JP5708301B2 - Secondary battery negative electrode, secondary battery, negative electrode slurry composition, and method for producing secondary battery negative electrode - Google Patents

Description

  The present invention relates to, for example, a negative electrode for a secondary battery provided in a secondary battery such as a lithium ion secondary battery, a slurry composition for negative electrode for producing the negative electrode for secondary battery, and a method for producing the negative electrode for secondary battery. The present invention also relates to a secondary battery including the secondary battery negative electrode.

  In order to improve the performance of secondary batteries such as lithium ion secondary batteries, improvement of electrodes, electrolytic solutions and other battery members has been studied. Of these, the electrode is usually a liquid composition in which a polymer serving as a binder (binder) is dispersed or dissolved in a solvent such as water or an organic solvent, an electrode active material, and optionally conductive carbon or the like. The conductive agent is mixed to obtain a slurry composition, and this slurry composition is applied to a current collector and dried. Regarding the electrode, in addition to studying the electrode active material and the current collector itself, studies have been made on binders and various additives for binding the electrode active material and the like to the current collector (for example, Patent Document 1). To 6).

  For example, Patent Document 1 and Patent Document 2 describe a slurry for a negative electrode of a non-aqueous secondary battery including a binder composed of a carbon material active material, a water-dispersed emulsion resin, and a water-soluble polymer. As the water-soluble polymer, polyvinyl alcohol, carboxymethyl cellulose, sodium polyacrylate, and the like are described. According to this, it is described that the coating film strength and the coating film density of the battery are improved.

  Patent Document 3 includes 0.02 to 13% by weight of a fluorine-containing unsaturated monomer, 10 to 38% by weight of an aliphatic conjugated diene monomer, and 0.1 to 10% by weight of an ethylenically unsaturated carboxylic acid monomer. And a binder for a secondary battery electrode comprising a copolymer latex obtained by emulsion polymerization of a monomer composed of 49 to 88.88% by weight of other monomers copolymerizable therewith. ing. According to this, it is described that it is excellent in blending stability, blocking resistance, suitability for dust removal, and binding power.

  Furthermore, Patent Document 4 describes a secondary battery electrode binder made of a polymer having a monomer unit derived from a fluorine atom-containing monomer such as alkyl fluoride (meth) acrylate. And it describes that a cellulose polymer, polyacrylate, etc. can be added in order to improve applicability | paintability or to improve charging / discharging characteristics. According to this, it is described that an electrode having a good binding property with the active material can be obtained.

  Patent Document 5 describes that a polymer having a group including various nitrogen groups such as phosphorus and a chalcogen element is used as a binder of a secondary battery electrode.

JP 2003-308441 A JP 2003-217573 A JP 2010-146870 A JP 2002-42819 A International Publication No. 2006/101182

  In the secondary battery, the particles of the electrode active material contained in the negative electrode may expand and contract with charge / discharge. When such expansion and contraction are repeated, the negative electrode gradually expands and the secondary battery may be deformed. Therefore, development of a technique capable of suppressing the swelling of the negative electrode as described above is desired.

Further, some of the conventional secondary batteries have a reduced capacity when stored in a high temperature environment of 60 ° C. or a low temperature environment of −25 ° C., for example. Therefore, it is desired to develop a technology that can suppress a decrease in the capacity of the secondary battery even when the secondary battery is stored in such an environment.
Furthermore, in the conventional secondary battery, it is desired to develop a technique for reducing a decrease in capacity due to repeated charge and discharge in a high temperature environment. Further, in order to improve the above performance, it is desired to improve the adhesion between the current collector and the electrode active material layer formed on the current collector in the production of an electrode for a secondary battery, and It is also desirable to efficiently produce a homogeneous product.

  Therefore, the object of the present invention is to suppress the swelling of the negative electrode associated with charging / discharging, the capacity is difficult to decrease when stored in either a high temperature environment or a low temperature environment, and the capacity is decreased due to repeated charging / discharging in a high temperature environment. A negative electrode for a secondary battery capable of realizing a small number of secondary batteries, a slurry composition for a negative electrode capable of efficiently producing the negative electrode for a secondary battery, a method for producing a negative electrode for a secondary battery, and the negative electrode for a secondary battery It is providing the secondary battery provided with.

As a result of studying to solve the above problems, the present inventor, as a polymer added to the electrode active material layer of the secondary battery negative electrode in addition to the binder, a sulfonic acid group-containing monomer unit, and a phosphate group The present inventors have found that the above-mentioned problems can be solved by adding a water-soluble polymer containing a monomer unit in a specific ratio.
That is, according to the present invention, the following [1] to [7] are provided.

[1] A negative electrode for a secondary battery comprising a negative electrode active material, a binder and a water-soluble polymer,
A secondary battery in which the water-soluble polymer is a copolymer containing 0.5% by weight to 20% by weight of a sulfonic acid group-containing monomer unit and 5-30% by weight of a phosphate group-containing monomer unit. Negative electrode.
[2] The negative electrode for a secondary battery according to [1], wherein the phosphate group-containing monomer is a phosphate group-containing (meth) acrylic ester.
[3] The sulfonic acid group-containing monomer is a monomer containing an amide group, a sulfonic acid group, and a polymerizable group, or has a sulfonic acid group and a polymerizable group, and has a functional group in addition thereto. The negative electrode for a secondary battery according to [1] or [2], which is a monomer that is not present.
[4] The negative electrode for a secondary battery according to any one of [1] to [3], wherein the 1% aqueous solution viscosity of the water-soluble polymer is 0.1 to 20000 mPa · s.
[5] A secondary battery comprising a positive electrode, a negative electrode, an electrolytic solution, and a separator,
The secondary battery whose said negative electrode is a negative electrode for secondary batteries as described in any one of [1]-[4].
[6] A negative electrode slurry composition comprising a negative electrode active material, a binder, a water-soluble polymer and water,
Slurry for negative electrode, wherein the water-soluble polymer is a copolymer containing 0.5% to 20% by weight of sulfonic acid group-containing monomer units and 5 to 30% by weight of phosphoric acid group-containing monomer units. Composition.
[7] A method for producing a negative electrode for a secondary battery, comprising applying the slurry composition for a negative electrode according to [6] to a surface of a current collector and drying.

According to the negative electrode for a secondary battery of the present invention, swelling of the negative electrode accompanying charge / discharge can be suppressed, the capacity can be made difficult to decrease when stored in either a high temperature environment or a low temperature environment, and in a high temperature environment. Thus, a secondary battery can be realized in which the capacity is less reduced by repeated charging and discharging. Furthermore, the negative electrode for a secondary battery of the present invention can be easily manufactured with a small amount of pinholes and high adhesion between the current collector and the negative electrode active material layer. It is a negative electrode which can be manufactured.
The secondary battery of the present invention can suppress the swelling of the negative electrode accompanying charging / discharging, hardly reduces the capacity when stored in either a high temperature environment or a low temperature environment, and the capacity decreases due to repeated charging / discharging in a high temperature environment. Less is.
If the slurry composition for negative electrodes of this invention is used, the negative electrode for secondary batteries of this invention can be manufactured. In particular, since the slurry has high stability, there is little occurrence of uneven distribution of particles dispersed in the slurry, and as a result, a battery with high performance can be easily manufactured.
According to the method for producing a negative electrode for a secondary battery of the present invention, the negative electrode for a secondary battery of the present invention can be produced.

  Hereinafter, the present invention will be described in detail with reference to embodiments and examples, but the present invention is not limited to the following embodiments and examples, and the claims of the present invention and equivalents thereof. Any change can be made without departing from the scope described above. In the present specification, “(meth) acryl” means “acryl” or “methacryl”. Further, “positive electrode active material” means an electrode active material for positive electrode, and “negative electrode active material” means an electrode active material for negative electrode. Furthermore, the “positive electrode active material layer” means an electrode active material layer provided on the positive electrode, and the “negative electrode active material layer” means an electrode active material layer provided on the negative electrode.

[1. Negative electrode for secondary battery]
The negative electrode for a secondary battery of the present invention (hereinafter appropriately referred to as “the negative electrode of the present invention”) includes a negative electrode active material, a binder, and a water-soluble polymer. Usually, the negative electrode of the present invention includes a current collector and a negative electrode active material layer formed on a surface of the current collector, and the electrode active material layer includes the negative electrode active material, a binder, and a water-soluble polymer. .

[1-1. Negative electrode active material]
The negative electrode active material is an electrode active material for a negative electrode, and is a material that transfers electrons in the negative electrode of the secondary battery.
For example, when the secondary battery of the present invention is a lithium ion secondary battery, a material that can occlude and release lithium is usually used as the negative electrode active material. Examples of the material that can occlude and release lithium include a metal-based active material, a carbon-based active material, and an active material that combines these materials.

