound; sulfonic acid compound; phosphoric acid compound; phosphorous acid compound; hypophosphorous acid compound, boric acid compound; silicic acid compound; , An anion or cation generated by introduction into an electrolyte solution raw material, electrolyte solution, gel electrolyte, or the like. The anion or cation may be generated by dissolving a part or all of the compound containing the element of the polyvalent ion in an electrolyte solution raw material, an electrolyte solution, a gel electrolyte, or the like. When the contained compound is insoluble, the anion or cation may be generated on a part of the surface of the compound when introduced into an electrolyte solution raw material, electrolyte solution, gel electrolyte or the like. The multivalent ions may be generated in the gel electrolyte using a compound having the element as a precursor. When the gel electrolyte of the present invention contains a polymer, the polyvalent ion may be derived from the polymer.
As will be described later, when the gel electrolyte of the present invention contains a polymer, the polyvalent ion is mainly a covalent bond, a coordinate bond, a ionic bond, a hydrogen bond, a π bond with a functional group of the polymer. The gel electrolyte becomes a gel electrolyte by interacting with non-covalent bonds such as van der Waals bonds and agostic interactions to form crosslinks.
Moreover, even when the gel electrolyte of this invention does not contain a polymer, it is possible to comprise a gel electrolyte. In this case, it is only necessary that the polyvalent ions and the inorganic compound described later coexist in the electrolyte solution, and the polyvalent ions together with the ions in the electrolyte solution can more suitably crosslink and bind the inorganic compound. Inferred. At this time, the element contained in the multivalent ion and the element contained in the inorganic compound may be the same or different, but at least one is more preferable.
The mass ratio of the polyvalent ions and the inorganic compound is preferably 50000/1 to 1/100000.

The inorganic compounds include alkali metals, alkaline earth metals, Sc, Y, lanthanides, Ti, Zr, Hf, V, Nb, Ta, Cr, Mo, W, Mn, Re, Fe, Ru, Co, Rh, Ir , Ni, Pd, Pt, Cu, Ag, Au, Zn, Cd, B, Al, Ga, In, Tl, Si, Ge, Sn, Pb, P, As, Sb, Bi, S, Se, Te, F Oxides containing at least one element selected from the group consisting of, Cl, Br, and I; composite oxides; layered double hydroxides such as hydrotalcite; hydroxides; clay compounds; solid solutions; clay compounds; Carboxylate compound; Carbonate compound; Hydrogen carbonate compound; Nitric acid compound; Sulfuric acid compound; Phosphoric acid compound such as hydroxyapatite; Phosphorous compound; Hypophosphorous acid compound; Boric acid Compounds; silicate compound; aluminate compound; sulfide; onium compound; salts. Preferably, an oxide containing at least one element selected from the above group of elements; a composite oxide; a layered double hydroxide such as hydrotalcite; a hydroxide; a clay compound; a solid solution; a clay compound; a zeolite; Phosphoric acid compounds such as hydroxyapatite; boric acid compounds; silicic acid compounds; aluminate compounds;

The hydrotalcite is the following formula:
[M ¹ _1-x M ² _x (OH) ₂ ] (A ⁿ⁻ ) _{x / n} · mH ₂ O
^{(M 1 = Mg, Fe,} Zn, Ca, Li, Ni, Co, Cu or the ^{like; M 2 = Al, Fe,} Mn , etc.; ^A n- = _CO ^{3 2-} or the like, m is 0 or a positive number, 0 .20 ≦ x ≦ 0.40), which are dehydrated by baking at 150 ° C. to 900 ° C., compounds obtained by decomposing anions within the layers, and anions within the layers A compound obtained by exchanging with a hydroxide ion or the like, Mg ₆ Al ₂ (OH) ₁₆ CO ₃ .mH ₂ O, which is a natural mineral, or the like may be used as the inorganic compound. When the gel electrolyte using hydrotalcite does not contain a polymer or oligomer, a polyvalent ion other than hydrotalcite and / or an inorganic compound is allowed to coexist or n = 0.33 hydrotalcite is used. More preferably it is used.
The hydroxyapatite is a compound typified by Ca ₁₀ (PO ₄ ) ₆ (OH) ₂ , a compound in which the amount of Ca is reduced depending on the conditions during preparation, a hydroxyapatite compound into which an element other than Ca is introduced, etc. May be used as the inorganic compound.

The inorganic compound may be generated in the gel electrolyte using a compound having the element as a precursor. The inorganic compound may be in a dissolved state, a dispersed state such as a colloid, or an insoluble state when it is introduced into an electrolytic solution raw material, an electrolytic solution, a gel electrolyte, etc. Or a negative charge is preferable, and the charged state of the particles can be inferred by measuring the zeta potential. As will be described later, when the gel electrolyte of the present invention contains a polymer, these inorganic compounds also mainly include a covalent bond, a coordinate bond, an ionic bond, a hydrogen bond, a π bond with a functional group of the polymer. The gel electrolyte becomes a gel electrolyte by interacting with non-covalent bonds such as van der Waals bonds and agostic interactions to form crosslinks. Moreover, even when the gel electrolyte of this invention does not contain a polymer, it is possible to comprise a gel electrolyte. In this case, it is only necessary that the inorganic compound be present in the electrolytic solution, and it is presumed that ions in the electrolytic solution and the inorganic compound are more preferably crosslinked and linked. At this time, the polyvalent ions may be contained, and the elements contained in the polyvalent ions and the elements contained in the inorganic compound may be the same or different, but at least one different one Is more preferable. Further, when a layered compound such as hydrotalcite is used, a polymer is formed in the layer, and as a result, a crosslinked state may be obtained. 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. In this case, the gel electrolyte is formed by using not only electrical interaction but coordination bond or the like as a preferable driving force.
Specific examples of the inorganic compound include a compound containing an element of a polyvalent ion. Such a compound generates an ion and forms a cross-link as a polyvalent ion, or the inorganic compound as described above. Whether to form a cross-linkage depends on the electrolytic solution raw material, the electrolytic solution, the gel electrolyte, etc. used, but in any case, a cross-linked structure is formed.

When the water-containing electrolyte described later is used as the electrolyte used when preparing the gel electrolyte of the present invention, the compound or inorganic compound that generates the polyvalent ions is highly expressed and charged. In addition to contributing to the permeability of gas generated during discharge, the side reaction that hydrogen and oxygen are generated by the progress of water decomposition reaction, which can occur thermodynamically, and the change in form, dissolution, and corrosion of the active material. It will also serve to suppress and significantly improve charge / discharge characteristics and coulomb efficiency. This is thought to be due to the favorable interaction of multivalent ions and inorganic compounds with the negative electrode surface and the suppression of zinc-containing compound diffusion.

The gel electrolyte may be a gel electrolyte composed only of polyvalent ions and / or inorganic compounds and an electrolytic solution, or may be a gel electrolyte containing a polymer or an oligomer. When the gel electrolyte includes an oligomer or a polymer, the oligomer or the polymer has a structure crosslinked with a polyvalent ion and / or an inorganic compound. Due to the use of these gel electrolytes, especially by being able to effectively and physically limit the diffusion of ions in and / or on the surface of the electrode active material, such as morphological changes such as shape change and dendrite, dissolution, It is assumed that corrosion can be suppressed. Moreover, the effect which suppresses the self-discharge at the time of the formation of a passive state and a charge state and the preservation | save in a charge state will be acquired by using such a gel electrolyte. It is presumed that the effect of suppressing the formation of this passive state and self-discharge is also obtained by the action of the gel electrolyte as described above. Furthermore, a storage battery formed using such a gel electrolyte can exhibit high cycle characteristics, rate characteristics, and coulomb efficiency while maintaining high electrical conductivity. Therefore, the gel electrolyte of the present invention can be used for any electrochemical device such as a primary battery, a secondary battery (storage battery), a capacitor, and a hybrid capacitor, but is preferably used for a storage battery.
In the following, the term “polymer” includes oligomers.

It is one of the preferred embodiments of the present invention that the gel electrolyte contains a polymer. When a polymer is used for the gel electrolyte, it is preferably gel-like and gelled by non-covalent bonds such as covalent bonds, coordinate bonds, ionic bonds, hydrogen bonds, π bonds, van der Waals bonds, etc. . More preferably, it is a polymer that forms a cross-linked structure by a functional group of the polymer and a polyvalent ion and / or an inorganic compound. Such a polymer is in a gel form, but as will be described later, the gel electrolyte contains an electrolytic solution. Conventionally, the cross-linked sites of the polymer are often decomposed under acidic conditions or basic conditions caused by the electrolytic solution and / or under an electric load, resulting in dissolution in the electrolytic solution. As a result, the deterioration of the gel electrolyte gradually proceeds. However, the presence of polyvalent ions and / or inorganic compounds allows the functional group of the polymer to become a cross-linking point by the polyvalent ions and / or inorganic compounds, not only suppressing the above degradation, but Or it becomes the structure bridge | crosslinked by the inorganic compound, and the gel-like compound which expresses a suitable battery characteristic will be formed. As a result, deterioration of the gel electrolyte can be sufficiently suppressed. As a result, shape change such as shape change and dendrite of electrode active material, dissolution, corrosion, suppression of passive formation, suppression during charging and storage in charging state It is possible to continuously suppress the self-discharge in the battery and to maintain high battery performance for a longer time.

Examples of the polymer used in the gel electrolyte include a polyalkane moiety-containing polymer represented by polyethylene and polypropylene; an unsaturated bond-containing polymer represented by polyhexene and polyoctene; an aromatic group-containing polymer represented by polystyrene and the like. An ether group-containing polymer represented by alkylene glycol, etc .; a hydroxyl group-containing polymer represented by polyvinyl alcohol, phenol resin, poly (α-hydroxymethyl acrylate), etc .; polyamide, nylon, polyacrylamide, polyvinyl pyrrolidone, N- Polymers containing amide bonds such as substituted polyacrylamides; Polymers containing imide bonds such as polymaleimides; Polymers such as poly (meth) acrylic acid, polymaleic acid, polyitaconic acid, and polymethylene glutaric acid Boxyl group-containing polymers; carboxylate-containing polymers represented by poly (meth) acrylate, polymaleate, polyitaconate, polymethylene glutarate, etc .; polyvinyl chloride, polyvinylidene fluoride, polytetrafluoroethylene, etc. A halogen-containing polymer of nitrile group-containing polymer such as polyacrylonitrile; an ester group-containing polymer typified by polyester; a polymer in which an epoxy group typified by epoxy resin is bonded by ring-opening; poly (2-hydroxy- Sodium 3-allyloxypropanesulfonate), poly (sodium methallylsulfonate), poly (sodium 2-sulfoethyl methacrylate), poly (sodium isoprenesulfonate), poly (2-acrylamido-2-methylpropanesulfonic acid) Nat Helium) Polyvinyl sulfonate site-containing polymer represented by sulfonic acids such as ^{sodium; AR 1 R 2 R 3 B} (A is .B representing N or P is a halogen anion or OH ^- represents the like anions. R ¹ , R ² and R ³ are the same or different and each 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 are bonded to each other. A quaternary ammonium salt or a quaternary phosphonium salt-containing polymer represented by a polymer to which a group represented by (2) is bonded; used for a cation / anion exchange membrane, etc. Ion exchange polymer; natural rubber; artificial rubber typified by styrene butadiene rubber (SBR); cellulose, cellulose acetate, hydroxyalkyl cellulose, dextrin, carbo Sugars typified by dimethyl cellulose and hydroxyethyl cellulose; ketone group-containing polymers typified by polyether ketone and polyether ether ketone; amino group-containing polymers typified by polyethyleneimine; thiocarboxylic acid (salt) group-containing polymers; Isocyanic acid site-containing polymer; thioisocyanic acid site-containing polymer; carbamate group site-containing polymer; thiocarbamate group site-containing polymer; carbamide group site-containing polymer; thiocarbamide group site-containing polymer; imide group site-containing polymer; Oxetane group-containing polymer; sulfide group-containing polymer; sulfone group-containing polymer; sulfonimide group-containing polymer; liquid crystal; liquid crystal site-containing polymer; A polymethylene lactone moiety-containing polymer; a heterocyclic ring and / or an ionized heterocyclic moiety-containing polymer; a polymer alloy; a heteroatom-containing polymer; Polymer is radical polymerization, radical (alternate) copolymerization, anion polymerization, anion (alternate) copolymerization, cationic polymerization, cationic (alternate) copolymerization, graft polymerization, graft (alternate) copolymerization from monomers corresponding to the structural unit. , Living polymerization, living (alternate) copolymerization, dispersion polymerization, emulsion polymerization, suspension polymerization, ring-opening polymerization, cyclization polymerization, polymerization by light, ultraviolet ray or electron beam irradiation, and the like. These polymers are aromatic groups, ether groups, ketone groups, hydroxyl groups, amide groups, imide groups, carboxyl groups, halogen groups, nitrile groups, ester groups, epoxy groups, carboxylate moieties, sulfonate moieties, ammonium salt moieties. In addition, a functional group such as a phosphonium salt moiety may be present in the main chain and / or side chain, and may exist as a binding site with a crosslinking agent.

Among these, aromatic group-containing polymers represented by polystyrene and the like; ether group-containing polymers represented by alkylene glycol and the like; hydroxyl group-containing polymers represented by polyvinyl alcohol and poly (α-hydroxymethyl acrylate); Amide bond-containing polymers represented by polyamide, nylon, polyacrylamide, polyvinylpyrrolidone, N-substituted polyacrylamide, etc .; Imide bond-containing polymers represented by polymaleimide, etc .; poly (meth) acrylic acid, polymaleic acid, polyitaconic acid, Carboxyl group-containing polymers typified by polymethylene glutarate, etc .; carboxylate-containing polymers typified by poly (meth) acrylate, polymaleate, polyitaconate, polymethylene glutarate, etc .; polyvinyl chloride, Polif Halogen-containing polymers such as vinylidene fluoride and polytetrafluoroethylene; polymers bonded by ring opening of epoxy groups such as epoxy resins; poly (2-hydroxy-3-allyloxypropane sodium sulfonate) / poly (methallylsulfone) Acid sodium), poly (sodium 2-sulfoethyl methacrylate), poly (sodium isoprene sulfonate), poly (sodium 2-acrylamido-2-methylpropane sulfonate), sodium sulfonate such as sodium polyvinyl sulfonate 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. C1-C7 alkyl group, hydroxyalkyl group, alkylcarbo And a quaternary ammonium salt represented by a polymer to which a group represented by R ¹ , R ² , and R ³ may be bonded to form a ring structure. And quaternary phosphonium salt-containing polymers; ion-exchangeable polymers used for cation / anion exchange membranes, etc .; natural rubber; artificial rubber typified by styrene butadiene rubber (SBR); cellulose, cellulose acetate, hydroxy Saccharides represented by alkyl cellulose, dextrin, carboxymethyl cellulose, and hydroxyethyl cellulose; amino group-containing polymers represented by polyethyleneimine; carbamate group site-containing polymers; carbamide group site-containing polymers; epoxy group site-containing polymers are preferred. 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 by an organic crosslinking agent compound other than the polyvalent ion and / or inorganic compound. May be cross-linked via a peroxide bond, carbon-carbon bond, carbon-nitrogen bond, carbamate bond, thiocarbamate bond, carbamide bond, thiocarbamide bond, thiocarbamate bond, oxazoline moiety-containing bond, triazine bond, etc. .

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

As a blending ratio of the polymer in the gel electrolyte and the polyvalent ion and / or the inorganic compound, a mass ratio of the polymer and at least one of the polyvalent ion and the inorganic compound is 5000000/1. It is preferable that it is 1/100000. At such a blending ratio, deterioration of the gel electrolyte is suppressed, shape change such as shape change and dendrite of the electrode active material, dissolution, corrosion, suppression of passive formation, suppression at the time of charging and charging state Effective suppression of self-discharge at the time can be performed sufficiently continuously, and high battery performance can be maintained for a longer time. More preferably, it is 2000000/1-1/10000, More preferably, it is 1000000/1-1/1000.

As the inorganic compound, the electrolytic solution, and the polymer used for the preparation of the gel electrolyte, it is preferable to use those subjected to deoxygenation treatment. Moreover, it is preferable to perform mixing of polyvalent ions and / or inorganic compounds, electrolytic solutions, and polymers in an inert atmosphere. When mixing is performed in an inert atmosphere using a raw material that has been subjected to deoxygenation treatment, the resulting gel electrolyte has good electrical characteristics. More preferably, the amount of dissolved oxygen in the gel electrolyte is as close to 0 mg / L as possible. By reducing the dissolved oxygen concentration, it becomes possible to reduce the dissolution of the zinc electrode active material into the electrolyte, and the shape change, dissolution, and corrosion reaction of the zinc electrode active material are suppressed, and the life of the electrode is improved. become. In addition, in the case of a strong alkaline aqueous solution-containing electrolyte, when carbon dioxide is mixed in, a large amount of carbonate is generated, which may lower the conductivity and adversely affect the battery performance. It is preferable to remove at the same time.

The gel electrolyte of the present invention has a cross-linked structure with polyvalent ions and / or inorganic compounds, and a storage battery using such a gel electrolyte is a morphological change such as shape change or dendrite of an electrode active material, dissolution, Suppresses corrosion and passive formation, suppresses self-discharge during charging and storage in a charged state, and exhibits high cycle characteristics, rate characteristics, and coulomb efficiency while maintaining high ionic conductivity It can be done. The reason for this is as described above. Moreover, this gel electrolyte can be used suitably also for a primary battery, and can suppress the form change of an electrode active material, and can express a high rate characteristic, maintaining high ionic conductivity.
Thus, a battery comprising a positive electrode, a negative electrode, and an electrolyte sandwiched between them, wherein the electrolyte is formed with the gel electrolyte of the present invention as an essential component, is also included in the present invention. One. The battery of the present invention having the gel electrolyte of the present invention which is the first present invention as an essential component of the electrolyte is also referred to as the first battery of the present invention. The first battery of the present invention may contain one of these essential components, or two or more of them.
As described above, since the gel electrolyte of the present invention can enhance various characteristics of the storage battery, it is preferable that the battery of the present invention (the first battery of the present invention) is a storage battery. This is one of the embodiments.

In the first battery of the present invention, the electrolyte may be all of the gel electrolyte of the present invention, or may partially contain the gel electrolyte of the present invention. A battery in which the electrolyte is the gel electrolyte of the present invention includes a battery in which the electrolyte is swollen by an electrolytic solution to become a gel electrolyte, and has a structure in which the electrolyte is sandwiched between a positive electrode and a negative electrode. Thus, the form in which the gel electrolyte of the present invention is used for the entire electrolyte sandwiched between the positive electrode and the negative electrode is also a preferred embodiment of the present invention.

In addition, in the battery in which a part of the electrolyte is the gel electrolyte of the present invention, the electrolyte is composed of the gel electrolyte of the present invention and another (gel) electrolyte or electrolyte other than the gel electrolyte. . For example, when the gel electrolyte is used for a primary battery or a secondary battery using a zinc-containing compound as a negative electrode and a water-containing electrolyte described later, the electrolyte is a gel electrolyte of the present invention, a polyvalent cation, and It becomes the form comprised from the gel electrolyte which does not contain an inorganic compound or water-containing electrolyte solution, etc. Furthermore, the gel electrolyte of the present invention can suppress morphological changes such as shape change and dendrite of electrode active materials, suppression of dissolution, corrosion and passive formation, and self-discharge during charging and storage in a charged state. Therefore, the electrolyte in contact with the negative electrode is preferably formed using the gel electrolyte of the present invention as an essential component. As described above, the battery is configured such that the gel electrolyte of the present invention is used for a part of the electrolyte sandwiched between the positive electrode and the negative electrode, and the electrolyte in contact with the negative electrode is formed by using the gel electrolyte of the present invention as an essential component. This is one of the preferred embodiments of the present invention. In this case, it is sufficient that at least a part of the electrolyte in contact with the negative electrode is formed with the gel electrolyte of the present invention as essential, but all of the electrolyte in contact with the negative electrode is formed with the gel electrolyte of the present invention as essential. Preferably there is. The gel electrolyte may be used in a battery that has been previously polymerized or kneaded between a polymer and an electrolytic solution, or a gel electrolyte raw material such as a monomer is placed in the battery. Later, it may be polymerized in the battery to make it. In addition, a gel electrolyte prepared in advance with a thickness of 1 nm or more and 5 mm or less on the electrode surface, or a gel electrolyte raw material is applied and then polymerized to form an electrolyte coating on the electrode surface. It may be formed. The gap between the electrode and the counter electrode may be the same as the gel electrolyte in contact with the electrode, or a different gel electrolyte or a liquid electrolyte may be used. By optimizing the properties and properties of the gel electrolyte at the position between the positive and negative electrodes, the performance, stability and life of the battery can be further enhanced.

When the electrolyte is composed of the gel electrolyte of the present invention and another (gel) electrolyte or electrolyte solution other than the gel electrolyte, the ratio of the gel electrolyte of the present invention to the total amount of 100% by mass of the electrolyte site Is preferably 0.001 to 100% by mass. More preferably, it is 0.01-100 mass%. In particular, when the electrolyte is composed of the gel electrolyte of the present invention and a water-containing electrolytic solution, the ratio of the gel electrolyte of the present invention to the total amount of the electrolyte of 100% by mass is preferably 0.01 to 100% by mass. More preferably, it is 0.02-100 mass%.

As the positive electrode active material, those normally used as the positive electrode active material of a primary battery or a secondary battery can be used, and are not particularly limited. For example, oxygen (when oxygen becomes a positive electrode active material, the positive electrode is oxygen Perovskite type compounds capable of reducing water and oxidizing water, cobalt-containing compounds, iron-containing compounds, copper-containing compounds, manganese-containing compounds, vanadium-containing compounds, nickel-containing compounds, iridium-containing compounds, platinum-containing compounds, etc. Poles), nickel-containing compounds such as nickel oxyhydroxide, nickel hydroxide, cobalt-containing nickel hydroxide, manganese-containing compounds such as manganese dioxide, silver oxide, lithium cobaltate, lithium manganate, lithium iron phosphate, etc. Can be mentioned. Among these, a battery using a zinc negative electrode mixture, and the positive electrode active material being a nickel compound is also a preferred embodiment of the present invention. Moreover, it is also one of the suitable embodiments of the present invention that the positive electrode active material such as an air battery or a fuel cell is oxygen. That is, it is one of the preferred embodiments of the present invention that the positive electrode of the battery of the present invention is an air electrode.
Moreover, as a form of the battery using the zinc negative electrode mixture of the present invention, a primary battery, a secondary battery capable of charging / discharging, use of mechanical charge (mechanical replacement of the zinc negative electrode), a zinc negative electrode of the present invention and Any form such as utilization of a third electrode (for example, an electrode for removing oxygen generated during charge / discharge) different from the positive electrode composed of the positive electrode active material as described above may be used.

As said negative electrode, what is normally used as a negative electrode of a battery can be used, Although it does not restrict | limit, For example, a lithium containing compound, a zinc containing compound, etc. are mentioned. Among these, when the negative electrode contains lithium and zinc, the shape change, dissolution, corrosion, and passivity formation of electrode active materials such as shape change and dendrite are particularly remarkable. The effect of the present invention that can be suppressed will be exhibited more remarkably. From this, it is also one of the preferred embodiments of the present invention that the negative electrode contains lithium and / or zinc in the first battery of the present invention. The gel electrolyte of the present invention can be used for a lithium ion battery using graphite as a negative electrode, an electrolyte such as an air battery or a fuel cell using an air electrode as a positive electrode, and as a separator or an ion exchange membrane. Can also be used.

As the electrolytic solution and the electrolytic solution used in preparing the gel electrolyte, those commonly used as the electrolytic solution for the battery can be used, and are not particularly limited. For example, the organic solution used for the organic solvent-based electrolytic solution Solvents include ethylene carbonate, propylene carbonate, dimethyl carbonate, diethyl carbonate, γ-butyrolactone, dimethoxymethane, diethoxymethane, dimethoxyethane, tetrahydrofuran, methyltetrahydrofuran, diethoxyethane, dimethyl sulfoxide, sulfolane, acetonitrile, benzonitrile, ions Liquids, fluorine-containing carbonates, fluorine-containing ethers, polyethylene glycols, fluorine-containing polyethylene glycols are preferred. Compound that generates hydroxide ions are preferred electrolyte containing (electrolyte), for example, aqueous potassium hydroxide, aqueous sodium hydroxide, and the like lithium hydroxide aqueous solution. In particular, an aqueous potassium hydroxide solution is preferable from the viewpoint of ion conductivity. The water-containing electrolyte can be used alone or in combination of two or more.
The water-containing electrolytic solution refers to an electrolytic solution (water-based electrolytic solution) that uses only water as an electrolytic solution raw material, or an electrolytic solution that uses a solution obtained by adding an organic solvent to water as an electrolytic solution raw material. In the case of a water-containing electrolyte containing an organic solvent-based electrolyte, the content of the water-based electrolyte is preferably 10 to 99.99% by mass with respect to a total of 100% by mass of the aqueous electrolyte and the organic solvent-based electrolyte. More preferably, it is 20-99.99 mass%.
The electrolyte is not particularly limited, but when a water-containing electrolyte is used, for example, a compound that generates hydroxide ions responsible for ion conduction in the system, such as potassium hydroxide, sodium hydroxide, lithium hydroxide, and the like. Preferably, when an organic solvent-based electrolyte is used, LiPF ₆ , LiBF ₄ , LiB (CN) ₄ , lithium bis (fluorosulfonyl) imide (LiFSI), lithium bis (trifluoromethylsulfonyl) imide (LiTFSI), etc. Is preferred.

The concentration of the electrolytic solution is preferably 0.01 to 50 mol / L of an electrolyte, for example, potassium hydroxide. By using an electrolytic solution having such a concentration, good battery performance can be exhibited. Moreover, More preferably, it is 1-20 mol / L, More preferably, it is 3-18 mol / L.

When the gel electrolyte is used for a primary battery or a secondary battery using a water-containing electrolytic solution having a zinc-containing compound as a negative electrode, the zinc electrolyte, zinc hydroxide, It is preferable to add at least one zinc compound selected from zinc phosphate, zinc pyrophosphate, zinc borate, zinc silicate, zinc aluminate, zinc metal, and tetrahydroxy zinc ions. As a result, changes in the shape of the electrode active material such as shape change and dendrite accompanying the dissolution of the zinc electrode active material during charge and discharge, formation of growth and passivation, and self-retention during charging and storage in the charged state Discharge can be further suppressed. In this case, elements other than zinc are used for the polyvalent ions and inorganic compounds to be used. The zinc compound in the gel electrolyte is preferably from 0.0001 mol / L to a saturated concentration.

In addition, when using a water-containing electrolyte, the dissolved oxygen concentration value (mg / L) (at 25 ° C.) of only the aqueous electrolyte to be used is
α = −0.26375 × β + 8.11
(Β represents the hydroxide ion concentration <mol / L> in the aqueous electrolyte used)
It is preferable that it is below the (alpha) value calculated by the type | formula. More preferably, the amount of dissolved oxygen is as close to 0 mg / L as possible. By reducing the dissolved oxygen concentration, it becomes possible to reduce the dissolution of the zinc electrode active material in the electrolyte, and the change in the shape, dissolution, corrosion, and passivation of the zinc electrode active material is suppressed, and the life of the electrode Will be improved. In order to make the dissolved oxygen concentration equal to or less than a predetermined amount, it can be achieved by operations such as deaeration of the electrolyte or the solvent used in the electrolyte and bubbling of an inert gas such as nitrogen or argon. In addition, in the case of a strong alkaline aqueous solution-containing electrolyte, when carbon dioxide is mixed in, a large amount of carbonate is generated, which may lower the conductivity and adversely affect the battery performance. It is preferable to remove at the same time. The equation of the dissolved oxygen concentration value is an equation derived from the corrosion state of dissolved oxygen and zinc metal. Further, 8.11 in the above formula is the saturation solubility of oxygen in pure water (25 ° C.). Furthermore, in 4M and 8M KOH aqueous solutions, a 4M and 8M KOH aqueous solution in which an arbitrary amount of oxygen (25 ° C) was dissolved (with an arbitrary amount of dissolved oxygen) was created, and the corrosion of zinc metal immersed in the liquid was created. The above equation is derived by observing the presence or absence with an SEM. By setting the dissolved oxygen amount to be equal to or less than the α value, the reaction represented by the formula of Zn + 1 / 2O ₂ + H ₂ O → Zn (OH) ₂ is suppressed, so that it is considered that corrosion hardly occurs.