  The metal-based active material is an active material containing a metal, and usually contains an element capable of inserting lithium (also referred to as dope) in the structure, and the theoretical electric capacity per weight when lithium is inserted is 500 mAh. An active material that is greater than / g. The upper limit of the theoretical electric capacity is not particularly limited, but may be, for example, 5000 mAh / g or less. As the metal-based active material, for example, lithium metal, a single metal that forms a lithium alloy and an alloy thereof, and oxides, sulfides, nitrides, silicides, carbides, phosphides, and the like thereof are used.

  Examples of the single metal forming the lithium alloy include single metals such as Ag, Al, Ba, Bi, Cu, Ga, Ge, In, Ni, P, Pb, Sb, Si, Sn, Sr, Zn, and Ti. Can be mentioned. Moreover, as a single metal alloy which forms a lithium alloy, the compound containing the said single metal is mentioned, for example. Among these, silicon (Si), tin (Sn), lead (Pb), and titanium (Ti) are preferable, and silicon, tin, and titanium are more preferable. Accordingly, a single metal of silicon (Si), tin (Sn), or titanium (Ti), an alloy containing these single metals, or a compound of these metals is preferable.

The metallic active material may further contain one or more nonmetallic elements. For example, SiC, SiO _x C _y (0 <x ≦ 3, 0 <y ≦ 5), Si ₃ N ₄ , Si ₂ N ₂ O, SiO _x (0 <x ≦ 2), SnO _x (0 <x ≦ 2), LiSiO, LiSnO and the like. Among these, SiO _x C _y capable of inserting and detaching lithium (also referred to as dedoping) at a low potential is preferable. For example, SiO _x C _y can be obtained by firing a polymer material containing silicon. Among SiO _x C _y , the range of 0.8 ≦ x ≦ 3 and 2 ≦ y ≦ 4 is preferably used in view of the balance between capacity and cycle characteristics.

  Lithium metal, elemental metal forming lithium alloy and oxides, sulfides, nitrides, silicides, carbides and phosphides of the alloys include oxides, sulfides, nitrides and silicides of lithium-insertable elements Products, carbides, phosphides and the like. Among these, an oxide is particularly preferable. For example, a lithium-containing metal composite oxide containing an oxide such as tin oxide, manganese oxide, titanium oxide, niobium oxide, and vanadium oxide and a metal element selected from the group consisting of Si, Sn, Pb, and Ti atoms is used. .

As the lithium-containing metal composite oxide, a lithium titanium composite oxide represented by Li _x Ti _y M _z O ₄ (0.7 ≦ x ≦ 1.5, 1.5 ≦ y ≦ 2.3, 0 ≦ z ≦ 1.6, and M represents an element selected from the group consisting of Na, K, Co, Al, Fe, Ti, Mg, Cr, Ga, Cu, Zn, and Nb.), Li _x Mn _y M A lithium manganese composite oxide represented by _z O ₄ (x, y, z and M are the same as defined in the lithium titanium composite oxide). Among these, Li _4/3 Ti _5/3 O ₄ , Li ₁ Ti ₂ O ₄ , Li _4/5 Ti _11/5 O ₄ , and Li _4/3 Mn _5/3 O ₄ are preferable.

  Among these, as the metal-based active material, an active material containing silicon is preferable. By using an active material containing silicon, the electric capacity of the secondary battery can be increased. In general, an active material containing silicon expands and contracts greatly (for example, about 5 times) with charge and discharge. However, in the negative electrode of the present invention, battery performance due to expansion and contraction of an active material containing silicon is increased. The decrease can be prevented by the water-soluble polymer according to the present invention.

Of the active materials containing silicon, SiC and SiO _x C _y are preferable, and SiO _x C _y is more preferable. In an active material containing a combination of these Si and C, when Li is inserted into and desorbed from Si (silicon) at a high potential, and Li is inserted into and desorbed from C (carbon) at a low potential Guessed. For this reason, since expansion and contraction are suppressed as compared with other metal-based active materials, the charge / discharge cycle characteristics of the secondary battery can be improved.

The carbon-based active material refers to an active material having carbon as a main skeleton into which lithium can be inserted, and examples thereof include a carbonaceous material and a graphite material.
The carbonaceous material is generally a carbon material with low graphitization (ie, low crystallinity) obtained by carbonizing a carbon precursor by heat treatment at 2000 ° C. or lower. In addition, although the minimum of the said heat processing is not specifically limited, For example, it is good also as 500 degreeC or more.

  Examples of the carbonaceous material include graphitizable carbon that easily changes the carbon structure depending on the heat treatment temperature, non-graphitic carbon having a structure close to an amorphous structure typified by glassy carbon, and the like.

  Examples of graphitizable carbon include carbon materials made from tar pitch obtained from petroleum or coal. Specific examples include coke, mesocarbon microbeads (MCMB), mesophase pitch carbon fibers, pyrolytic vapor grown carbon fibers, and the like. MCMB is carbon fine particles obtained by separating and extracting mesophase microspheres generated in the process of heating pitches at around 400 ° C. The mesophase pitch-based carbon fiber is a carbon fiber using as a raw material mesophase pitch obtained by growing and coalescing the mesophase microspheres. Pyrolytic vapor-grown carbon fibers are (1) a method of pyrolyzing acrylic polymer fibers, etc., (2) a method of spinning by spinning a pitch, or (3) using nanoparticles such as iron as a catalyst. Carbon fiber obtained by catalytic vapor deposition (catalytic CVD) method in which hydrocarbons are vapor-phase pyrolyzed.

  Examples of the non-graphitizable carbon include a phenol resin fired body, polyacrylonitrile-based carbon fiber, pseudo-isotropic carbon, furfuryl alcohol resin fired body (PFA), and hard carbon.

  The graphite material is a graphite material having high crystallinity close to that of graphite obtained by heat-treating graphitizable carbon at 2000 ° C. or higher. In addition, although the upper limit of the said heat processing temperature is not specifically limited, For example, it is good also as 5000 degrees C or less.

  Examples of the graphite material include natural graphite and artificial graphite. Examples of artificial graphite include artificial graphite mainly heat-treated at 2800 ° C. or higher, graphitized MCMB heat-treated at 2000 ° C. or higher, graphitized mesophase pitch-based carbon fiber heat-treated mesophase pitch-based carbon fiber at 2000 ° C. or higher, etc. Is mentioned.

  Among the carbon-based active materials, a carbonaceous material is preferable. By using the carbonaceous material, the resistance of the secondary battery can be reduced, and a secondary battery having excellent input / output characteristics can be manufactured.

  In addition, a negative electrode active material may be used individually by 1 type, and may be used combining two or more types by arbitrary ratios.

  As a preferable embodiment of the negative electrode active material, an active material obtained by combining a metal-based active material and a carbon-based active material can be given. In this case, in particular, a combination of SiOC as a metal-based active material and a graphite material as a carbon-based active material can be mentioned as a particularly preferable embodiment. In this case, the ratio between SiOC and the graphite material can be SiOC / graphite = 5/95 to 50/50 weight ratio. By combining such ratios, there is an advantage that the battery capacity can be increased and the cycle characteristics are not impaired because the expansion and contraction is relatively small.

  The negative electrode active material is preferably sized in the form of particles. When the shape of the particles is spherical, a higher density electrode can be formed during electrode molding.

  The volume average particle diameter of the particles of the negative electrode active material is appropriately selected in consideration of other constituent requirements of the secondary battery, and is usually 0.1 μm or more, preferably 1 μm or more, more preferably 5 μm or more, and usually 100 μm or less. , Preferably 50 μm or less, more preferably 20 μm or less.

  The 50% cumulative volume diameter of the particles of the negative electrode active material is usually 1 μm or more, preferably 5 μm or more, more preferably 10 μm or more, preferably from the viewpoint of improving battery characteristics such as initial efficiency, load characteristics, and cycle characteristics. 30 μm or less. The 50% cumulative volume diameter can be obtained as a particle diameter at which the cumulative volume calculated from the small diameter side in the measured particle size distribution is 50% by measuring the particle size distribution by a laser diffraction method.

The tap density of the negative electrode active material is not particularly limited, but 0.6 g / cm ³ or more is preferably used.

The specific surface area of the negative electrode active material is usually 2 m ² / g or more, preferably 3 m ² / g or more, more preferably 5 m ² / g or more, and usually 20 m ² / g or less, preferably from the viewpoint of improving the output density. It is 15 m ² / g or less, more preferably 10 m ² / g or less. In addition, the specific surface area of a negative electrode active material can be measured by BET method, for example.

[1-2. binder]
The binder is a component that binds the electrode active material to the surface of the current collector in the negative electrode. In the negative electrode of the present invention, the binder binds the negative electrode active material, thereby preventing the negative electrode active material from being detached from the negative electrode active material layer. Further, the binder usually binds particles other than the negative electrode active material contained in the negative electrode active material layer, and also plays a role of maintaining the strength of the negative electrode active material layer.

  As the binder, it is preferable to use a binder that is excellent in performance of holding the negative electrode active material and has high adhesion to the current collector. Usually, a polymer is used as the binder. In this case, the polymer may be a homopolymer or a copolymer. Among them, the polymer as the binder is preferably a polymer containing an aliphatic conjugated diene monomer unit. Since the aliphatic conjugated diene monomer unit is a low-rigidity and flexible repeating unit, by using a polymer containing the aliphatic conjugated diene monomer unit as a binder, the negative electrode active material layer, the current collector, Sufficient adhesion can be obtained.

The aliphatic conjugated diene monomer unit is a repeating unit obtained by polymerizing an aliphatic conjugated diene monomer. Examples of the aliphatic conjugated diene monomer include 1,3-butadiene, 2-methyl-1,3-butadiene, 2,3-dimethyl-1,3-butadiene, and 2-chloro-1,3-butadiene. Substituted linear conjugated pentadienes, substituted and side chain conjugated hexadienes, and the like. Of these, 1,3-butadiene is preferred.
In addition, one kind of aliphatic conjugated diene monomer may be used alone, or two or more kinds may be used in combination at any ratio. Therefore, the polymer as the binder may contain only one type of aliphatic conjugated diene monomer unit, or may contain two or more types in combination at any ratio.

  In 100 parts by weight of the polymer as the binder, the ratio of the aliphatic conjugated diene monomer unit is usually 20 parts by weight or more, preferably 30 parts by weight or more, and usually 70 parts by weight or less, preferably 60 parts by weight or less. More preferably, it is 55% by weight or less. By setting the ratio of the aliphatic conjugated diene monomer unit to the lower limit value or more of the above range, the flexibility of the negative electrode can be increased, and by setting the ratio to the upper limit value or less, the negative electrode active material layer and the current collector It is possible to obtain sufficient adhesion to the electrode and to improve the resistance of the electrode to electrolyte.

  The polymer as the binder preferably contains an aromatic vinyl monomer unit. The aromatic vinyl monomer unit is stable, and the negative electrode active material layer can be stabilized by reducing the solubility of the polymer containing the aromatic vinyl monomer unit in the electrolytic solution.

The aromatic vinyl monomer unit is a repeating unit obtained by polymerizing an aromatic vinyl monomer. Examples of aromatic vinyl monomers include styrene, α-methylstyrene, vinyl toluene, divinyl benzene and the like. Of these, styrene is preferred. Therefore, when combined with the fact that the polymer as the binder preferably contains an aliphatic conjugated diene monomer unit such as butadiene, the polymer as the binder is an aliphatic conjugated diene monomer unit and an aromatic vinyl. A polymer containing a monomer unit is preferred, and for example, a styrene / butadiene copolymer is preferred.
In addition, an aromatic vinyl-type monomer may be used individually by 1 type, and may be used combining two or more types by arbitrary ratios. Therefore, the polymer as a binder may contain only one type of aromatic vinyl monomer, or may contain two or more types in combination at any ratio.

  When an aromatic vinyl monomer is used, the polymer as a binder includes an unreacted aliphatic conjugated diene monomer and an unreacted aromatic vinyl monomer as residual monomers. There is. In that case, the amount of the unreacted aliphatic conjugated diene monomer contained in the polymer as the binder is preferably 50 ppm or less, more preferably 10 ppm or less, and the unreacted aromatic contained in the polymer as the binder. The amount of the vinyl monomer is preferably 1000 ppm or less, more preferably 200 ppm or less. When the amount of the aliphatic conjugated diene monomer contained in the polymer as a binder is kept within the above range, the negative electrode slurry composition according to the present invention is applied to the surface of the current collector and dried to produce a negative electrode. Furthermore, it is possible to prevent the surface of the negative electrode from being roughened by foaming or causing an environmental load due to odor. Moreover, when the amount of the aromatic vinyl monomer contained in the polymer as the binder is kept within the above range, it is possible to suppress the environmental load and the roughness of the negative electrode surface that occur according to the drying conditions, and further, the polymer as the binder. Electrolytic solution resistance can be improved.

  In 100 parts by weight of the polymer as the binder, the ratio of the aromatic vinyl monomer units is usually 30 parts by weight or more, preferably 35 parts by weight or more, and usually 79.5 parts by weight or less, preferably 69 parts by weight. It is as follows. By setting the ratio of the aromatic vinyl monomer unit to the lower limit value or more of the above range, the electrolytic solution resistance of the secondary battery negative electrode of the present invention can be improved, and by setting the ratio to the upper limit value or less. When the negative electrode slurry composition according to the present invention is applied to a current collector, sufficient adhesion between the negative electrode active material layer and the current collector can be obtained.

  The polymer as the binder preferably contains an ethylenically unsaturated carboxylic acid monomer unit. The ethylenically unsaturated carboxylic acid monomer unit includes a carboxyl group (—COOH group) that enhances the adsorptivity to the negative electrode active material and the current collector, and is a repeating unit having high strength. Desorption of the negative electrode active material can be stably prevented, and the strength of the negative electrode can be improved.

The ethylenically unsaturated carboxylic acid monomer unit is a repeating unit obtained by polymerizing an ethylenically unsaturated carboxylic acid monomer. Examples of the ethylenically unsaturated carboxylic acid monomer include monocarboxylic and dicarboxylic acids such as acrylic acid, methacrylic acid, crotonic acid, maleic acid, fumaric acid and itaconic acid, and anhydrides thereof. Especially, it is preferable to use the monomer chosen from the group which consists of acrylic acid, methacrylic acid, and itaconic acid individually or in combination from a stability viewpoint of the slurry composition for negative electrodes which concerns on this invention.
In addition, an ethylenically unsaturated carboxylic acid monomer may be used individually by 1 type, and may be used combining two or more types by arbitrary ratios. Therefore, the polymer as the binder may contain only one type of ethylenically unsaturated carboxylic acid monomer unit, or may contain two or more types in combination at any ratio.

  In 100 parts by weight of the polymer as the binder, the ratio of the ethylenically unsaturated carboxylic acid monomer units is usually 0.5 parts by weight or more, preferably 1 part by weight or more, more preferably 2 parts by weight or more. It is 10 parts by weight or less, preferably 8 parts by weight or less, more preferably 7 parts by weight or less. By setting the ratio of the ethylenically unsaturated carboxylic acid monomer unit to be equal to or higher than the lower limit of the above range, the stability of the slurry composition for negative electrode according to the present invention can be increased, and the lower limit is set to the upper limit. Thus, the viscosity of the negative electrode slurry according to the present invention can be prevented from becoming excessively high, and can be easily handled.

  The polymer as the binder may contain any repeating unit other than those described above as long as the effects of the present invention are not significantly impaired. Examples of the monomer corresponding to the arbitrary repeating unit include a vinyl cyanide monomer, an unsaturated carboxylic acid alkyl ester monomer, an unsaturated monomer containing a hydroxyalkyl group, and an unsaturated carboxylic acid. And acid amide monomers. In addition, these may be used individually by 1 type and may be used combining two or more types by arbitrary ratios.

  Examples of the vinyl cyanide monomer include acrylonitrile, methacrylonitrile, α-chloroacrylonitrile, α-ethylacrylonitrile and the like. Of these, acrylonitrile and methacrylonitrile are preferable. In addition, these may be used individually by 1 type and may be used combining two or more types by arbitrary ratios.

  Examples of unsaturated carboxylic acid alkyl ester monomers include methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, butyl acrylate, glycidyl methacrylate, dimethyl fumarate, diethyl fumarate, dimethyl maleate, diethyl maleate, and dimethyl itaco. Nate, monomethyl fumarate, monoethyl fumarate, 2-ethylhexyl acrylate and the like. Of these, methyl methacrylate is preferable. In addition, these may be used individually by 1 type and may be used combining two or more types by arbitrary ratios.

  Examples of the unsaturated monomer containing a hydroxyalkyl group include β-hydroxyethyl acrylate, β-hydroxyethyl methacrylate, hydroxypropyl acrylate, hydroxypropyl methacrylate, hydroxybutyl acrylate, hydroxybutyl methacrylate, 3-chloro-2- Examples include hydroxypropyl methacrylate, di- (ethylene glycol) maleate, di- (ethylene glycol) itaconate, 2-hydroxyethyl maleate, bis (2-hydroxyethyl) maleate, 2-hydroxyethyl methyl fumarate and the like. Among these, β-hydroxyethyl acrylate is preferable. In addition, these may be used individually by 1 type and may be used combining two or more types by arbitrary ratios.