The (gel) electrolyte other than the gel electrolyte of the present invention is not particularly limited as long as it can be used as a battery electrolyte. For example, lithium or the like can be used even in the absence of a liquid such as an electrolyte. It does not contain a solid electrolyte capable of conducting anions such as cations and hydroxide ions, and the above polyvalent ions and / or inorganic compounds, and other compounds (crosslinking agents) can be used for ester bonds, amide bonds, and ions. Bond, van der Waals bond, agostic interaction, hydrogen bond, acetal bond, ketal bond, ether bond, peroxide bond, carbon-carbon bond, carbon-nitrogen bond, urea bond, thiourea bond, carbamate bond, carbamide bond, oxazoline A gel electrolyte that is cross-linked through a site-containing bond, a triazine bond, or the like can be given.

In the first battery of the present invention, the gel electrolyte may also serve as a separator, but separately from this, a separator can also be used. The separator is a member that separates the positive electrode and the negative electrode and holds the electrolyte solution to ensure ionic conductivity between the positive electrode and the negative electrode. In addition, in the case of a battery using a zinc negative electrode, the zinc electrode active material is prevented from being deteriorated and dendrite is formed, the positive and negative electrodes are moistened, and liquid drainage is avoided. The gel electrolyte and separator may have pores, micropores, and gas diffusion layers.
The separator is not particularly limited, but non-woven fabric, filter paper, polyethylene, polypropylene, polytetrafluoroethylene, polyvinylidene fluoride, cellulose, fibrillated cellulose, viscose rayon, cellulose acetate, hydroxyalkyl cellulose, carboxymethyl cellulose, polyvinyl alcohol, High molecular weight polymers such as cellophane, polystyrene, polyacrylonitrile, polyacrylamide, polyvinyl chloride, polyamide, polyimide, vinylon, nylon, poly (meth) acrylic acid, copolymers thereof, agar, gel compounds, organic inorganic Hybrid compounds, ion-exchange membrane polymers and their copolymers, cyclized polymers and their copolymers, poly (meth) acrylate-containing polymers and their copolymers, sulfonates Yes polymers and their copolymers, quaternary ammonium salt-containing polymers and their copolymers, quaternary phosphonium salts polymers and their copolymers, inorganic such as ceramics.
The separator may contain the polyvalent cation and / or inorganic compound, a surfactant, an electrolytic solution, and the like. As the separator, one kind or two or more kinds of separators may be used, and any number can be used as long as resistance does not increase and battery performance does not deteriorate.

Next, the second present invention will be described. The negative electrode mixture of the present invention contains a negative electrode active material and a polymer, and contains a polymer in addition to the negative electrode active material. By making the negative electrode mixture like this, it is effective for shape change of electrode active material such as shape change and dendrite, dissolution, formation of corrosion and passivation, self-discharge during charging and storage in charged state Can be suppressed. When the negative electrode mixture is added to the negative electrode active material and contains a polymer, a film made of a polymer is formed on the entire surface or part of the particle surface of the negative electrode active material. By effectively limiting the diffusion of water, etc. physically and chemically, it is possible to change the shape of the electrode active material such as shape change and dendrite, dissolve, form corrosion, passivate, and store it in a charged state or in a charged state. It is considered that self-discharge is effectively suppressed. Furthermore, the storage battery formed using the negative electrode mixture of the present invention can exhibit high cycle characteristics, rate characteristics, and coulomb efficiency while maintaining high electrical conductivity. This is presumed to be because, in addition to suppressing the change in the active material form of the negative electrode, the effects of improving the hydrophilic / hydrophobic balance, improving the ionic conductivity, and improving the electronic conductivity are also exhibited. The negative electrode mixture of the present invention may contain other components such as a conductive additive as long as it contains a negative electrode active material and a polymer. Moreover, each of these components may contain 1 type, and may contain 2 or more types. When the negative electrode mixture of the present invention contains other components other than the negative electrode active material and the polymer, the total amount of the negative electrode active material and the polymer included in the negative electrode mixture of the present invention is 100 mass of the total amount of the negative electrode mixture. It is preferable that it is 20-99.99 mass% with respect to%. More preferably, it is 30-99.9 mass%.
Thus, it can be set as the battery which exhibits the outstanding characteristic by using the electrode formed using the negative mix of this invention. An electrode formed using such a negative electrode mixture of the present invention is also one aspect of the present invention. The electrode of the present invention is preferably used as a negative electrode, and the negative electrode formed using the negative electrode mixture of the present invention is also referred to as the negative electrode of the present invention.

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

The average particle size of the zinc-containing compound is preferably 500 μm to 1 nm, more preferably 100 μm to 5 nm, still more preferably 20 μm to 10 nm, and particularly preferably 10 μm to 100 nm.
When zinc oxide is used as the zinc compound, the average particle size is 100 μm to 100 nm when zinc oxide is added to ion-exchanged water and ultrasonically dispersed for 5 minutes and then measured with a particle size distribution analyzer. More preferably, it is 50 μm to 200 nm, more preferably 10 μm to 300 nm, and the mode diameter is preferably 20 μm to 50 nm, more preferably 10 μm to 70 nm, still more preferably, The median diameter is preferably 10 μm to 100 nm, more preferably 7 μm to 150 nm, and still more preferably 5 μm to 500 nm.

The specific surface area of the zinc-containing compound is more preferably 0.01 m ² / g or more and 60 m ² / g or less, and still more preferably 0.1 m ² / g or more and 50 m ² / g or less.
The specific surface area can be measured by a specific surface area measuring apparatus or the like by a nitrogen adsorption BET method.

The reason why the average particle size of the zinc-containing compound is preferably 500 μm to 1 nm is considered as follows.
The negative electrode mixture of a battery containing a zinc-containing compound preferably further contains a conductive additive. When the negative electrode of the battery is formed from a zinc negative electrode mixture containing a zinc-containing compound and a conductive additive, in order to function as a negative electrode (current flows), the zinc-containing compounds, the zinc-containing compound and the conductive auxiliary, It is preferable that the zinc-containing compound, the conductive additive, and the current collector are bound. However, if charging / discharging is repeated or rapid charging / discharging is performed, the zinc-containing compound and the zinc-containing compound and the conductive material inevitably are connected. Dissociation of the auxiliary agent, the zinc-containing compound, the conductive auxiliary agent, and the current collector or the passivation of the zinc-containing compound may proceed, leading to a decrease in battery performance. However, when particles having an average particle diameter as described above are used as the zinc-containing compound, the zinc-containing compounds, the zinc-containing compound and the conductive auxiliary, the zinc-containing compound, the conductive auxiliary and the current collector efficiently contact each other, Zinc-containing compounds, zinc-containing compounds and conductive assistants, zinc-containing compounds, conductive assistants and current collectors can be completely dissociated, and as a result, deterioration of battery performance can be suppressed. It becomes possible. Moreover, the polymer contained in the said negative electrode mixture can further strengthen the efficient contact of zinc containing compounds, a zinc containing compound, a conductive support agent, a zinc containing compound, a conductive support agent, and a collector.

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

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

In the negative electrode mixture of the second aspect of the present invention, the blending amount of the negative electrode active material is preferably 50 to 99.9% by mass with respect to 100% by mass of the total amount of the negative electrode mixture. When the amount of the negative electrode active material is in such a range, better battery performance is exhibited when the negative electrode formed from the negative electrode mixture is used as the negative electrode of the battery. More preferably, it is 55-99.5 mass%, More preferably, it is 60-99 mass%.

As a polymer which the said negative electrode mixture contains, the 1 type (s) or 2 or more types of the same thing as the polymer which can be used for the gel electrolyte mentioned above can be used.

The blending amount of the polymer is preferably 0.01 to 100% by mass with respect to 100% by mass of the negative electrode active material in the negative electrode mixture. When the blending amount of the polymer is within such a range, when the negative electrode formed from the negative electrode mixture is used as the negative electrode of the battery, better battery performance is exhibited. More preferably, it is 0.01-60 mass%, More preferably, it is 0.01-40 mass%.

Examples of the conductive auxiliary agent include conductive carbon, conductive ceramics, and metal.
Examples of the conductive carbon include graphite, natural graphite, artificial graphite, glassy carbon, amorphous carbon, graphitizable carbon, non-graphitizable carbon, carbon nanofoam, activated carbon, graphene, nanographene, graphene nanoribbon, fullerene, carbon black, graphite Carbon black, ketjen black, vapor grown carbon fiber, pitch-based carbon fiber, mesocarbon microbeads, metal coated carbon, carbon coated metal, fibrous carbon, boron containing carbon, nitrogen containing carbon, multilayer / single Examples include single-walled carbon nanotubes, carbon nanohorns, Vulcan, acetylene black, carbon treated with a hydrophilic treatment by introducing an oxygen-containing functional group, and SiC-coated carbon.
Examples of the conductive ceramics include Bi and / or Co and / or Nb and / or Y-containing compounds fired with zinc oxide. Examples of the metal include zinc metal.

Among the conductive aids, graphite, natural graphite, artificial graphite, graphitizable carbon, non-graphitizable carbon, graphene, carbon black, graphitized carbon black, ketjen black, vapor-grown carbon fiber, pitch-based carbon fiber, Mesocarbon microbeads, fibrous carbon, multi-wall / single-wall carbon nanotubes, vulcanized carbon, acetylene black, carbon treated with a hydrophilic treatment by introducing an oxygen-containing functional group, and metallic zinc are preferred. The metal zinc may be used for an actual battery such as an alkaline battery or an air battery, or may be one whose surface is coated with another element, carbon or the like.
The said conductive support agent can be used by 1 type, or 2 or more types. Conductive carbon is preferably not subjected to coating treatment with a low molecular weight surfactant in order to make the most of its conductivity. Metallic zinc can also act as an active material.

When metallic zinc is used as the conductive aid, metallic zinc may be added as a negative electrode mixture in the negative electrode preparation stage, and zinc oxide, zinc hydroxide, etc., which are zinc-containing compounds when charged and discharged It is also possible to use zinc metal produced from the above as a conductive aid. In this case, the zinc-containing compound functions as a negative electrode active material and a conductive additive.

In order to suppress the side reaction, the conductive auxiliary agent may cause a water decomposition side reaction at the time of charge / discharge when a water-containing electrolyte is used when a storage battery is produced using the conductive auxiliary agent. A specific element may be introduced into the conductive additive. Specific elements include B, Ba, Bi, Br, Ca, Cd, Ce, Cl, F, Ga, Hg, In, La, Mn, N, Nb, Nd, P, Pb, Sc, Sn, Sb, Sr, Ti, Tl, Y, Zr, etc. are mentioned. When conductive carbon is used as one of the conductive assistants, specific elements include B, Bi, Br, Ca, Cd, Ce, Cl, F, In, La, Mn, N, Nb, and Nd. , P, Pb, Sc, Sn, Tl, Y, Zr are preferable.
Here, introducing a specific element into a conductive assistant means that the conductive assistant is a compound having the constituent elements of these elements.

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

Moreover, the average particle diameter of a conductive support agent is 500 micrometers-1 nm, More preferably, they are 200 micrometers-5 nm, More preferably, they are 100 micrometers-10 nm. The reason why the average particle diameter of the conductive assistant is preferably such a value is the same as the reason why the average particle diameter described above is preferable as the zinc-containing compound, and the average particle diameter is used. Thus, it is possible to reduce the number of places where the zinc-containing compound and the conductive auxiliary agent, the zinc-containing compound, the conductive auxiliary agent, and the current collector are completely dissociated, and as a result, it is possible to suppress a decrease in battery performance. .
The specific surface area and average particle diameter of the conductive carbon can be measured by the same method as that for the zinc-containing compound described above.

When the conductive carbon is used as a conductive auxiliary agent, and the conductive carbon has a shape having an edge portion, the water decomposition side reaction proceeds even at the edge portion of the conductive carbon, etc. Therefore, the specific surface area of the conductive carbon is preferably 0.1 m ² / g or more and 1500 m ² / g or less, more preferably 1 m ² / g or more and 1200 m ² / g or less, more preferably, ^{1 m} 2 / g or more, or less 900 meters ² / g, particularly preferably, ^{1 m} 2 / g or more, 250 meters ² / g or less, and most preferably, ^{1 m} 2 / g or more, ^{50 m} 2 / g It is as follows.

The edge portion of the conductive carbon can be reduced by graphitization. A negative electrode having a negative electrode mixture using conductive carbon as a conductive additive is expected to be able to withstand charge / discharge conditions at a high rate, and is particularly good when a storage battery using the negative electrode is applied as an on-vehicle application. It is expected that it will exhibit excellent performance. In addition, it suppresses self-discharge during charging and storage in the charged state, and also suppresses changes in the shape of the negative electrode active material by depositing zinc in the mesopores and micropores of the conductive carbon. Is also expected. Furthermore, since water may be decomposed at the edge part of conductive carbon during charging and discharging, high cycle characteristics, rate characteristics, and expression of Coulomb efficiency are expected by reducing the edge part by graphitization treatment. Is done.

As a compounding quantity of the said conductive support agent, it is preferable that it is 0.0001-100 mass% with respect to 100 mass% of negative electrode active materials in a negative mix. When metal zinc is used as a conductive additive at the time of preparing the negative electrode mixture, the metal zinc is not a zinc-containing compound but is calculated as a conductive additive. In addition, zinc metal generated from zinc oxide or zinc hydroxide, which is a zinc-containing compound, can also be used as a conductive aid in the system. In that case, the zinc-containing compound used at the time of preparing the negative electrode mixture is Calculation is performed considering the negative electrode active material. In addition, zinc metal produced during charging / discharging from zinc oxide, zinc hydroxide or the like, which is a zinc-containing compound, will also function as a conductive aid in the system, but it is 0 when preparing a zinc negative electrode mixture or a zinc negative electrode. Since it is not a valent zinc metal, it is not considered here as a conductive additive. That is, the preferable compounding quantity of the conductive support agent here is a preferable quantity of the conductive support agent mix | blended at the time of preparation of a zinc negative electrode mixture or a zinc negative electrode. When the blending amount of the conductive auxiliary is within such a range, better battery performance is exhibited when the negative electrode formed from the negative electrode mixture is used as the negative electrode of the battery. More preferably, it is 0.0005-60 mass%, More preferably, it is 0.001-40 mass%.

The negative electrode mixture may further contain other components. Examples of the other components include compounds having at least one element selected from the group consisting of elements belonging to Groups 1 to 17 of the periodic table, organic compounds, organic compound salts, and the like.
Here, in the case of a battery configured using a water-containing electrolyte as an electrolyte, it is preferable to an organic solvent-based electrolyte from the viewpoint of safety. A side reaction that a hydrogen decomposition reaction proceeds and hydrogen is generated may occur due to a chemical reaction or self-discharge during charging or storage in a charged state. However, the negative electrode mixture of the present invention includes, as other components, a compound having at least one element selected from the group consisting of elements belonging to Groups 1 to 17 of the periodic table, an organic compound, and an organic compound salt. Assuming that it contains at least one selected from the group consisting of: a negative electrode formed from the negative electrode mixture of the present invention, and even when a battery is constructed using a water-containing electrolyte, water during charging and discharging It is possible to effectively suppress the generation of hydrogen due to decomposition of. In addition, suppression of self-discharge during storage in a charged state, suppression of changes in the active material form of the negative electrode, suppression of solubility of zinc species due to salt formation with zinc species such as tetrahydroxyzinc ions when a zinc compound is used for the negative electrode In addition, it is expected that effects such as improved affinity with water, improved anion conductivity, and improved electron conductivity will be exhibited at the same time, and charge / discharge characteristics and Coulomb efficiency will be significantly improved.
Thus, the negative electrode mixture of the present invention further includes other components, and the other components are compounds having at least one element selected from the group consisting of elements belonging to Groups 1 to 17 of the periodic table. It is also one of preferred embodiments of the present invention to contain at least one selected from the group consisting of organic compounds and organic compound salts.

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

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. Complex oxides; layered double hydroxides; hydroxides; clay compounds; solid solutions; halides; carboxylate compounds; carbonates; bicarbonates; nitrates; sulfates; Phosphate, phosphite, hypophosphite, borate, ammonium salt, sulfide, onium compound, hydrogen storage compound and the like.
Specifically, silver oxide, aluminum oxide, barium oxide, bismuth oxide, bismuth-containing composite oxide, calcium oxide, calcium-containing composite oxide, cadmium oxide, cerium oxide, cerium-containing composite oxide, cobalt oxide, chromium oxide, Cesium oxide, copper oxide, iron oxide, gallium oxide, mercury oxide, indium oxide, indium-containing composite oxide, potassium oxide, lanthanum oxide, lithium oxide, magnesium oxide, manganese monoxide, manganese dioxide, sodium oxide, niobium oxide, oxide Neodymium, lead oxide, rubidium oxide, silicon oxide, phosphorus oxide, tin oxide, scandium oxide, strontium oxide, antimony oxide, titanium oxide, tellurium oxide, vanadium oxide, yttrium oxide, ytterbium oxide, zirconium oxide, scandium oxide Stabilized zirconium oxide, zirconium oxide stabilized with yttrium oxide, zirconium-containing composite oxide, aluminum hydroxide, barium hydroxide, calcium hydroxide, strontium hydroxide, cerium hydroxide, cesium hydroxide, indium hydroxide, water Potassium oxide, lanthanum hydroxide, lithium hydroxide, magnesium hydroxide, manganese hydroxide, sodium hydroxide, rubidium hydroxide, tin hydroxide, antimony hydroxide, titanium hydroxide, zirconium hydroxide, silver chloride, chloroauric acid, Lithium chloride, magnesium chloride, sodium chloride, rubidium chloride, tin chloride, silver acetate, aluminum acetate, lithium acetate, barium acetate, bismuth acetate, calcium acetate, calcium tartrate, calcium glutamate, cadmium acetate, cerium acetate, cobalt acetate , Chromium acetate, cesium acetate, copper acetate, iron acetate, gallium acetate, mercury acetate, indium acetate, potassium acetate, lanthanum acetate, magnesium acetate, manganese acetate, sodium acetate, sodium tartrate, sodium glutamate, niobium acetate, neodymium acetate, acetic acid Lead, rubidium acetate, tin acetate, strontium acetate, antimony acetate, tellurium acetate, zinc acetate, silver carbonate, aluminum carbonate, barium carbonate, bismuth carbonate, calcium carbonate, cerium carbonate, cobalt carbonate, cesium carbonate, gallium carbonate, indium carbonate, Potassium carbonate, lanthanum carbonate, lithium carbonate, magnesium carbonate, sodium carbonate, lead carbonate, rubidium carbonate, tin carbonate, 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, sulfuric acid Vanadium, zirconium sulfate, calcium lignin sulfonate, sodium lignin sulfonate, aluminum nitrate, barium nitrate, bismuth nitrate, calcium nitrate, cesium nitrate, cerium nitrate, gallium nitrate, indium nitrate, potassium nitrate, lanthanum nitrate, lithium nitrate, magnesium nitrate, Sodium nitrate, lead nitrate, rubidium nitrate, tin nitrate, strontium nitrate, antimony nitrate, titanium nitrate, tellurium nitrate, vanadium nitrate, zirconium nitrate, potassium silicate, silicic acid Lucium, magnesium silicate, barium silicate, potassium aluminate, calcium aluminate, magnesium aluminate, barium aluminate, lithium phosphate, sodium phosphate, potassium phosphate, calcium phosphate, magnesium phosphate, barium phosphate, boric acid Lithium, sodium borate, potassium borate, magnesium borate, calcium borate, barium borate, bismuth sulfide, calcium sulfide, indium sulfide, cerium sulfide, zirconium sulfide, gold, silver, potassium fluoride, sodium fluoride, fluoride Lithium hydride, layered double hydroxide (hydrotalcite, etc.), clay compound, lipolite, hydroxyapatite, solid solution such as cerium oxide-zirconium oxide, ettringite, and cement are particularly preferable.

Moreover, the compound which has at least 1 element selected from the group which consists of an element which belongs to the 1st-17th group of the said periodic table is converted into a nanoparticulate etc., and the same as the said zinc containing compound and / or a conductive support agent. If the average particle diameter is small, side reactions that occur when a water-containing electrolytic solution is used as the above-described electrolytic solution can be further effectively suppressed. The compound having at least one element selected from the group consisting of elements belonging to Groups 1 to 17 of the periodic table is the zinc-containing compound before or after the preparation of the zinc negative electrode mixture or during the preparation of the zinc negative electrode mixture. In addition, at least one of a conductive additive, an organic compound, and an organic compound salt may be supported, coprecipitated, alloyed, solidified, or kneaded. It may be prepared by a sol-gel method. Thus, the compound having at least one element selected from the group consisting of elements belonging to Groups 1 to 17 of the periodic table preferably has an average particle diameter of 1000 μm or less, more preferably 200 μm or less. More preferably, it is 100 μm or less, particularly preferably 75 μm or less, and most preferably 20 μm or less. On the other hand, the lower limit of the average particle diameter is preferably 1 nm.
The average particle diameter can be measured by the same method as the average particle diameter of the zinc-containing compound described above.
Examples of the shape of the particles include fine powder, powder, granule, granule, scale, polyhedron, and rod. In addition, the particles having an average particle size in the above-described range are, for example, a method of pulverizing particles with a ball mill or the like, dispersing the obtained coarse particles in a dispersant to obtain a desired particle size, 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 compound having at least one element selected from the group consisting of elements belonging to Groups 1 to 17 of the periodic table preferably has a specific surface area of 0.01 m ² / g or more, more preferably 0.8. 1 m ² / g or more, more preferably 0.5 m ² / g or more. On the other hand, the upper limit value of the specific surface area is preferably 200 m ² / g. The specific surface area can be measured in the same manner as the specific surface areas of the zinc-containing compound and the conductive additive described above.

Examples of the organic compound and organic compound salt include the same polymers as those used in the gel electrolyte described above, analgen, benzene, trihydroxybenzene, toluene, piperonaldehyde, lignin, carbowax, carbazole, amino acid, amino acid salt Glutaric acid, glutarate, betaine site-containing compound, gelatin, trialkyl phosphoric acid, soap, soap derivative, polyacetylene site-containing polymer, polymethylene lactone site-containing polymer, low molecular weight surfactant and the like can be used.

When the organic compound or organic compound salt is a polymer, radical polymerization, radical (alternate) copolymerization, anion polymerization, anion (alternate) copolymerization, cationic polymerization, cation (cation) (cation ( (Alternate) copolymerization, graft polymerization, graft (alternate) copolymerization, living polymerization, living (alternate) copolymerization, dispersion polymerization, emulsion polymerization, suspension polymerization, ring-opening polymerization, cyclization polymerization, light, ultraviolet light and electron beam irradiation Can be obtained by polymerization or the like. At this time, the compound containing at least one element selected from the group consisting of the zinc-containing compound particles, the conductive auxiliary agent particles, and the elements belonging to Groups 1 to 17 of the periodic table, in the polymer and / or on the surface It is also possible to form a single particle. In addition, the polymer may cause a reaction such as hydrolysis in the electrolytic solution.
An organic compound and an organic compound salt improve the dispersibility of the particles, and suppress the change in the active material form of the binder, the thickener, and the zinc electrode that bind the particles to each other and the current collector. Expected to work as a material that exhibits the effects of suppressing the dissolution of the active material of the zinc electrode, improving the hydrophilicity / hydrophobicity balance, improving the anion conductivity, improving the electron conductivity, and when using a water-containing electrolyte, Side reactions during charge / discharge when water decomposition reaction proceeds and hydrogen is generated, which can usually occur thermodynamically, morphological change and corrosion reaction of zinc electrode active material, and storage in charged state or charged state In addition, the self-discharge at the time is suppressed, and the charge / discharge characteristics, the coulomb efficiency, and the storage stability of the battery are significantly improved. One of the causes of this effect is considered to be derived from the fact that the organic compound or organic compound salt suitably covers or adsorbs the surface of zinc oxide. It was newly found in the present invention that such an effect is seen in organic compounds and organic compound salts.

Preferably, the organic compound or organic compound salt is a poly (meth) acrylic acid moiety-containing polymer, a poly (meth) acrylate moiety-containing polymer, a poly (meth) acrylic ester moiety-containing polymer, or poly (α-hydroxymethylacrylic). Acid salt) site-containing polymer, polyacrylonitrile site-containing polymer, polyacrylamide site-containing polymer, poly (N, N-dialkylacrylamide) site-containing polymer, polyvinyl alcohol site-containing polymer, polyethylene oxide site-containing polymer, polypropylene oxide site-containing polymer, Polybutene oxide moiety-containing polymer, epoxy ring-opening moiety-containing polymer, polyethylene moiety-containing polymer, polypropylene moiety-containing polymer, polybutene moiety-containing polymer, polyisoprenol moiety-containing polymer Polymer, polymethallyl alcohol moiety-containing polymer, polyallyl alcohol moiety-containing polymer, polyhexene moiety-containing polymer, polyoctene moiety-containing polymer, polybutadiene moiety-containing polymer, polyisoprene moiety-containing polymer, aromatic ring moiety-containing polymer represented by polystyrene, polyvinyl Pyrrolidone site-containing polymer, polyacetylene site-containing polymer, polyether ketone site-containing polymer, ketone group site-containing polymer, ether group site-containing polymer, sulfide group-containing polymer, sulfone group-containing polymer, carbamate group-containing polymer, thiocarbamate group-containing polymer, Carbamide group-containing polymer, thiocarbamide group-containing polymer, thiocarboxylic acid (salt) group-containing polymer, ester group-containing polymer, cyclopolymerization site-containing polymer , Polyvinyl alcohol moiety-containing polymer, lignin, carbowax, carbazole, amino acid, amino acid salt, glutaric acid, glutarate, betaine moiety-containing compound, gelatin, trialkyl phosphate, soap, soap derivative, cellulose, cellulose acetate, hydroxyalkyl Cellulose, dextrin, carboxymethyl cellulose, hydroxyethyl cellulose, ethylene glycol, ethylene glycol oligomer, polyethylene glycol chain-containing compound obtained by adding ethylene oxide to alcohols such as isoprenol and methallyl alcohol, polypropylene glycol chain-containing compound, polybutene glycol chain-containing compound, Polyaminoimine moiety-containing polymer, polyacetylene moiety-containing polymer, polyethyleneimine, etc. Polymer, Polyamide moiety-containing polymer, Polypeptide moiety-containing polymer, Polytetrafluoroethylene moiety-containing polymer, Polyvinylidene fluoride moiety-containing polymer, Polymerate moiety-containing polymer, Polyitaconate moiety-containing polymer, Cation / anion exchange membrane, etc. Exchange polymer, sulfonic acid moiety-containing polymer, poly (2-hydroxy-3-allyloxypropane sodium sulfonate) / poly (sodium methallylsulfonate) / poly (sodium 2-sulfoethyl methacrylate) ) ・ Poly (sodium isoprene sulfonate) ・ Poly (sodium 2-acrylamido-2-methylpropane sulfonate) ・ Polystyrene sulfonate, sodium polyvinyl sulfonate, etc. Polymer, quaternary ammonium salt, quaternary ammonium salt moiety-containing polymer, quaternary phosphonium salt, quaternary phosphonium salt moiety-containing polymer, isocyanate group-containing polymer, isocyanate group-containing polymer, thioisocyanate group-containing polymer, imide Group part-containing polymer, epoxy group part-containing polymer, oxetane group part-containing polymer, hydroxyl group part-containing polymer, liquid crystal, liquid crystal part-containing polymer, heterocyclic ring and / or ionized heterocyclic part-containing polymer, polymer alloy, heteroatom-containing It is a polymer.