  Examples of the unsaturated carboxylic acid amide monomer include acrylamide, methacrylamide, N-methylol acrylamide, N-methylol methacrylamide, N, N-dimethylacrylamide and the like. Of these, acrylamide and methacrylamide are preferable. In addition, these may be used individually by 1 type and may be used combining two or more types by arbitrary ratios.

  Further, as the polymer as the binder, for example, monomers used in usual emulsion polymerization such as ethylene, propylene, vinyl acetate, vinyl propionate, vinyl chloride, vinylidene chloride may be used. In addition, these may be used individually by 1 type and may be used combining two or more types by arbitrary ratios.

  The weight average molecular weight of the polymer as a binder is preferably 10,000 or more, more preferably 20,000 or more, preferably 1,000,000 or less, more preferably 500,000 or less. When the weight average molecular weight of the polymer as the binder is in the above range, the strength of the negative electrode of the present invention and the dispersibility of the negative electrode active material are easily improved. In addition, what is necessary is just to obtain | require the weight average molecular weight of a water-insoluble polymer as a polystyrene conversion value which used tetrahydrofuran as a developing solvent by gel permeation chromatography (GPC).

  The glass transition temperature of the binder is preferably −75 ° C. or higher, more preferably −55 ° C. or higher, particularly preferably −35 ° C. or higher, and usually 40 ° C. or lower, preferably 30 ° C. or lower, more preferably 20 ° C. or lower. Especially preferably, it is 15 degrees C or less. When the glass transition temperature of the binder is within the above range, characteristics such as flexibility, binding property and winding property of the negative electrode, and adhesion between the negative electrode active material layer and the current collector are highly balanced, which is preferable.

  Usually, the binder is a water-insoluble polymer. Therefore, in the negative electrode slurry composition of the present invention, the binder is not dissolved in water as a solvent but is dispersed as particles. In addition, a polymer being water-insoluble means that an insoluble content becomes 90% by weight or more when 0.5 g of the polymer is dissolved in 100 g of water at 25 ° C. On the other hand, a polymer being water-soluble means that at 25 ° C., 0.5 g of the polymer is dissolved in 100 g of water and the insoluble content is less than 0.5% by weight.

  When the binder is present as particles, the number average particle size of the binder particles is preferably 50 nm or more, more preferably 70 nm or more, preferably 500 nm or less, more preferably 400 nm or less. When the number average particle diameter of the binder is in the above range, the strength and flexibility of the obtained negative electrode can be improved. The presence of particles can be easily measured by transmission electron microscopy, Coulter counter, laser diffraction scattering method, or the like.

The binder is produced, for example, by polymerizing a monomer composition containing the above-described monomer in an aqueous solvent.
The ratio of each monomer in the monomer composition is usually the repeating unit in the polymer as a binder (for example, an aliphatic conjugated diene monomer unit, an aromatic vinyl monomer unit, an ethylenic monomer). The ratio of saturated carboxylic acid monomer units and the like). That is, usually, by polymerizing a monomer composition having a certain composition, a polymer having a unit based on each monomer can be obtained with such a composition. The same applies to the production of the water-soluble polymer described later.

  The aqueous solvent is not particularly limited as long as the binder particles can be dispersed. Usually, the boiling point at normal pressure is usually 80 ° C. or higher, preferably 100 ° C. or higher, and usually 350 ° C. or lower. Preferably, it is selected from 300 ° C. or lower aqueous solvents. Examples of the aqueous solvent will be given below. In the following examples, the number in parentheses after the solvent name is the boiling point (unit: ° C) at normal pressure, and the value after the decimal point is rounded off or rounded down.

  Examples of the aqueous solvent include water (100); ketones such as diacetone alcohol (169) and γ-butyrolactone (204); ethyl alcohol (78), isopropyl alcohol (82), and normal propyl alcohol (97). Alcohols: propylene glycol monomethyl ether (120), methyl cellosolve (124), ethyl cellosolve (136), ethylene glycol tertiary butyl ether (152), butyl cellosolve (171), 3-methoxy-3-methyl-1-butanol (174), Ethylene glycol monopropyl ether (150), diethylene glycol monobutyl pyrether (230), triethylene glycol monobutyl ether (271), dipropylene glycol monomethyl ether (1 Glycol ethers such as 8); 1,3-dioxolane (75), 1,4-dioxolane (101), ethers such as tetrahydrofuran (66); and the like. Among these, water is particularly preferable from the viewpoint that it is not flammable and a dispersion of binder particles can be easily obtained. In addition, water may be used as the main solvent, and an aqueous solvent other than the above-described water may be mixed and used within a range where the dispersed state of the binder particles can be ensured.

  The polymerization method is not particularly limited, and any method such as a solution polymerization method, a suspension polymerization method, a bulk polymerization method, and an emulsion polymerization method can be used. As the polymerization method, any method such as ionic polymerization, radical polymerization, and living radical polymerization can be used. It is easy to obtain a high molecular weight product, and since the polymer is obtained in a state of being dispersed in water as it is, no redispersion treatment is required, and it can be used for production of the negative electrode slurry composition according to the present invention. From the viewpoint of production efficiency, the emulsion polymerization method is particularly preferable.

  The emulsion polymerization method is usually performed by a conventional method. For example, the method is described in “Experimental Chemistry Course” Vol. 28, (Publisher: Maruzen Co., Ltd., edited by The Chemical Society of Japan). That is, water, an additive such as a dispersant, an emulsifier, a crosslinking agent, a polymerization initiator, and a monomer are added to a sealed container equipped with a stirrer and a heating device so as to have a predetermined composition, and the composition in the container This is a method in which a product is stirred to emulsify monomers and the like in water, and the temperature is increased while stirring to initiate polymerization. Or after emulsifying the said composition, it is the method of putting into a sealed container and starting reaction similarly.

  Examples of the polymerization initiator include organic compounds such as lauroyl peroxide, diisopropyl peroxydicarbonate, di-2-ethylhexyl peroxydicarbonate, t-butyl peroxypivalate, 3,3,5-trimethylhexanoyl peroxide. Peroxides; azo compounds such as α, α′-azobisisobutyronitrile; ammonium persulfate; potassium persulfate and the like. In addition, a polymerization initiator may be used individually by 1 type, and may be used combining two or more types by arbitrary ratios.

  An emulsifier, a dispersant, a polymerization initiator, and the like are generally used in these polymerization methods, and the amount used is usually an amount generally used. In the polymerization, seed polymerization may be performed using seed particles.

The polymerization temperature and the polymerization time can be arbitrarily selected depending on the polymerization method and the kind of the polymerization initiator. Usually, the polymerization temperature is about 30 ° C. or more, and the polymerization time is about 0.5 to 30 hours.
Further, additives such as amines may be used as a polymerization aid.

Further, an aqueous dispersion of binder particles obtained by these methods is used, for example, alkali metal (for example, Li, Na, K, Rb, Cs) hydroxide, ammonia, inorganic ammonium compound (for example, NH ₄ Cl). , It may be mixed with a basic aqueous solution containing an organic amine compound (eg, ethanolamine, diethylamine, etc.) and the pH may be adjusted to a range of usually 5 to 10, preferably 5 to 9. Among these, pH adjustment with an alkali metal hydroxide is preferable because it improves the binding property (peel strength) between the current collector and the negative electrode active material.

  The binder particles described above may be composite polymer particles composed of two or more types of polymers. The composite polymer particles are prepared by polymerizing at least one monomer component by a conventional method, then polymerizing at least one other monomer component, and polymerizing by a conventional method (two-stage polymerization method), etc. Can also be obtained. In this way, by polymerizing the monomer stepwise, it is possible to obtain core-shell structured particles having a core layer present inside the particle and a shell layer covering the core layer.

  The amount of the binder is usually 0.1 parts by weight or more, preferably 0.2 parts by weight or more, particularly preferably 0.5 parts by weight or more, and usually 10 parts by weight or less, based on 100 parts by weight of the negative electrode active material. The amount is preferably 5 parts by weight or less, particularly preferably 2 parts by weight or less. If the amount of the binder is less than the lower limit, the adhesiveness can be lowered, which is not preferable. If the amount of the binder exceeds the above upper limit, the low temperature output characteristics can be lowered, which is not preferable.

[1-3. Water-soluble polymer]
The water-soluble polymer according to the present invention includes a sulfonic acid group-containing monomer unit and a phosphoric acid group-containing monomer unit in a specific constituent ratio. By including such a specific water-soluble polymer, the negative electrode of the present invention can suppress the swelling of the negative electrode accompanying charging and discharging, and the capacity is not easily reduced when stored in either a high temperature environment or a low temperature environment. Thus, a secondary battery can be realized in which the capacity is less reduced by repeated charging and discharging. Further, by using the water-soluble polymer according to the present invention, the slurry composition for negative electrode of the present invention can be made excellent in coating property when applied to a current collector, and the negative electrode active in the negative electrode can be improved. The adhesion between the material layer and the current collector can also be improved, and the storage stability of the slurry can also be improved.

  Although not limited by a specific theory, the reason why such an excellent effect can be obtained is considered to be, for example, as follows. That is, in the negative electrode, particularly when a negative electrode active material containing SiOC is used, it is required to increase the dispersibility of the negative electrode active material and reduce the interface resistance. Here, as the water-soluble polymer used in addition to the binder, dispersibility can be improved by using a water-soluble polymer containing a phosphate group, but if it contains a lot of phosphate groups, the durability of the resulting battery is lowered. sell. Here, by using together those containing a sulfonic acid group in addition to a phosphoric acid group, the effect of improving the dispersibility based on the sulfonic acid group can be obtained while improving the durability. In addition to these, other effects such as improvement of proton conductivity based on the phosphate group are combined, and as a result, it is considered that the above effects can be obtained.

The sulfonic acid group-containing monomer unit is a repeating unit obtained by polymerizing a sulfonic acid group (—SO ₃ H) -containing monomer. Examples of the sulfonic acid group-containing monomer include a monomer having a sulfonic acid group and a polymerizable group and a functional group other than those or a salt thereof, an amide group, a sulfonic acid group, and a polymerizable group. Examples thereof include a monomer or a salt thereof, a monomer or a salt thereof containing a hydroxyl group and a sulfonic acid group, and a combination thereof.

  Examples of the monomer having a sulfonic acid group and a polymerizable group and having no functional group other than those include a monomer obtained by sulfonating one of conjugated double bonds of a diene compound such as isoprene and butadiene, Examples thereof include vinyl sulfonic acid, styrene sulfonic acid, allyl sulfonic acid, allyl alkyl ether sulfonic acid, sulfoethyl methacrylate, sulfopropyl methacrylate, and sulfobutyl methacrylate. Moreover, as the salt, lithium salt, sodium salt, potassium salt etc. are mentioned, for example.

  Examples of the monomer containing an amide group, a sulfonic acid group, and a polymerizable group include 2-acrylamido-2-methylpropanesulfonic acid (AMPS). Moreover, as the salt, lithium salt, sodium salt, potassium salt etc. are mentioned, for example. In addition, these may be used individually by 1 type and may be used combining two or more types by arbitrary ratios.

  Examples of the monomer containing a hydroxyl group, a sulfonic acid group, and a polymerizable group include 3-allyloxy-2-hydroxypropanesulfonic acid (HAPS). Moreover, as the salt, lithium salt, sodium salt, potassium salt etc. are mentioned, for example.

  Among these, a monomer containing an amide group, a sulfonic acid group, and a polymerizable group or a monomer having a sulfonic acid group and a polymerizable group and having no other functional group is preferable. A monomer containing a sulfonic acid group and a polymerizable group is more preferable, and in particular, 2-acrylamido-2-methylpropanesulfonic acid is used, and the peel strength of the negative electrode, slurry stability, and low-temperature output characteristics of the battery Since the ability to improve is especially high, it is preferable.

  In addition, a sulfonic acid group containing monomer may be used individually by 1 type, and may be used combining two or more types by arbitrary ratios. Therefore, the water-soluble polymer according to the present invention may contain only one type of sulfonic acid group-containing monomer unit, or may contain two or more types in combination at any ratio.

  In the water-soluble polymer according to the present invention, the ratio of the sulfonic acid group-containing monomer unit is 0.5% by weight or more, preferably 1% by weight or more, and 20% by weight or less, preferably 10%. % By weight or less, more preferably 5% by weight or less. The durability of the secondary battery can be improved by setting the amount of the sulfonic acid group-containing monomer unit to be not less than the lower limit of the above range. Moreover, the fall of the low temperature characteristic of a secondary battery can be prevented by setting it as an upper limit or less.

The phosphate group-containing monomer unit is a repeating unit obtained by polymerizing a phosphate group-containing monomer. As the phosphoric acid group that the phosphoric acid group-containing monomer may have, a monomer having a group —O—P (═O) (— OR ¹ ) —OR ² group (R ¹ and R ² are independently , Hydrogen atom, or any organic group), or a salt thereof. Specific examples of the organic group as R ¹ and R ² include an aliphatic group such as an octyl group and an aromatic group such as a phenyl group.
As a phosphate group containing monomer, the compound containing a phosphate group and an allyloxy group, and a phosphate group containing (meth) acrylic acid ester can be mentioned, for example. Use of a phosphoric acid group-containing (meth) acrylic acid ester is preferable because dispersibility and ion conductivity can be improved, and as a result, output characteristics and high-temperature storage characteristics can be improved.
Examples of the compound containing a phosphate group and an allyloxy group include 3-allyloxy-2-hydroxypropane phosphate.
Examples of phosphoric acid group-containing (meth) acrylic acid esters include dioctyl-2-methacryloyloxyethyl phosphate, diphenyl-2-methacryloyloxyethyl phosphate, monomethyl-2-methacryloyloxyethyl phosphate, dimethyl-2-methacryloyloxy Ethyl phosphate, monoethyl-2-methacryloyloxyethyl phosphate, diethyl-2-methacryloyloxyethyl phosphate, monoisopropyl-2-methacryloyloxyethyl phosphate, diisopropyl-2-methacryloyloxyethyl phosphate, mono n-butyl-2 -Methacryloyloxyethyl phosphate, di-n-butyl-2-methacryloyloxyethyl phosphate, monobutoxyethyl-2-methacryloyloxyethyl phosphate, dibu Kishiechiru-2-methacryloyloxyethyl phosphate, mono (2-ethylhexyl) -2-methacryloyloxyethyl phosphate, and di (2-ethylhexyl) -2-methacryloyloxyethyl phosphate.

  In addition, a phosphate group containing monomer may be used individually by 1 type, and may be used combining two or more types by arbitrary ratios. Therefore, the water-soluble polymer according to the present invention may contain only one type of phosphoric acid group-containing monomer unit, or may contain two or more types in combination at any ratio.

  In the water-soluble polymer according to the present invention, the proportion of the phosphate group-containing monomer unit is 5% by weight or more, preferably 10% by weight or more, 30% by weight or less, preferably 25% by weight. It is as follows. By making the amount of the phosphoric acid-containing monomer unit more than the lower limit of the above range, the effects based on the phosphoric acid group-containing monomer unit, such as improved adhesion between the current collector and the negative electrode active material layer, can be obtained. Can be obtained. Moreover, by setting it as the upper limit value or less, an appropriate degree of polymerization can be obtained in the polymerization of the water-soluble polymer, and an undesirable effect such as a decrease in durability can be prevented.

  The water-soluble polymer according to the present invention may contain any other unit in addition to the sulfonic acid group-containing monomer unit and the phosphoric acid group-containing monomer unit. The ratio of arbitrary units in the water-soluble polymer is 60 to 94.5% by weight. As an arbitrary unit, a unit based on an arbitrary monomer that can be copolymerized with a sulfonic acid group-containing monomer and a phosphoric acid group-containing monomer can be adopted.

  Arbitrary units can include (i) (meth) acrylic acid ester monomer units, (ii) ethylenically unsaturated carboxylic acid monomer units, and (iii) other units. Particularly preferred are (i) (meth) acrylic acid ester monomer units and (ii) ethylenically unsaturated carboxylic acid monomer units.

  (i) The (meth) acrylic acid ester monomer unit is a repeating unit obtained by polymerizing a (meth) acrylic acid ester monomer. As the (meth) acrylic acid ester monomer giving such an arbitrary unit, any (meth) acrylic acid ester other than the sulfonic acid group-containing monomer and the phosphoric acid group-containing monomer can be adopted. Specifically, for example, methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, t-butyl acrylate, pentyl acrylate, hexyl acrylate, heptyl acrylate, octyl acrylate, 2-ethylhexyl acrylate, nonyl acrylate, Acrylic acid alkyl esters such as decyl acrylate, lauryl acrylate, n-tetradecyl acrylate, stearyl acrylate; methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, t-butyl methacrylate, pentyl methacrylate, hexyl methacrylate , Heptyl methacrylate, octyl methacrylate DOO, 2-ethylhexyl methacrylate, nonyl methacrylate, decyl methacrylate, lauryl methacrylate, n- tetradecyl methacrylate, and methacrylic acid alkyl esters such as stearyl methacrylate.

  In addition, a (meth) acrylic acid ester monomer may be used individually by 1 type, and may be used combining two or more types by arbitrary ratios. Therefore, the water-soluble polymer according to the present invention may contain only one type of (meth) acrylic acid ester monomer unit, or may contain two or more types in combination at any ratio.