As a compounding quantity of said other component, it is preferable that it is 0.1-100 mass% with respect to 100 mass% of negative electrode active materials in a negative mix. More preferably, it is 0.5-80 mass%, More preferably, it is 1.0-60 mass%.

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

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

The slurry or paste mixture may be applied, pressed or adhered to one side of the current collector, or may be applied, pressed or bonded to both sides. It dries at 0-250 degreeC during coating and / or after coating. More preferably, it is 15-200 degreeC as drying temperature. Drying may be performed by vacuum drying. The drying time is preferably 5 minutes to 48 hours. You may repeat the process of coating and drying. Moreover, it is preferable to press with a roll press machine etc. at the pressure of 0.01-20 t after drying. More preferably, the pressing pressure is 0.1 to 15 t. You may apply the temperature of 10-500 degreeC at the time of a press.

The negative electrode (negative electrode mixture electrode) obtained in this way, particularly when used as a negative electrode for a secondary battery, suppresses concentration of current and decomposition of water in the negative electrode, and forms the negative electrode active material Deterioration due to change, dissolution, corrosion, passivation, generation of hydrogen / oxygen during charge / discharge, and self-discharge during charge or storage in charge state 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-100 micrometers, More preferably, it is 20 nm-50 micrometers.

The negative electrode mixture of the present invention contains a negative electrode active material and a polymer, and a storage battery using a negative electrode formed from such a negative electrode mixture retains high ionic conductivity and electrical conductivity, High cycle characteristics, rate characteristics, and coulomb efficiency can be exhibited. Moreover, the primary battery using the negative electrode formed from the negative electrode mixture of the present invention can exhibit high rate characteristics while maintaining high ionic conductivity and electrical conductivity.
Thus, a battery comprising a positive electrode, a negative electrode, and an electrolyte sandwiched between them, wherein the negative electrode is formed with the negative electrode mixture of the present invention as an essential component, is also included in the present invention. It is one of. The battery of the present invention having the negative electrode formed from the negative electrode mixture of the present invention which is the second present invention as an essential component is also referred to as the second battery of the present invention. The second battery of the present invention may contain one of these essential components, or may contain two or more.
Although the negative electrode mixture of the present invention can be used for both primary batteries and secondary batteries (storage batteries), as described above, the negative electrode mixture of the present invention enhances various performances of storage batteries. Therefore, it is preferably used for a storage battery. That is, it is one of the preferred embodiments of the present invention that the second battery of the present invention is a storage battery.

In the second battery of the present invention, the polymer is a binder that binds particles such as a negative electrode active material or a conductive aid, or particles and a current collector, and / or a dispersant that disperses the particles. And / or can act as a thickener.

The negative electrode in the second battery of the present invention is formed by using the negative electrode mixture of the present invention as an essential component. Here, when the negative electrode active material contained in the negative electrode mixture is a lithium-containing compound and a zinc-containing compound, the formed negative electrode contains lithium and zinc. Negative electrodes containing lithium and zinc are usually prominent, especially in the form of electrode active materials such as shape change and dendrite, dissolution, corrosion, passive formation, self-discharge during charging and storage in the charged state. However, when the negative electrode mixture of the present invention is used, this can be effectively suppressed. That is, when the formed negative electrode contains lithium and zinc, the effect of the present invention is more remarkably exhibited. From this, it is also one of the preferred embodiments of the present invention that the negative electrode contains lithium and / or zinc in the second battery of the present invention.

As a positive electrode in the 2nd battery of this invention, the thing similar to the positive electrode used for the 1st battery of this invention can be used. In addition, as the electrolyte in the second battery of the present invention, the gel electrolyte of the first invention, the electrolyte other than the gel electrolyte of the first invention, that is, an organic solvent-based electrolyte, an aqueous electrolyte, Any of the water-organic solvent mixed electrolytes can be used.

As described above, it is also included in the present invention that the first and second aspects of the present invention are implemented in combination, and the effects of the present invention will be further remarkably exhibited by combining them. That is, a battery comprising a positive electrode, a negative electrode, and an electrolyte sandwiched between them, wherein the electrolyte is formed using the gel electrolyte of the present invention as an essential component, and the negative electrode is a negative electrode of the present invention. A battery formed using a mixture as an essential component is also one of the preferred embodiments of the present invention.

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

When the battery of the present invention is a storage battery, the charge / discharge rate of the storage battery is preferably 0.01 C or more and 100 C or less. More preferably, it is 0.05C or more and 80C or less, More preferably, it is 0.1C or more and 60C or less, Especially preferably, it is 0.1C or more and 30C or less. It is preferable that the storage battery can be used in both a cold region and a tropical region on the earth, and it is preferable that the storage battery can be used at a temperature of −50 ° C. to 100 ° C. For example, in the case of a nickel zinc battery, the capacity of the zinc negative electrode may be larger, smaller, or the same as the capacity of the nickel positive electrode, and either overcharge or overdischarge may occur. When using this storage battery for in-vehicle use, it is preferable to set the charging depth and / or the discharging depth shallow. As a result, the life of the storage battery can be extended and the generation of oxygen due to side reactions can be greatly suppressed. In a storage battery using a zinc electrode, it is preferable that oxygen generated in the system is consumed by (i) a bond with zinc of the negative electrode or (ii) a reaction at a third electrode different from the positive electrode / negative electrode. However, by selecting charging / discharging conditions and fundamentally suppressing oxygen generation, it is possible to easily achieve a long life and sealing of the storage battery. The nickel electrode may be a nickel electrode used for a nickel cadmium battery or a nickel metal hydride battery. By adding carbon, a lanthanoid compound, or the like to the nickel electrode, it is possible to increase the oxygen generation overvoltage and suppress oxygen generation as much as possible. In addition, the polyvalent ions and / or inorganic compounds and / or electrolytes contained in the gel electrolyte can suppress oxygen generation as much as possible. Additives contained in the electrolytic solution and the gel electrolyte can also improve the performance of the nickel electrode. In addition, the polyvalent ions and / or inorganic compounds and / or electrolytes contained in the gel electrolyte suppress oxygen generation as much as possible, or the gel electrolyte has a flexible skeleton structure as compared with conventional gel electrolytes. The gas diffuses at a high speed, and it can be expected that the generated oxygen can be quickly transported to the counter electrode or the third electrode.

The gel electrolyte of the present invention has the above-described configuration, and a battery formed using such a gel electrolyte can be used to change the shape of the electrode active material, such as shape change or dendrite, dissolution, corrosion, passive formation, charging. The gel electrolyte can exhibit high cycle characteristics, rate characteristics, and coulombic efficiency while maintaining high ionic conductivity while suppressing self-discharge during storage in a state or in a charged state. Accordingly, the gel electrolyte of the present invention can be suitably used for forming a battery electrolyte having excellent battery performance. Further, the negative electrode mixture of the present invention has the above-described configuration, and a battery formed using such a negative electrode mixture can also be used to change the shape of the electrode active material such as shape change and dendrite, to form passive state, and to charge. Suppresses self-discharge during storage in a state of charge or in a charged state, and the negative electrode mixture exhibits high cycle characteristics, rate characteristics, and coulomb efficiency while maintaining high ionic conductivity and electrical conductivity. be able to. From this, the negative electrode mixture of the present invention can be suitably used for forming a negative electrode of a battery excellent in battery performance.

FIG. 1 is a graph showing the results of the charge / discharge test of Example 3, showing a charge curve and a discharge curve at the seventh cycle. FIG. 2 is a graph showing the results of the charge / discharge test of Example 4, showing a charge curve and a discharge curve at the 20th cycle. FIG. 3 is a graph showing the results of the charge / discharge test of Example 5, showing a charge curve and a discharge curve at the 20th cycle. FIG. 4 is a graph showing the results of the charge / discharge test of Example 6, showing the discharge curves for the first cycle, the fifth cycle, the 30th cycle, and the 60th cycle. FIG. 5 is a graph showing the results of the charge / discharge test of Example 7, showing the discharge curves of the first cycle, the fifth cycle, the 30th cycle, and the 60th cycle.

The present invention will be described in more detail with reference to the following examples. However, the present invention is not limited to these examples.

In the following examples, various measurements were performed by the following methods.
<Weight average molecular weight>
It measured with the following apparatuses and measurement conditions.
Pump: L-7110 (manufactured by Hitachi, Ltd.)
Detector: UV 214 nm (Nihon Waters Co., Ltd., Model 481 type or Hitachi Ltd. L-7400)
Calibration curve: Sodium polyacrylate standard sample (manufactured by Sowa Kagaku Co., Ltd.)
Developing solvent: Pure water was added to 34.5 g of disodium hydrogen phosphate dodecahydrate and 46.2 g of sodium dihydrogen phosphate dihydrate to make a total amount of 5,000 g, and then with a 0.45 micron membrane filter. Filtered aqueous solution.
Column: GF-7MHQ (made by Showa Denko KK) or TSK-GEL G3000PWXL (made by Tosoh Corporation)
Eluent flow rate: 0.5 mL / min Column temperature: 35 ° C
<Average particle size>
The average particle size other than the average particle size of the zinc oxides of Examples 3 to 23 was measured and observed for 200 representative particles using an S-3500 scanning electron microscope (SEM) manufactured by Hitachi High-Technologies Corporation. The average value was calculated.
<Average particle diameter, mode diameter, median diameter>
The average particle diameter, mode diameter, and median diameter of the zinc oxides of Examples 3 to 23 were measured using a laser analysis / scattering particle size distribution measuring apparatus LA-950V2 Wet manufactured by HORIBA, and the particles were added to ion-exchanged water. The measured values after scattering and ultrasonic irradiation for 5 minutes are described.
<True density>
The measurement was performed using Accupic II-1340 manufactured by Shimadzu Corporation.
<Specific surface area>
It measured using the fully automatic BET specific surface area measuring apparatus by a mountec company.
<Amount of dissolved oxygen>
Measurement was performed using an oxygen meter (UC-12-SOL type / electrode used: UC-203 type) manufactured by Central Science Co., Ltd.

Example 1
Hydrotalcite [Mg _0.8 Al _0.2 (OH) ₂ ] (CO ₃ ) was added to a 4 mol / L potassium hydroxide aqueous solution (dissolved oxygen amount 5.2 mg / L) (10 mL) in which zinc oxide was dissolved until saturation. ^2- ) By adding _0.1 · mH ₂ O (1.5 g) and sodium polyacrylate (weight average molecular weight 6.5 million) (0.8 g) and stirring for 3 days, the hydrotalcite crosslinked acrylate gel was Prepared.
Zinc oxide (average particle size: 20 nm) 10.5 g, acetylene black (AB) 0.36 g, tin oxide (average particle size: about 50 μm) 0.87 g are put in a bottle, using a zirconia ball for 12 hours by a ball mill. Crushed. The obtained solid was sieved to make the average particle size 25 μm or less. 1.29 g of this solid, 2.17 g of a 12% polyvinylidene fluoride / N-methylpyrrolidone solution, and 1.2 g of N-methylpyrrolidone were added to a glass vial, and the mixture was stirred overnight with a stirrer using a stirrer bar. The obtained slurry was coated on a copper foil using an automatic coating apparatus, dried at 80 ° C. for 12 hours, and then dried in vacuum (room temperature) for 6 hours. The copper foil coated with the zinc mixture was pressed at a press pressure of 1 t, and the film thickness of the zinc mixture was 10 μm. This was punched with a punching machine to obtain a zinc mixture electrode, and a working electrode having an apparent area of 0.48 cm ² (zinc mixture weight: 11.8 mg). The counter electrode is a zinc plate, the reference electrode is zinc wire, and the electrolyte is a 4 mol / L aqueous potassium hydroxide solution in which zinc oxide is saturated until saturated. A site cross-linked acrylic acid gel (thickness: 5 mm) was set, and a charge / discharge test was conducted at a current value of 1.52 mA using a triode cell (charge / discharge time: 1 hour / -0.1 V each and 0.1. Cut off at 4V). After repeating charging and discharging 100 times, the cell was disassembled and the zinc electrode was observed. It was visually confirmed that the change in the shape of the active material of the zinc electrode mixture and the growth of dendrite were suppressed.

(Comparative Example 1)
Zinc oxide (average particle size: 20 nm) 10.5 g, acetylene black (AB) 0.36 g, tin oxide (average particle size: about 50 μm) 0.87 g are put in a bottle, using a zirconia ball for 12 hours by a ball mill. Crushed. The obtained solid was sieved to make the average particle size 25 μm or less. 1.29 g of this solid, 2.17 g of a 12% polyvinylidene fluoride / N-methylpyrrolidone solution, and 1.2 g of N-methylpyrrolidone were added to a glass vial, and the mixture was stirred overnight with a stirrer using a stirrer bar. The obtained slurry was coated on a copper foil using an automatic coating apparatus, dried at 80 ° C. for 12 hours, and then dried in vacuum (room temperature) for 6 hours. The copper foil coated with the zinc mixture was pressed at a press pressure of 1 t, and the film thickness of the zinc mixture was 10 μm. This was punched with a punching machine to obtain a zinc mixture electrode, and a working electrode having an apparent area of 0.48 cm ² (zinc mixture weight: 12.0 mg). A zinc electrode is used for the counter electrode, a zinc wire is used for the reference electrode, and a 4 mol / L potassium hydroxide aqueous solution (dissolved oxygen amount 5.2 mg / L) in which zinc oxide is dissolved is used for the electrolyte. Using the cell, a charge / discharge test was performed at a current value of 1.53 mA (charge / discharge time: 1 hour each / cut off at −0.1 V and 0.4 V). After repeating charge and discharge 100 times, the cell was disassembled and the zinc electrode was observed. As a result, it was visually confirmed that the zinc electrode mixture was swollen by the change in the shape of the active material and the growth of dendrite.