  In the water-soluble polymer according to the present invention, the ratio of the (meth) acrylic acid ester monomer unit is not particularly limited, and includes a sulfonic acid group-containing monomer and a phosphoric acid group-containing monomer, and Can be the remainder of any other unit. That is, it can be in the range of 50 to 94.5% by weight in the water-soluble polymer. In particular, it is preferably 70% by weight or more, and preferably 90% by weight or less. By setting the ratio of the (meth) acrylic acid ester monomer unit within this range, good flexibility can be imparted to the negative electrode active material layer.

(ii) The ethylenically unsaturated carboxylic acid monomer unit is a repeating unit obtained by polymerizing an ethylenically unsaturated carboxylic acid monomer.
Examples of the ethylenically unsaturated carboxylic acid monomer include ethylenically unsaturated monocarboxylic acid and derivatives thereof, ethylenically unsaturated dicarboxylic acid and acid anhydrides thereof, and derivatives thereof. Examples of the ethylenically unsaturated monocarboxylic acid include acrylic acid, methacrylic acid, crotonic acid and the like. Examples of ethylenically unsaturated monocarboxylic acid derivatives include 2-ethylacrylic acid, isocrotonic acid, α-acetoxyacrylic acid, β-trans-aryloxyacrylic acid, α-chloro-β-E-methoxyacrylic acid, β-diaminoacrylic acid and the like can be mentioned. Examples of the ethylenically unsaturated dicarboxylic acid include maleic acid, fumaric acid, itaconic acid and the like. Examples of the acid anhydride of the ethylenically unsaturated dicarboxylic acid include maleic anhydride, acrylic anhydride, methyl maleic anhydride, dimethyl maleic anhydride and the like. Examples of derivatives of ethylenically unsaturated dicarboxylic acids include methyl maleate such as methylmaleic acid, dimethylmaleic acid, phenylmaleic acid, chloromaleic acid, dichloromaleic acid, fluoromaleic acid; diphenyl maleate, nonyl maleate, Examples thereof include maleic acid esters such as decyl maleate, dodecyl maleate, octadecyl maleate and fluoroalkyl maleate. Among these, ethylenically unsaturated monocarboxylic acids such as acrylic acid and methacrylic acid are preferable. It is because the dispersibility with respect to water of the obtained water-soluble polymer can be improved more.

  In addition, an ethylenically unsaturated carboxylic acid monomer may be used individually by 1 type, and may be used combining two or more types by arbitrary ratios. Therefore, the water-soluble polymer according to the present invention may contain only one type of ethylenically unsaturated carboxylic acid monomer unit, or may contain two or more types in combination at any ratio.

  When the water-soluble polymer according to the present invention contains an ethylenically unsaturated carboxylic acid monomer unit, the ratio is usually 20% by weight or more, preferably 25% by weight or more, based on the total amount of the water-soluble polymer. Usually, it is 60 wt% or less, preferably 50 wt% or less. By making the amount of the ethylenically unsaturated carboxylic acid monomer unit more than the lower limit of the above range, the adsorptivity of the water-soluble polymer to the negative electrode active material is improved, and the dispersibility of the negative electrode active material and the current collector are increased. Adhesion can be increased. In addition, since the flexibility of the water-soluble polymer can be increased by setting it to the upper limit or less, the flexibility of the negative electrode is improved to prevent the negative electrode from being chipped or cracked, thereby improving the durability. Can do.

  (iii) The other unit is obtained by polymerizing a sulfonic acid group-containing monomer and a phosphoric acid group-containing monomer and, if included, a monomer copolymerizable with the monomer of any other unit described above. Is a repeating unit obtained. Examples of monomers that provide such units include carboxylic acid ester monomers having two or more carbon-carbon double bonds, such as ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, trimethylolpropane triacrylate; Styrene monomers such as chlorostyrene, vinyl toluene, t-butyl styrene, vinyl benzoic acid, methyl vinyl benzoate, vinyl naphthalene, chloromethyl styrene, hydroxymethyl styrene, α-methyl styrene, divinyl benzene; acrylamide, N- Amide monomers such as methylolacrylamide; α, β-unsaturated nitrile compound monomers such as acrylonitrile and methacrylonitrile; Olefin monomers such as ethylene and propylene; Halogen atoms such as vinyl chloride and vinylidene chloride Monomers; vinyl ester monomers such as vinyl acetate, vinyl propionate, vinyl butyrate and vinyl benzoate; vinyl ether monomers such as methyl vinyl ether, ethyl vinyl ether and butyl biether; methyl vinyl ketone and ethyl vinyl Examples thereof include vinyl ketone monomers such as ketone, butyl vinyl ketone, hexyl vinyl ketone, and isopropenyl vinyl ketone; and heterocyclic compound-containing vinyl compound monomers such as N-vinyl pyrrolidone, vinyl pyridine, and vinyl imidazole. These monomers may be used individually by 1 type, and may be used combining two or more types by arbitrary ratios.

  In the water-soluble polymer according to the present invention, the ratio of (iii) other units is preferably 0 wt% to 10 wt%, more preferably 0 wt% to 5 wt%.

  The weight average molecular weight of the water-soluble polymer is usually smaller than that of the polymer to be a binder, preferably 100 or more, more preferably 500 or more, particularly preferably 1000 or more, preferably 500000 or less, more preferably 250,000 or less. Particularly preferably, it is 100,000 or less. By making the weight average molecular weight of the water-soluble polymer more than the lower limit of the above range, it is possible to increase the strength of the water-soluble polymer and form a stable protective layer covering the negative electrode active material. In addition, the high temperature storage characteristics of the secondary battery can be improved. Moreover, since the water-soluble polymer can be softened by setting it to the upper limit value or less of the above range, for example, it is possible to suppress swelling of the negative electrode and improve adhesion of the negative electrode active material layer to the current collector. In addition, what is necessary is just to obtain | require the weight average molecular weight of a water-soluble polymer as a value of polyethylene oxide conversion which used GPC as the developing solvent the solution which dissolved 0.85 g / ml sodium nitrate in 10 volume% aqueous solution of acetonitrile.

  The glass transition temperature of the water-soluble polymer is usually 0 ° C. or higher, preferably 5 ° C. or higher, and is usually 100 ° C. or lower, preferably 50 ° C. or lower. When the glass transition temperature of the water-soluble polymer is in the above range, both the adhesion and flexibility of the negative electrode can be achieved. The glass transition temperature of the water-soluble polymer can be adjusted by combining various monomers.

  The water-soluble polymer has a viscosity of 0.1 mPa · s or more, more preferably 0.5 mPa · s or more, particularly preferably 1 mPa · s or more, preferably 20000 mPa · s when a 1% by weight aqueous solution is used. s or less, more preferably 15000 mPa · s or less, particularly preferably 10,000 mPa · s or less. By making the viscosity above the lower limit of the above range, the strength of the water-soluble polymer can be increased to improve the durability of the negative electrode, and by making the viscosity below the upper limit, It is possible to improve the coating property and improve the adhesion strength between the current collector and the negative electrode active material layer. The viscosity can be adjusted by, for example, the molecular weight of the water-soluble polymer. In addition, the said viscosity is a value when it measures at 25 degreeC and rotation speed 60rpm using an E-type viscosity meter.

  As a method for producing a water-soluble polymer, for example, the above-mentioned sulfonic acid group-containing monomer, phosphoric acid group-containing monomer, ethylenically unsaturated carboxylic acid monomer and (meth) acrylic acid ester monomer are used. The monomer composition may be produced by polymerization in an aqueous solvent. The aqueous solvent and the polymerization method may be the same as in the production of the binder, for example. Thereby, an aqueous solution in which a water-soluble polymer is usually dissolved in an aqueous solvent is obtained. The water-soluble polymer may be taken out from the aqueous solution thus obtained. Usually, a negative electrode slurry composition is produced using the water-soluble polymer dissolved in an aqueous solvent, and the negative electrode slurry composition is prepared. To produce a negative electrode.

  Since the aqueous solution containing a water-soluble polymer in an aqueous solvent is usually acidic, it may be alkalized to pH 7 to pH 13 as necessary. Thereby, the handleability of aqueous solution can be improved and the coating property of the slurry composition for negative electrodes can be improved. Examples of the method for alkalinizing to pH 7 to pH 13 include alkaline metal aqueous solutions such as lithium hydroxide aqueous solution, sodium hydroxide aqueous solution and potassium hydroxide aqueous solution; alkaline earth metal aqueous solutions such as calcium hydroxide aqueous solution and magnesium hydroxide aqueous solution; The method of mixing aqueous alkali solution, such as aqueous ammonia solution, is mentioned. In addition, the said alkaline aqueous solution may be used individually by 1 type, and may be used combining two or more types by arbitrary ratios.

  The amount of the water-soluble polymer is usually less than the binder and is preferably 0.1 parts by weight or more, more preferably 0.2 parts by weight or more, particularly preferably 0.5 parts by weight with respect to 100 parts by weight of the negative electrode active material. It is at least 20 parts by weight, preferably at most 20 parts by weight, more preferably at most 10 parts by weight, particularly preferably at most 5 parts by weight. If the amount of the water-soluble polymer is less than the lower limit, the durability may be lowered, which is not preferable. If the amount of the water-soluble polymer exceeds the upper limit, the low-temperature output characteristics can be lowered, which is not preferable.

[1-4. Components that may be contained in the negative electrode active material layer]
In the negative electrode of the present invention, the negative electrode active material layer may contain other components in addition to the above-described negative electrode active material, binder, and water-soluble polymer. Examples of the component include a viscosity modifier, a conductive agent, a reinforcing material, a leveling agent, and an electrolyte solution additive. These are not particularly limited as long as they do not affect the battery reaction. Moreover, these components may be used individually by 1 type, and may be used combining two or more types by arbitrary ratios.

  A viscosity modifier is a component used in order to adjust the viscosity of the slurry composition for negative electrodes of this invention, and to improve the dispersibility and coating property of a slurry composition for negative electrodes. Usually, the viscosity modifier contained in the negative electrode slurry composition remains in the negative electrode active material layer.

  As the viscosity modifier, it is preferable to use a water-soluble polysaccharide. Examples of polysaccharides include natural polymers and cellulose semisynthetic polymers. In addition, a viscosity modifier may be used individually by 1 type, and may be used combining two or more types by arbitrary ratios.

  Examples of natural polymers include polysaccharides and proteins derived from plants or animals. In addition, natural polymers that have been subjected to fermentation treatment with microorganisms, heat treatment, or the like can also be exemplified. These natural polymers can be classified as plant natural polymers, animal natural polymers, microbial natural polymers, and the like.

  Examples of plant-based natural polymers include gum arabic, gum tragacanth, galactan, guar gum, carob gum, caraya gum, carrageenan, pectin, cannan, quince seed (malmello), arche colloid (gasso extract), starch (rice, corn, potato, Derived from wheat and the like), glycyrrhizin and the like. Examples of animal-based natural polymers include collagen, casein, albumin, gelatin, and the like. Furthermore, examples of the microbial natural polymer include xanthan gum, dextran, succinoglucan, and bullulan.

  Cellulosic semisynthetic polymers can be classified into nonionic, anionic and cationic.

  Nonionic cellulose semisynthetic polymers include, for example, alkylcelluloses such as methylcellulose, methylethylcellulose, ethylcellulose, and microcrystalline cellulose; hydroxyethylcellulose, hydroxybutylmethylcellulose, hydroxypropylcellulose, hydroxypropylmethylcellulose, hydroxyethylmethylcellulose, hydroxypropyl And hydroxyalkylcelluloses such as methylcellulose stearoxy ether, carboxymethylhydroxyethylcellulose, alkylhydroxyethylcellulose, and nonoxynylhydroxyethylcellulose;

  Examples of the anionic cellulose semisynthetic polymer include alkyl celluloses obtained by substituting the above nonionic cellulose semisynthetic polymer with various derivative groups, and sodium salts and ammonium salts thereof. Specific examples include sodium cellulose sulfate, methyl cellulose, methyl ethyl cellulose, ethyl cellulose, carboxymethyl cellulose (CMC) and salts thereof.

  Examples of the cationic cellulose semisynthetic polymer include low nitrogen hydroxyethyl cellulose dimethyl diallyl ammonium chloride (polyquaternium-4), O- [2-hydroxy-3- (trimethylammonio) propyl] hydroxyethyl cellulose (polyquaternium- 10), O- [2-hydroxy-3- (lauryldimethylammonio) propyl] chloride ethyl chloride (polyquaternium-24), and the like.

  Among these, cellulose-based semisynthetic polymers, sodium salts thereof, and ammonium salts thereof are preferable because they can have cationic, anionic, and amphoteric characteristics. Among them, an anionic cellulose semisynthetic polymer is particularly preferable from the viewpoint of dispersibility of the negative electrode active material.

  The degree of etherification of the cellulose semisynthetic polymer is preferably 0.5 or more, more preferably 0.6 or more, preferably 1.0 or less, more preferably 0.8 or less. Here, the degree of etherification refers to the degree of substitution of hydroxyl groups (three) per anhydroglucose unit in cellulose with a substitution product such as a carboxymethyl group. The degree of etherification can theoretically take a value of 0-3. When the degree of etherification is in the above range, the cellulosic semi-synthetic polymer adsorbs on the surface of the negative electrode active material and is compatible with water, so it has excellent dispersibility, and the negative electrode active material is at the primary particle level. Can be finely dispersed.

  Further, when a polymer (including a polymer) is used as the viscosity modifier, the average degree of polymerization of the viscosity modifier calculated from the intrinsic viscosity obtained from an Ubbelohde viscometer is preferably 500 or more, more preferably 1000 or more. It is preferably 2500 or less, more preferably 2000 or less, and particularly preferably 1500 or less. The average degree of polymerization of the viscosity modifier may affect the fluidity of the negative electrode slurry composition of the present invention, the film uniformity of the negative electrode active material layer, and the process in the process. By making the average degree of polymerization within the above range, the stability of the negative electrode slurry composition of the present invention over time can be improved, and coating without agglomerates and without thickness unevenness becomes possible.

The amount of the viscosity modifier is preferably 0 part by weight or more and preferably 0.5 part by weight or less with respect to 100 parts by weight of the negative electrode active material. By making the quantity of a viscosity modifier into the said range, the viscosity of the slurry composition for negative electrodes of this invention can be made into the suitable range which is easy to handle.
In the negative electrode of the present invention, since the water-soluble polymer increases the viscosity, the viscosity can be adjusted within a preferable range without adding a large amount of a thickener other than the water-soluble polymer. Therefore, it is possible to avoid problems caused by adding a large amount of thickener. For example, a decrease in conductivity due to the addition of a large amount of thickener can be avoided. Moreover, generation | occurrence | production of the pinhole by a thickener remaining undissolved in a slurry can be reduced.

  The conductive agent is a component that improves electrical contact between the negative electrode active materials. By including the conductive agent, the discharge rate characteristics of the secondary battery of the present invention can be improved.

  As the conductive agent, for example, acetylene black, ketjen black, carbon black, graphite, vapor grown carbon fiber, conductive carbon such as carbon nanotube, and the like can be used. In addition, a electrically conductive agent may be used individually by 1 type, and may be used combining two or more types by arbitrary ratios.

  The amount of the conductive agent is preferably 1 to 20 parts by weight, more preferably 1 to 10 parts by weight with respect to 100 parts by weight of the negative electrode active material.

  As the reinforcing material, for example, various inorganic and organic spherical, plate-like, rod-like or fibrous fillers can be used. By using the reinforcing material, a tough and flexible negative electrode can be obtained, and a secondary battery exhibiting excellent long-term cycle characteristics can be realized.

  The amount of the reinforcing material is usually 0.01 parts by weight or more, preferably 1 part by weight or more, and usually 20 parts by weight or less, preferably 10 parts by weight or less, with respect to 100 parts by weight of the negative electrode active material. By setting the amount of the reinforcing agent in the above range, the secondary battery can exhibit high capacity and high load characteristics.

  Examples of the leveling agent include surfactants such as alkyl surfactants, silicone surfactants, fluorine surfactants, and metal surfactants. By using a leveling agent, it is possible to prevent the repelling that occurs during the application of the negative electrode slurry composition or to improve the smoothness of the negative electrode.

  The amount of the leveling agent is preferably 0.01 to 10 parts by weight with respect to 100 parts by weight of the negative electrode active material. When the leveling agent is in the above range, the productivity, smoothness, and battery characteristics during the production of the negative electrode are excellent. Moreover, by containing a surfactant, the dispersibility of the negative electrode active material and the like in the negative electrode slurry composition can be improved, and the smoothness of the negative electrode obtained thereby can be improved.

Examples of the electrolytic solution additive include vinylene carbonate. By using the electrolytic solution additive, for example, decomposition of the electrolytic solution can be suppressed.
The amount of the electrolytic solution additive is preferably 0.01 to 10 parts by weight with respect to 100 parts by weight of the negative electrode active material. By setting the amount of the electrolytic solution additive in the above range, a secondary battery excellent in cycle characteristics and high temperature characteristics can be realized.

Moreover, the negative electrode active material layer may contain nanoparticles, such as fumed silica and fumed alumina, for example. When the nanoparticle is included, the thixotropy of the negative electrode slurry composition can be adjusted, so that the leveling property of the negative electrode of the present invention obtained thereby can be improved.
The amount of the nanoparticles is preferably 0.01 to 10 parts by weight with respect to 100 parts by weight of the negative electrode active material. When the nanoparticles are in the above range, the stability and productivity of the negative electrode slurry composition can be improved, and high battery characteristics can be realized.