(Example 2)
Zinc oxide (average particle size: 20 nm) 10.5 g and acetylene black (AB) 1.5 g are placed in a bottle, and a quaternary ammonium salt (counter anion: hydroxyl group) is bonded to the polystyrene aromatic ring. A 12% polyvinylidene fluoride / N-methylpyrrolidone solution was added and pulverized for 12 hours by a ball mill. The obtained slurry was coated on a copper foil using an automatic coating apparatus, dried at 80 ° C. for 12 hours, and then dried in vacuum (room temperature) for 6 hours. The copper foil coated with the zinc mixture was pressed at a press pressure of 1 t, and the film thickness of the zinc mixture was 10 μm. This was punched with a punching machine to obtain a zinc mixture electrode, and a working electrode with an apparent area of 0.48 cm ² . A zinc electrode is used for the counter electrode, a zinc wire is used for the reference electrode, and a 4 mol / L potassium hydroxide aqueous solution (dissolved oxygen amount 5.2 mg / L) in which zinc oxide is dissolved is used for the electrolyte. A charge / discharge test was performed using the cell (charge / discharge time: 1 hour each / cut off at −0.1 V and 0.4 V). The initial coulomb efficiency was about 70%. Moreover, it was confirmed by SEM observation of the zinc electrode after repeating the charge / discharge test 60 times that the shape change of the active material was suppressed.

(Comparative Example 2)
Zinc oxide (average particle size: 20 nm) 10.5 g and acetylene black (AB) 1.5 g were put in a bottle, and a 12% polyvinylidene fluoride / N-methylpyrrolidone solution was added thereto and pulverized for 12 hours by a ball mill. The obtained slurry was coated on a copper foil using an automatic coating apparatus, dried at 80 ° C. for 12 hours, and then dried in vacuum (room temperature) for 6 hours. The copper foil coated with the zinc mixture was pressed at a press pressure of 1 t, and the film thickness of the zinc mixture was 10 μm. This was punched with a punching machine to obtain a zinc mixture electrode, and a working electrode with an apparent area of 0.48 cm ² . A zinc electrode is used for the counter electrode, a zinc wire is used for the reference electrode, and a 4 mol / L potassium hydroxide aqueous solution (dissolved oxygen amount 5.2 mg / L) in which zinc oxide is dissolved is used for the electrolyte. A charge / discharge test was performed using the cell (charge / discharge time: 1 hour each / cut off at −0.1 V and 0.4 V). The initial coulomb efficiency was about 30%. Moreover, it was confirmed by the SEM observation of the zinc electrode after repeating the charge / discharge test 60 times that the morphological change of the active material occurred.

(Example 3)
Hydroxyapatite Ca ₁₀ (PO ₄ ) ₆ (OH) ₂ (1.6 g) and polymoles of 6 mol / L potassium hydroxide aqueous solution (dissolved oxygen amount 4.8 mg / L) (10 mL) in which zinc oxide was dissolved until saturation Sodium acrylate (weight average molecular weight 1,500,000) (1.0 g) was added and stirred for 3 days to prepare a hydroxyapatite crosslinked acrylate gel.
Zinc oxide (average particle diameter: about 1.1 μm, mode diameter: about 820 nm, median diameter: about 760 nm, true density: about 5.98 g / cm ³ , specific surface area: about 4 m ² / g) 27.6 g, acetylene black (Average particle diameter: about 50 nm, specific surface area: about 40 m ² / g) 0.90 g, cerium (IV) oxide (manufactured by Wako Pure Chemical Industries, Ltd.) 2.4 g, ethanol (99.5%, Wako Pure Chemical Industries, Ltd.) 92.7 g) (manufactured by Co., Ltd.) and 92.7 g of water were added to the ball mill and mixed with the ball mill. Then, it dried at 100 degreeC under pressure reduction for 2 hours with the evaporator, and also dried at 110 degreeC under pressure reduction with the stationary type vacuum dryer overnight. The solid after drying was pulverized for 60 seconds at a rotation speed of 18000 rpm using a pulverizer (X-Treme MX1200XTM manufactured by WARING). 1.1 g of the obtained solid, 12 g of a 12% polyvinylidene fluoride / N-methylpyrrolidone solution, and 0.9 g of N-methylpyrrolidone were added to a glass vial, and the mixture was stirred overnight with a stirrer using a stirrer bar. The obtained slurry was coated on a copper foil using an automatic coating apparatus and dried at 80 ° C. for 12 hours. The copper foil coated with the zinc mixture was pressed at a press pressure of 3 t so that the film thickness of the zinc mixture was 10 μm or less. This was punched with a punching machine (diameter: 15.95 mm) to make a zinc mixture electrode, and used as a working electrode (zinc mixture weight: 5.4 mg) with an apparent area of 1.1 cm ² . The counter electrode is set with a nickel electrode (active material: cobalt-coated nickel hydroxide, capacity set to three times or more that of the zinc electrode), and the hydroxyapatite crosslinked acrylate gel (thickness: 1 mm) prepared above as the gel electrolyte. Then, a charge / discharge test was performed using a coin cell at a current value of 0.79 mA (charge / discharge time: 3 hours 20 minutes / 1.9 V and 1.2 V cut off). The charge / discharge cycle can be at least 20 times or more, and it was confirmed by SEM observation of the zinc electrode after the charge / discharge test that no change in the shape of the active material or formation of passive state occurred. A charge curve and a discharge curve at the seventh cycle are shown in FIG.

Example 4
Hydrotalcite [Mg _0.67 Al _0.33 (OH) ₂ ] (CO ₃ ) was added to an 8 mol / L potassium hydroxide aqueous solution (dissolved oxygen amount 3.5 mg / L) (10 mL) in which zinc oxide was dissolved until saturation. ^2- ) By adding _0.165 · mH ₂ O (1.5 g) and sodium polyacrylate (weight average molecular weight 1,500,000) (1.0 g) and stirring for 3 days, the hydrotalcite crosslinked acrylate gel was Prepared.
Zinc oxide (average particle diameter: about 1.1 μm, mode diameter: about 820 nm, median diameter: about 760 nm, true density: about 5.98 g / cm ³ , specific surface area: about 4 m ² / g) 27.6 g, acetylene black (Average particle diameter: about 50 nm, specific surface area: about 40 m ² / g) 0.90 g, cerium (IV) oxide (manufactured by Wako Pure Chemical Industries, Ltd.) 2.4 g, ethanol (99.5%, Wako Pure Chemical Industries, Ltd.) 92.7 g) (manufactured by Co., Ltd.) and 92.7 g of water were added to the ball mill and mixed with the ball mill. Then, it dried at 100 degreeC under pressure reduction for 2 hours with the evaporator, and also dried at 110 degreeC under pressure reduction with the stationary type vacuum dryer overnight. The solid after drying was pulverized for 60 seconds at a rotation speed of 18000 rpm using a pulverizer (X-Treme MX1200XTM manufactured by WARING). 1.1 g of the obtained solid, 12 g of a 12% polyvinylidene fluoride / N-methylpyrrolidone solution, and 0.9 g of N-methylpyrrolidone were added to a glass vial, and the mixture was stirred overnight with a stirrer using a stirrer bar. The obtained slurry was coated on a copper foil using an automatic coating apparatus and dried at 80 ° C. for 12 hours. The copper foil coated with the zinc mixture was pressed at a press pressure of 3 t so that the film thickness of the zinc mixture was 10 μm or less. This was punched out with a punching machine (diameter: 15.95 mm) to form a zinc mixture electrode, and the working electrode (zinc mixture weight: 2.3 mg) having an apparent area of 0.50 cm ² was used. Set the counter electrode with a nickel electrode (active material: cobalt-coated nickel hydroxide, capacity set to more than three times that of the zinc electrode), and the hydrotalcite crosslinked acrylate gel (thickness: 1 mm) prepared above as the gel electrolyte Then, a charge / discharge test was performed using a coin cell at a current value of 1.1 mA (charge / discharge time: cut off at 1 hour / 1.9 V and 1.2 V each). The charge / discharge cycle can be at least 50 times or more, and it was confirmed by SEM observation of the zinc electrode after the charge / discharge test that no change in the shape of the active material or formation of passive state occurred. A charge curve and a discharge curve at the 20th cycle are shown in FIG.

(Example 5)
Hydrotalcite [Mg _0.8 Al _0.2 (OH) ₂ ] (CO ₃ ) was added to 8 mol / L potassium hydroxide aqueous solution (dissolved oxygen amount 3.5 mg / L) (10 g) in which zinc oxide was dissolved until saturation. ^2- ) Hydrotalcite crosslinked acrylic acid gel is prepared by adding _0.1 · mH ₂ O (1.5 g) and sodium polyacrylate (weight average molecular weight 1,500,000) (1.0 g) and stirring for 3 days. did.
Zinc oxide (average particle diameter: about 1.1 μm, mode diameter: about 820 nm, median diameter: about 760 nm, true density: about 5.98 g / cm ³ , specific surface area: about 4 m ² / g) 27.6 g, acetylene black (Average particle diameter: about 50 nm, specific surface area: about 40 m ² / g) 0.9 g, zirconium oxide (IV) (manufactured by Wako Pure Chemical Industries, Ltd.) 2.4 g, ethanol (99.5%, Wako Pure Chemical Industries, Ltd.) 92.7 g) (manufactured by Co., Ltd.) and 92.7 g of water were added to the ball mill and mixed with the ball mill. Then, it dried at 100 degreeC under pressure reduction for 2 hours with the evaporator, and also dried at 110 degreeC under pressure reduction with the stationary type vacuum dryer overnight. The solid after drying was pulverized for 60 seconds at a rotation speed of 18000 rpm using a pulverizer (X-Treme MX1200XTM manufactured by WARING). 1.1 g of the obtained solid, 12 g of a 12% polyvinylidene fluoride / N-methylpyrrolidone solution, and 0.9 g of N-methylpyrrolidone were added to a glass vial, and the mixture was stirred overnight with a stirrer using a stirrer bar. The obtained slurry was coated on a copper foil using an automatic coating apparatus and dried at 80 ° C. for 12 hours. The copper foil coated with the zinc mixture was pressed at a press pressure of 3 t so that the film thickness of the zinc mixture was 10 μm or less. This was punched out with a punching machine (diameter: 15.95 mm) to form a zinc mixture electrode, which was used as a working electrode (zinc mixture weight: 2.0 mg) having an apparent area of 0.50 cm ² . The counter electrode is set with a nickel electrode (active material: cobalt-coated nickel hydroxide, the capacity is set to be at least three times that of the zinc electrode), and the hydrotalcite cross-linked acrylic acid gel (thickness: 1 mm) prepared above as the gel electrolyte. The charge / discharge test was conducted using a coin cell at a current value of 0.98 mA (charge / discharge time: cut off at 1 hour / 1.9 V and 1.2 V each), and the charge / discharge cycle can be at least 50 times, By SEM observation of the zinc electrode after the charge / discharge test, it was confirmed that no change in the shape of the active material or formation of passive state occurred. A charge curve and a discharge curve at the 20th cycle are shown in FIG.

(Example 6)
Zinc oxide (average particle diameter: about 1.1 μm, mode diameter: about 820 nm, median diameter: about 760 nm, true density: about 5.98 g / cm ³ , specific surface area: about 4 m ² / g) 27.6 g, acetylene black (Average particle diameter: about 50 nm, specific surface area: about 40 m ² / g) 0.90 g, cerium (IV) oxide (manufactured by Wako Pure Chemical Industries, Ltd.) 2.4 g, ethanol (99.5%, Wako Pure Chemical Industries, Ltd.) 92.7 g) (manufactured by Co., Ltd.) and 92.7 g of water were added to the ball mill and mixed with the ball mill. Then, it dried at 100 degreeC under pressure reduction for 2 hours with the evaporator, and also dried at 110 degreeC under pressure reduction with the stationary type vacuum dryer overnight. The solid after drying was pulverized for 60 seconds at a rotation speed of 18000 rpm using a pulverizer (X-Treme MX1200XTM manufactured by WARING). 1.0 g of the obtained solid, 0.080 g of a 50% styrene butadiene rubber (SBR) dispersion aqueous solution, and an aqueous solution containing 45% of a polymer (aquaric) obtained by copolymerizing sodium acrylate and a sodium sulfonate-containing monomer. 0.033 g and 0.43 g of water were added to a glass vial, and the mixture was stirred with a stirrer for 1 hour using a stirrer bar. The obtained slurry was coated on a copper foil using an automatic coating apparatus and dried at 80 ° C. for 12 hours. The copper foil coated with the zinc mixture was pressed at a press pressure of 3 t so that the film thickness of the zinc mixture was 10 μm or less. This was punched out with a punching machine (diameter: 15.95 mm) to form a zinc mixture electrode, and the working electrode (zinc mixture weight: 8.22 mg) having an apparent area of 0.48 cm ² was used. A zinc electrode is used for the counter electrode, a zinc wire is used for the reference electrode, and a 4 mol / L potassium hydroxide aqueous solution (dissolved oxygen amount 5.2 mg / L) in which zinc oxide is dissolved is used for the electrolyte. Using the cell, a charge / discharge test was performed at a current value of 4.63 mA (charge / discharge time: 1 hour each / cut off at −0.1 V and 0.4 V). It was found that stable charging / discharging at least 60 times is possible. FIG. 4 shows a discharge curve for the first cycle, a charge curve for the fifth cycle, a charge curve for the 30th cycle, and a charge curve for the 60th cycle.

(Example 7)
Zinc oxide (average particle diameter: about 1.1 μm, mode diameter: about 820 nm, median diameter: about 760 nm, true density: about 5.98 g / cm ³ , specific surface area: about 4 m ² / g) 27.6 g, acetylene black (Average particle diameter: about 50 nm, specific surface area: about 40 m ² / g) 0.90 g, cerium (IV) oxide (manufactured by Wako Pure Chemical Industries, Ltd.) 2.4 g, ethanol (99.5%, Wako Pure Chemical Industries, Ltd.) 92.7 g) (manufactured by Co., Ltd.) and 92.7 g of water were added to the ball mill and mixed with the ball mill. Then, it dried at 100 degreeC under pressure reduction for 2 hours with the evaporator, and also dried at 110 degreeC under pressure reduction with the stationary type vacuum dryer overnight. The solid after drying was pulverized for 60 seconds at a rotation speed of 18000 rpm using a pulverizer (X-Treme MX1200XTM manufactured by WARING). 2.1 g of the obtained solid, 0.48 g of a polyvinylidene fluoride-dispersed aqueous solution, 0.088 g of an aqueous solution containing 45% of a polymer (HW-1) obtained by copolymerizing sodium acrylate and a compound obtained by adding ethylene oxide to isoprenol. Then, 0.80 g of water was added to the glass vial and stirred with a stirrer for 1 hour using a stirrer bar. The obtained slurry was coated on a copper foil using an automatic coating apparatus and dried at 80 ° C. for 12 hours. The copper foil coated with the zinc mixture was pressed at a press pressure of 3 t so that the film thickness of the zinc mixture was 10 μm or less. This was punched out with a punching machine (diameter: 15.95 mm) to form a zinc mixture electrode, and the working electrode (zinc mixture weight: 7.71 mg) having an apparent area of 0.48 cm ² was used. A zinc electrode is used for the counter electrode, a zinc wire is used for the reference electrode, and a 4 mol / L potassium hydroxide aqueous solution (dissolved oxygen amount 5.2 mg / L) in which zinc oxide is dissolved is used for the electrolyte. Using the cell, a charge / discharge test was performed at a current value of 4.04 mA (charge / discharge time: 1 hour each / cut off at −0.1 V and 0.4 V). It was found that stable charging / discharging at least 60 times is possible. FIG. 5 shows a first cycle discharge curve, a fifth cycle charge curve, a thirty cycle charge curve, and a sixty cycle charge curve.

(Example 8)
Hydrotalcite [Mg _0.8 Al _{0.2 was} added to 8 mol / L potassium hydroxide + 20 g / L lithium hydroxide aqueous solution (dissolved oxygen amount 2.9 mg / L) (8.0 g) in which zinc oxide was dissolved until saturation. (OH) ₂ ] (CO ₃ ²⁻ ) _0.1 · mH ₂ O (1.6 g) and polyvinylpyrrolidone (1.0 g) were added and stirred for 1 day to prepare a hydrotalcite-crosslinked vinylpyrrolidone gel. .
The same zinc mixture electrode as in Example 4 was used, and the working electrode (zinc mixture weight: 2.3 mg) having an apparent area of 0.50 cm ² was used. The counter electrode is set with a nickel electrode (active material: cobalt-coated nickel hydroxide, the capacity is set to three or more times that of the zinc electrode) and the hydrotalcite-crosslinked polyvinylpyrrolidone gel (thickness: 1 mm) prepared above as the gel electrolyte. Then, a charge / discharge test was performed using a coin cell at a current value of 1.10 mA (charge / discharge time: 1 hour / 1.9 V and 1.2 V each cut off). The charge / discharge cycle can be at least 50 times or more, and it was confirmed by SEM observation of the zinc electrode after the charge / discharge test that no change in the shape of the active material or formation of passive state occurred. The discharge capacity at the 20th cycle was 550 mAh / g.

Example 9
Hydrotalcite [Mg _0.8 Al _{0.2 was} added to 8 mol / L potassium hydroxide + 20 g / L lithium hydroxide aqueous solution (dissolved oxygen amount 2.9 mg / L) (7.8 g) in which zinc oxide was dissolved until saturation. 45 (OH) ₂ ] (CO ₃ ²⁻ ) _0.1 · mH ₂ O (1.6 g) and 45% of a polymer (HW-1) copolymerized with sodium acrylate and a compound obtained by adding ethylene oxide to isoprenol. A hydrotalcite crosslinked HW-1 gel was prepared by adding an aqueous solution containing 0.5% (0.5 g) and stirring for 1 day.
The same zinc mixture electrode as in Example 4 was used, and the working electrode (zinc mixture weight: 2.8 mg) having an apparent area of 0.50 cm ² was used. The counter electrode is set with a nickel electrode (active material: cobalt-coated nickel hydroxide, capacity set to three times or more that of the zinc electrode), and the hydrotalcite cross-linked HW-1 gel (thickness: 1 mm) prepared as a gel electrolyte. Then, a charge / discharge test was performed using a coin cell at a current value of 1.34 mA (charge / discharge time: cut off at 1 hour / 1.9 V and 1.2 V each). The discharge capacity at the sixth cycle was 565 mAh / g.

(Example 10)
Hydrotalcite [Mg _0.8 Al _{0.2 was} added to 8 mol / L potassium hydroxide + 20 g / L lithium hydroxide aqueous solution (dissolved oxygen amount 2.9 mg / L) (7.5 g) in which zinc oxide was dissolved until saturation. (OH) ₂ ] (CO ₃ ²⁻ ) _0.1 · mH ₂ O (1.6 g) and an aqueous solution (2.5 g) containing 45% of a polymer obtained by copolymerizing sodium acrylate and sodium maleate were added. Hydrotalcite crosslinked polymer gel was prepared by stirring for 1 day.
The same zinc mixture electrode as in Example 4 was used, and the working electrode (zinc mixture weight: 2.1 mg) having an apparent area of 0.50 cm ² was used. The counter electrode is set with the nickel electrode (active material: cobalt-coated nickel hydroxide, the capacity is set to three times or more that of the zinc electrode), the hydrotalcite crosslinked polymer gel (thickness: 1 mm) prepared as the gel electrolyte, A charge / discharge test was performed using a coin cell at a current value of 1.03 mA (charge / discharge time: 1 hour / 1.9 V and 1.2 V cut off each). The discharge capacity at the fifth cycle was 533 mAh / g.

(Example 11)
Hydrotalcite [Mg _0.8 Al _{0.2 was} added to 8 mol / L potassium hydroxide + 20 g / L lithium hydroxide aqueous solution (dissolved oxygen amount 2.9 mg / L) (7.8 g) in which zinc oxide was dissolved until saturation. (OH) ₂ ] (CO ₃ ²⁻ ) _0.1 · mH ₂ O (1.6 g) and an aqueous solution (2.2 g) containing 45% sodium acrylate polymer having a phosphate group at the end were added for 1 day. By stirring, a hydrotalcite crosslinked polymer gel was prepared.
The same zinc mixture electrode as in Example 4 was used, and the working electrode having an apparent area of 0.50 cm ² (zinc mixture weight: 1.74 mg) was used. The counter electrode is set with the nickel electrode (active material: cobalt-coated nickel hydroxide, the capacity is set to three times or more that of the zinc electrode), the hydrotalcite crosslinked polymer gel (thickness: 1 mm) prepared as the gel electrolyte, A charge / discharge test was performed using a coin cell at a current value of 0.787 mA (charge / discharge time: cut off at 1 hour / 1.9 V and 1.2 V each). The discharge capacity at the 15th cycle was 496 mAh / g.

(Example 12)
Hydrotalcite [Mg _0.8 Al _{0.2 was} added to 8 mol / L potassium hydroxide + 20 g / L lithium hydroxide aqueous solution (dissolved oxygen amount 2.9 mg / L) (7.8 g) in which zinc oxide was dissolved until saturation. (OH) ₂ ] (CO ₃ ²⁻ ) _0.1 · mH ₂ O (1.6 g) and an aqueous solution containing 40% of a copolymer of sodium methacrylate and a compound obtained by adding ethylene oxide to methacrylic acid. (0.3 g) was added and stirred for 1 day to prepare a hydrotalcite crosslinked polymer gel.
The same zinc mixture electrode as in Example 4 was used, and the working electrode (zinc mixture weight: 1.67 mg) having an apparent area of 0.50 cm ² was used. The counter electrode is set with the nickel electrode (active material: cobalt-coated nickel hydroxide, the capacity is set to three times or more that of the zinc electrode), the hydrotalcite crosslinked polymer gel (thickness: 1 mm) prepared as the gel electrolyte, A charge / discharge test was performed using a coin cell at a current value of 0.793 mA (charge / discharge time: 1 hour / 1.9 V and 1.2 V cut off each). The discharge capacity at the 10th cycle was 413 mAh / g.

(Example 13)
Hydrotalcite [Mg _0.8 Al _{0.2 was} added to 8 mol / L potassium hydroxide + 20 g / L lithium hydroxide aqueous solution (dissolved oxygen amount 2.9 mg / L) (7.8 g) in which zinc oxide was dissolved until saturation. (OH) ₂ ] (CO ₃ ²⁻ ) _0.1 · mH ₂ O (1.6 g), sodium methacrylate and a compound obtained by adding ethylene oxide to methacrylic acid, and a part thereof as a diepoxy compound A hydrotalcite cross-linked polymer gel was prepared by adding an aqueous solution (0.3 g) containing 20% of the cross-linked polymer by stirring for 1 day.
The same zinc mixture electrode as in Example 4 was used, and the working electrode (zinc mixture weight: 1.94 mg) having an apparent area of 0.50 cm ² was used. The counter electrode is set with the nickel electrode (active material: cobalt-coated nickel hydroxide, the capacity is set to three times or more that of the zinc electrode), the hydrotalcite crosslinked polymer gel (thickness: 1 mm) prepared as the gel electrolyte, A charge / discharge test was performed using a coin cell at a current value of 0.922 mA (charge / discharge time: 1 hour each / cut off at 1.9 V and 1.2 V). The discharge capacity at the 20th cycle was 422 mAh / g.

(Example 14)
Hydrotalcite [Mg _0.8 Al _{0.2 was} added to 8 mol / L potassium hydroxide + 20 g / L lithium hydroxide aqueous solution (dissolved oxygen amount 2.9 mg / L) (7.8 g) in which zinc oxide was dissolved until saturation. (OH) ₂ ] (CO ₃ ²⁻ ) _0.1 · mH ₂ O (1.2 g), zirconium hydroxide hydrate (0.4 g), sodium polyacrylate (weight average molecular weight 1,500,000) (1. 0 g) was added and stirred for 1 day to prepare a hydrotalcite / zirconium hydroxide crosslinked acrylate gel.
The same zinc mixture electrode as in Example 4 was used, and the working electrode (zinc mixture weight: 2.64 mg) having an apparent area of 0.50 cm ² was used. The counter electrode is a nickel electrode (active material: cobalt-coated nickel hydroxide, capacity is set to three times or more that of the zinc electrode), hydrotalcite / zirconium hydroxide crosslinked acrylate gel prepared as a gel electrolyte (thickness: 1 mm) was set, and a charge / discharge test was performed using a coin cell at a current value of 1.26 mA (charge / discharge time: 1 hour / 1.9 V and 1.2 V cut off each). The discharge capacity at the 20th cycle was 517 mAh / g.

(Example 15)
Zirconium hydroxide hydrate (1.6 g) in 8 mol / L potassium hydroxide +20 g / L lithium hydroxide aqueous solution (dissolved oxygen amount 2.9 mg / L) (2.3 g) in which zinc oxide was dissolved until saturation Sodium acrylate (weight average molecular weight 1,500,000) (1.0 g) was added and stirred for 1 day to prepare a zirconium hydroxide crosslinked acrylate gel.
The same zinc mixture electrode as in Example 4 was used, and the working electrode (zinc mixture weight: 1.32 mg) having an apparent area of 0.50 cm ² was used. The counter electrode is a nickel electrode (active material: cobalt-coated nickel hydroxide, the capacity is set to three times or more that of the zinc electrode), and the zirconium hydroxide crosslinked acrylate gel (thickness: 1 mm) prepared above is used as the gel electrolyte. Then, a charge / discharge test was performed using a coin cell at a current value of 0.629 mA (charge / discharge time: cut off at 1 hour / 1.9 V and 1.2 V each). The discharge capacity at the 10th cycle was 424 mAh / g.

(Example 16)
Hydrotalcite [Mg _0.8 Al _{0.2 was} added to 8 mol / L potassium hydroxide + 20 g / L lithium hydroxide aqueous solution (dissolved oxygen amount 2.9 mg / L) (9.2 g) in which zinc oxide was dissolved until saturation. (OH) ₂ ] (CO ₃ ²⁻ ) _0.1 · mH ₂ O (1.2 g), ettringite (0.4 g), sodium polyacrylate (weight average molecular weight 1,500,000) (0.2 g) and 1 Hydrotalcite / etringite cross-linked acrylate gel was prepared by stirring for days.
The same zinc mixture electrode as in Example 4 was used, and the working electrode (zinc mixture weight: 1.49 mg) having an apparent area of 0.50 cm ² was used. The counter electrode is a nickel electrode (active material: cobalt-coated nickel hydroxide, the capacity is set to three times or more that of the zinc electrode), and the hydrotalcite / ettringite crosslinked acrylate gel prepared as the gel electrolyte (thickness: 1 mm) And a charge / discharge test was conducted using a coin cell at a current value of 0.709 mA (charge / discharge time: 1 hour / 1.9 V and 1.2 V cut off each). The discharge capacity at the 10th cycle was 561 mAh / g.

(Example 17)
8 mol / L potassium hydroxide dissolved in zinc oxide until saturated to 20 g / L lithium hydroxide aqueous solution (dissolved oxygen amount 2.9 mg / L) (6.1 g) was added to ettringite (1.6 g), sodium polyacrylate ( An ettringite cross-linked acrylate gel was prepared by adding a weight average molecular weight of 1.5 million) (1.0 g) and stirring for 1 day.
The same zinc mixture electrode as in Example 4 was used, and the working electrode (zinc mixture weight: 1.03 mg) having an apparent area of 0.50 cm ² was used. The counter electrode is set with a nickel electrode (active material: cobalt-coated nickel hydroxide, the capacity is set to three or more times that of the zinc electrode), the ettringite cross-linked acrylate gel (thickness: 1 mm) prepared as a gel electrolyte, A charge / discharge test was performed using a coin cell at a current value of 0.487 mA (charge / discharge time: cut off at 1 hour / 1.9 V and 1.2 V each). The discharge capacity at the 20th cycle was 495 mAh / g.

(Example 18)
Hydrotalcite [Mg _0.67 Al _0.33] was dissolved in 8 mol / L potassium hydroxide + 20 g / L lithium hydroxide aqueous solution (dissolved oxygen amount 2.9 mg / L) (7.8 g) in which zinc oxide was dissolved until saturation. (OH) ₂ ] (CO ₃ ²⁻ ) _0.165 · mH ₂ O (1.6 g) was added and stirred for 1 day to prepare a hydrotalcite crosslinked gel.
The same zinc mixture electrode as in Example 4 was used, and the working electrode (zinc mixture weight: 2.56 mg) having an apparent area of 0.50 cm ² was used. The counter electrode is set with a nickel electrode (active material: cobalt-coated nickel hydroxide, capacity set to 3 times or more that of the zinc electrode), and the hydrotalcite crosslinked gel (thickness: 1 mm) prepared above as the gel electrolyte. Was used to conduct a charge / discharge test at a current value of 1.24 mA (charge / discharge time: cut off at 1 hour / 1.9 V and 1.2 V each). The discharge capacity at the third cycle was 513 mAh / g.

(Example 19)
Ettlingite (1.6 g) is added to 8 mol / L potassium hydroxide + 20 g / L lithium hydroxide aqueous solution (dissolved oxygen amount 2.9 mg / L) (5.8 g) in which zinc oxide is saturated until saturated, and stirred for 1 day. Thus, an ettringite cross-linked gel was prepared.
The same zinc mixture electrode as in Example 4 was used, and the working electrode (zinc mixture weight: 1.02 mg) having an apparent area of 0.50 cm ² was used. The counter electrode is set with a nickel electrode (active material: cobalt-coated nickel hydroxide, capacity set to three times or more that of the zinc electrode), and the ettringite cross-linked gel (thickness: 1 mm) prepared above as a gel electrolyte, and a coin cell is used. Then, a charge / discharge test was performed at a current value of 0.484 mA (charge / discharge time: 1 hour / 1.9 V and 1.2 V each cut off). The discharge capacity at the 20th cycle was 495 mAh / g.

(Example 20)
Slowly add 8 mol / L potassium hydroxide + 20 g / L lithium hydroxide aqueous solution (dissolved oxygen amount 2.9 mg / L) (10 g) in which zinc oxide was dissolved in acrylic acid (1.1 g) until saturation, followed by hydro Talsite [Mg _0.8 Al _0.2 (OH) ₂ ] (CO ₃ ²⁻ ) _0.1 · mH ₂ O (0.5 g) was added and stirred. A 4% ammonium persulfate aqueous solution (0.4 g) was added thereto, and the above solution was applied to the same zinc mixture electrode as in Example 4 and polymerized under nitrogen to form hydrotalcite-crosslinked acrylic acid on the electrode. A gel film was formed.
Also, hydrotalcite [Mg _0.8 Al _{0 was} added to 8 mol / L potassium hydroxide + 20 g / L lithium hydroxide aqueous solution (dissolved oxygen amount 2.9 mg / L) (7.8 g) in which zinc oxide was dissolved until saturation. _.2 (OH) ₂ ] (CO ₃ ²⁻ ) _0.1 · mH ₂ O (1.6 g) and sodium acrylate polymer (weight average molecular weight: 1,500,000) (1.0 g) were added and stirred for 1 day. Thus, hydrotalcite crosslinked acrylate gel was prepared.
The same zinc mixture electrode as in Example 4 was used, and the electrode was used so as to have an apparent area of 0.50 cm ² working electrode (zinc mixture weight: 1.64 mg). Set the counter electrode with a nickel electrode (active material: cobalt-coated nickel hydroxide, capacity set to more than three times that of the zinc electrode), and the hydrotalcite crosslinked acrylate gel (thickness: 1 mm) prepared above as the gel electrolyte Then, a charge / discharge test was performed using a coin cell at a current value of 0.778 mA (charge / discharge time: cut off at 1 hour / 1.9 V and 1.2 V each). The discharge capacity at the 20th cycle was 590 mAh / g.

(Example 21)
8 mol / L potassium hydroxide + 20 g / L lithium hydroxide aqueous solution (dissolved oxygen amount 2) in which zinc oxide was dissolved in acrylic acid (1.1 g) in which N, N′-methylenebisacrylamide (10 mg) was dissolved. .9 mg / L) (10 g) was slowly added, followed by the addition of calcium nitrate (65 mg) and stirring. 4% ammonium persulfate aqueous solution (0.4 g) was added thereto, and the above solution was applied to the same zinc mixture electrode as in Example 4 and polymerized under nitrogen to crosslink the electrode with calcium and amide bonds. An acrylate gel film was formed.
Also, hydrotalcite [Mg _0.8 Al _{0 was} added to 8 mol / L potassium hydroxide + 20 g / L lithium hydroxide aqueous solution (dissolved oxygen amount 2.9 mg / L) (7.8 g) in which zinc oxide was dissolved until saturation. _.2 (OH) ₂ ] (CO ₃ ²⁻ ) _0.1 · mH ₂ O (1.6 g) and sodium acrylate polymer (weight average molecular weight: 1,500,000) (1.0 g) were added and stirred for 1 day. Thus, hydrotalcite crosslinked acrylate gel was prepared.
The same zinc mixture electrode as in Example 4 was used, and the electrode was used so that the apparent electrode had a working area of 0.50 cm ² (zinc mixture weight: 1.90 mg). Set the counter electrode with a nickel electrode (active material: cobalt-coated nickel hydroxide, capacity set to more than three times that of the zinc electrode), and the hydrotalcite crosslinked acrylate gel (thickness: 1 mm) prepared above as the gel electrolyte Then, a charge / discharge test was performed using a coin cell at a current value of 0.903 mA (charge / discharge time: cut off at 1 hour / 1.9 V and 1.2 V each). The discharge capacity at the 10th cycle was 505 mAh / g.

(Example 22)
Hydrotalcite [Mg _0.8 Al _{0.2 was} added to 8 mol / L potassium hydroxide + 20 g / L lithium hydroxide aqueous solution (dissolved oxygen amount 2.9 mg / L) (8.1 g) in which zinc oxide was dissolved until saturation. (OH) ₂ ] (CO ₃ ²⁻ ) _0.1 · mH ₂ O (1.6 g), sodium polyacrylate (weight average molecular weight 1,500,000) (0.2 g), and propylene carbonate (0.2 g) were added. Hydrotalcite crosslinked acrylate gel was prepared by stirring for 1 day.
The same zinc mixture electrode as in Example 4 was used, and the working electrode (zinc mixture weight: 1.65 mg) having an apparent area of 0.50 cm ² was used. The counter electrode the nickel electrode (active material: cobalt coating nickel hydroxide, capacity set to more than three times the zinc electrode), hydrotalcite site cross-linking acrylate gel as a gel electrolyte prepared above (thickness: 1 mm) And a charge / discharge test was performed using a coin cell at a current value of 0.784 mA (charge / discharge time: 1 hour / 1.9 V and 1.2 V cut off each). The discharge capacity at the second cycle was 180 mAh / g.

(Comparative Example 3)
To acrylic acid (1.1 g) in which N, N′-methylenebisacrylamide (10 mg) was dissolved, 8 mol / L potassium hydroxide (10 g) in which zinc oxide was further dissolved until saturation was slowly added. An aqueous solution of ammonium persulfate (0.4 g) was added and polymerized under nitrogen to form an acrylate gel electrolyte crosslinked with amide bonds.
The same zinc mixture electrode as in Example 4 was used, and the working electrode (zinc mixture weight: 1.88 mg) having an apparent area of 0.50 cm ² was used. The counter electrode is a nickel electrode (active material: cobalt-coated nickel hydroxide, the capacity is set to be more than three times that of the zinc electrode), and an acrylate gel cross-linked with the amide bond prepared above (thickness: 1 mm) as the gel electrolyte. It was set and a charge / discharge test was performed using a coin cell at a current value of 0.891 mA (charge / discharge time: 1 hour / 1.9 V and 1.2 V cut off), but charge / discharge could not be performed at all. There wasn't.

Batteries constructed using the gel electrolyte of the present invention or the negative electrode mixture of the present invention can suppress the growth of dendrite even when charging and discharging are repeated by using these gel electrolyte and negative electrode mixture. Was confirmed.
In addition, the battery constituted using the gel electrolyte of the present invention or the negative electrode mixture of the present invention does not undergo any change in the shape of the active material or formation of passive state even after repeated charge and discharge, and is stable repeatedly. It was confirmed that the charge and discharge were possible and the cycle characteristics, rate characteristics, and coulomb efficiency were excellent.
In the above examples, the gel electrolyte and the negative electrode mixture are formed using a specific polymer or the like, but by using the gel electrolyte or the negative electrode mixture of the present invention, such a gel electrolyte or negative electrode mixture is used. A storage battery composed of a mixture is excellent in battery performance such as cycle characteristics, rate characteristics, coulomb efficiency, etc., when the gel electrolyte or negative electrode mixture of the present invention is used. is there. Therefore, it can be said from the results of the above-described embodiments that the present invention can be applied in the entire technical scope of the present invention and in various forms disclosed in this specification, and can exhibit advantageous effects.

Claims (13)

A gel electrolyte used in a secondary battery,
The gel electrolyte includes a polymer and has a crosslinked structure of at least an inorganic compound,
The dissolved oxygen concentration value (mg / L) (at 25 ° C.) measured in a state in which the zinc-containing compound was dissolved in the aqueous electrolyte solution,
α = −0.26375 × β + 8.11
(Β represents the hydroxide ion concentration <mol / L> in the aqueous electrolyte used)
A gel electrolyte for a secondary battery comprising an aqueous electrolyte selected from the group consisting of potassium hydroxide, sodium hydroxide and lithium hydroxide, which is not more than the α value calculated by the formula: The inorganic compound includes alkali metal, alkaline earth metal, Sc, Y, lanthanoid, Ti, Zr, Hf, V, Nb, Ta, Cr, Mo, W, Mn, Re, Fe, Ru, Co, Rh, Ir , Ni, Pd, Pt, Cu, Ag, Au, Zn, Cd, B, Al, Ga, In, Tl, Si, Ge, Sn, Pb, P, As, Sb, Bi, S, Se, Te, F Oxides containing at least one element selected from the group consisting of, Cl, Br, and I; complex oxides; layered double hydroxides; hydroxides; clay compounds; solid solutions; zeolites; halides; Compound; bicarbonate compound; nitric acid compound; sulfuric acid compound; sulfonic acid compound; phosphoric acid compound; phosphorous compound; hypophosphorous acid compound, boric acid compound; silicic acid compound; Things, and the gel electrolyte for a secondary battery according to claim 1, characterized in that either salt. The gel electrolyte for a secondary battery according to claim 1 or 2 , wherein the inorganic compound is any one of a layered double hydroxide; a hydroxide; a sulfuric acid compound; and a phosphoric acid compound. The inorganic compound has the following formula:
[M ¹ _1-x M ² _x (OH) ₂ ] (A ⁿ⁻ ) _{x / n} · mH ₂ O
^{(M 1 = Mg, Fe,} Zn, Ca, Li, Ni, Co, Cu; M 2 = Al, Fe, Mn; A n- = CO 3 2- or OH ^-, m is 0 or a positive number, 0 The gel electrolyte for a secondary battery according to any one of claims 1 to 3 , wherein the gel electrolyte is a hydrotalcite represented by .20≤x≤0.40). A secondary battery composed of a positive electrode, a negative electrode, and an electrolyte sandwiched between them,
The negative electrode includes a zinc-containing compound,
The secondary battery is characterized in that the electrolyte is formed by using the gel electrolyte for a secondary battery according to any one of claims 1 to 4 . The secondary battery to claim 5, characterized in that the gel electrolyte for a secondary battery according to any one of the positive electrode and the claims 1-4 in the electrolyte of all sandwiched between the negative electrode was used The secondary battery as described. In the secondary battery, the gel electrolyte for the secondary battery according to any one of claims 1 to 4 is used for a part of the electrolyte sandwiched between the positive electrode and the negative electrode, and the electrolyte in contact with the negative electrode is the gel for the secondary battery. The secondary battery according to claim 6 , wherein the secondary battery is formed by using an electrolyte as an essential component. A negative electrode mixture used in a battery,
The negative electrode mixture includes a negative electrode active material and a polymer,
The polymer is an aromatic group-containing polymer; an ether group-containing polymer; a hydroxyl group-containing polymer; an amide bond-containing polymer; an imide bond-containing polymer; a halogen-containing polymer; a polymer bonded by ring opening of an epoxy group; Polymer; Quaternary ammonium salt or quaternary phosphonium salt-containing polymer; Ion exchange polymer; Natural rubber; Artificial rubber; Sugar; Amino group-containing polymer; Carbamate group site-containing polymer; Carbamide group site-containing polymer; Epoxy group site Any of the containing polymers,
The negative electrode mixture includes B, Ba, Bi, Br, Ca, Cd, Ce, Cl, F, Ga, Hg, In, La, Mn, N, Nb, Nd, P, Pb, Sc, Sn, Sb, A negative electrode mixture comprising, as a conductive additive, a compound having a constituent element selected from the group consisting of Sr, Ti, Tl, Y, and Zr. An electrode formed using the negative electrode mixture according to claim 8 . A battery composed of a positive electrode, a negative electrode, and an electrolyte sandwiched between them,
The battery, wherein the negative electrode is formed by using the negative electrode mixture according to claim 8 as an essential component. A secondary battery composed of a positive electrode, a negative electrode, and an electrolyte sandwiched between them,
The electrolyte is formed with a gel electrolyte having a crosslinked structure of at least an inorganic compound as an essential component,
A secondary battery, wherein the negative electrode is formed using the negative electrode mixture according to claim 8 as an essential component. The battery according to claim 10 , wherein the negative electrode contains lithium or zinc. The secondary battery according to claim 5 , wherein the negative electrode contains lithium or zinc.

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