[1-5. Current collector and negative electrode active material layer]
The negative electrode of the present invention includes a negative electrode active material layer containing the above-described negative electrode active material, binder and water-soluble polymer, and other components used as necessary. This negative electrode active material layer is usually provided on the surface of the current collector. At this time, the negative electrode active material layer may be provided on at least one side of the current collector, but is preferably provided on both sides.

  The current collector for the negative electrode is not particularly limited as long as it has electrical conductivity and is electrochemically durable, but a metal material is preferable because of its heat resistance. Examples of the material for the current collector for the negative electrode include iron, copper, aluminum, nickel, stainless steel, titanium, tantalum, gold, and platinum. Among these, copper is particularly preferable as the current collector used for the secondary battery negative electrode. In addition, the said material may be used individually by 1 type, and may be used combining two or more types by arbitrary ratios.

The shape of the current collector is not particularly limited, but a sheet shape having a thickness of about 0.001 mm to 0.5 mm is preferable.
In order to increase the adhesive strength with the negative electrode active material layer, the current collector is preferably used after roughening the surface in advance. Examples of the roughening method include a mechanical polishing method, an electrolytic polishing method, and a chemical polishing method. In the mechanical polishing method, usually, a polishing cloth with an abrasive particle fixed thereto, a grindstone, an emery buff, a wire brush provided with a steel wire or the like is used. Further, an intermediate layer may be formed on the surface of the current collector in order to increase the adhesive strength and conductivity of the negative electrode active material layer.

Usually, a negative electrode active material layer is provided on the surface of the current collector.
The thickness of the negative electrode active material layer is usually 5 μm or more, preferably 30 μm or more, and is usually 300 μm or less, preferably 250 μm or less. When the thickness of the negative electrode active material layer is in the above range, load characteristics and cycle characteristics can be improved.

  The content ratio of the negative electrode active material in the negative electrode active material layer is preferably 85% by weight or more, more preferably 88% by weight or more, preferably 99% by weight or less, more preferably 97% by weight or less. By making the content rate of a negative electrode active material into the said range, the negative electrode which shows a softness | flexibility and a binding property, while showing a high capacity | capacitance is realizable.

[2. Manufacturing method of negative electrode for secondary battery]
The method for producing the negative electrode for secondary battery of the present invention (hereinafter referred to as “the method for producing the negative electrode of the present invention” as appropriate) is not particularly limited. For example, the slurry composition for negative electrode of the present invention is prepared, You may manufacture by the manufacturing method including apply | coating a slurry composition to the surface of an electrical power collector, and making it dry.

  The negative electrode slurry composition of the present invention is a slurry-like composition containing a negative electrode active material, a binder, a water-soluble polymer, and water. Moreover, the slurry composition for negative electrodes of this invention may contain components other than a negative electrode active material, a binder, a water-soluble polymer, and water as needed. The amount of the negative electrode active material, the binder, the water-soluble polymer, and the components included as necessary is usually the same as the amount of each component included in the negative electrode active material layer. In such a slurry composition for negative electrode of the present invention, a part of the water-soluble polymer is usually dissolved in water, but another part of the water-soluble polymer is adsorbed on the surface of the negative electrode active material. Thus, the negative electrode active material is covered with a stable layer of a water-soluble polymer, and the dispersibility of the negative electrode active material in the solvent is improved. For this reason, the slurry composition for negative electrodes of this invention has the favorable coating property at the time of apply | coating to a collector.

  Water functions as a solvent or a dispersion medium in the negative electrode slurry composition, and the negative electrode active material is dispersed, the binder is dispersed in the form of particles, and the water-soluble polymer is dissolved. At this time, a liquid other than water may be used as a solvent in combination with water. It is preferable to combine a binder and a liquid that dissolves the water-soluble polymer because the dispersion of the negative electrode active material is stabilized by adsorbing the binder and the water-soluble polymer to the surface.

  The type of liquid to be combined with water is preferably selected from the viewpoint of drying speed and environment. Preferred examples include cycloaliphatic hydrocarbons such as cyclopentane and cyclohexane; aromatic hydrocarbons such as toluene and xylene; ketones such as ethyl methyl ketone and cyclohexanone; ethyl acetate, butyl acetate, γ-butyrolactone, Esters such as ε-caprolactone; Acylonitriles such as acetonitrile and propionitrile; Ethers such as tetrahydrofuran and ethylene glycol diethyl ether: Alcohols such as methanol, ethanol, isopropanol, ethylene glycol, and ethylene glycol monomethyl ether; N- Examples include amides such as methylpyrrolidone and N, N-dimethylformamide, among which N-methylpyrrolidone (NMP) is preferable. In addition, these may be used individually by 1 type and may be used combining two or more types by arbitrary ratios.

  The amount of water and the liquid is preferably adjusted so that the viscosity of the slurry composition for negative electrode of the present invention is suitable for coating. Specifically, the concentration of the solid content of the slurry composition for negative electrode of the present invention is preferably 30% by weight or more, more preferably 40% by weight or more, preferably 90% by weight or less, more preferably 80% by weight. It is used by adjusting to the following amount.

  The slurry composition for negative electrode of the present invention may be produced by mixing the negative electrode active material, the binder, the water-soluble polymer, water, and components used as necessary. The mixing method is not particularly limited, and examples thereof include a method using a mixing apparatus such as a stirring type, a shaking type, and a rotary type. In addition, a method using a dispersion kneader such as a homogenizer, a ball mill, a sand mill, a roll mill, a planetary mixer, and a planetary kneader can be used.

  The negative electrode slurry of the present invention can be produced by applying the slurry composition for negative electrode on the surface of the current collector and drying it to form a negative electrode active material layer on the surface of the current collector.

  The method for applying the negative electrode slurry composition of the present invention to the surface of the current collector is not particularly limited. Examples of the method include a doctor blade method, a dip method, a reverse roll method, a direct roll method, a gravure method, an extrusion method, and a brush coating method.

  Examples of the drying method include drying with warm air, hot air, and low-humidity air, vacuum drying, and drying by irradiation with (far) infrared rays or electron beams. The drying time is usually 5 to 30 minutes, and the drying temperature is usually 40 ° C to 180 ° C.

  Further, after applying and drying the negative electrode slurry composition on the surface of the current collector, it is preferable to subject the negative electrode active material layer to a pressure treatment using, for example, a die press or a roll press, if necessary. . By the pressure treatment, the porosity of the negative electrode active material layer can be lowered. The porosity is preferably 5% or more, more preferably 7% or more, preferably 30% or less, more preferably 20% or less. By setting the porosity to the lower limit value or more of the above range, a high volume capacity can be easily obtained, the negative electrode active material layer can be made difficult to peel from the current collector, and by setting the porosity to the upper limit value or less, high charging efficiency can be achieved. And discharge efficiency is obtained.

  Furthermore, when a negative electrode active material layer contains a curable polymer, it is preferable to harden the said polymer after formation of a negative electrode active material layer.

[3. Secondary battery]
The secondary battery of the present invention includes the negative electrode of the present invention. Usually, the secondary battery of the present invention includes a positive electrode, a negative electrode, an electrolytic solution, and a separator, and includes the negative electrode of the present invention as the negative electrode.
Since the negative electrode of the present invention is provided, the secondary battery of the present invention can suppress swelling of the negative electrode associated with charge / discharge, and can make it difficult to reduce the capacity when stored in either a high temperature environment or a low temperature environment. In addition, the high-temperature cycle characteristics and low-temperature output characteristics of the secondary battery of the present invention can be improved, and the adhesion of the negative electrode active material layer to the current collector can be improved.

[3-1. Positive electrode]
The positive electrode usually includes a current collector and a positive electrode active material layer including a positive electrode active material and a positive electrode binder formed on the surface of the current collector.

  The current collector of the positive electrode is not particularly limited as long as it is an electrically conductive and electrochemically durable material. As the current collector for the positive electrode, for example, the current collector used for the negative electrode of the present invention may be used. Among these, aluminum is particularly preferable.

  For example, when the secondary battery of the present invention is a lithium ion secondary battery, a material capable of inserting and removing lithium ions is used as the positive electrode active material. Such positive electrode active materials are roughly classified into those made of inorganic compounds and those made of organic compounds.

Examples of the positive electrode active material made of an inorganic compound include transition metal oxides, transition metal sulfides, lithium-containing composite metal oxides of lithium and transition metals, and the like.
Examples of the transition metal include Ti, V, Cr, Mn, Fe, Co, Ni, Cu, and Mo.

Examples of the transition metal oxide include MnO, MnO ₂ , V ₂ O ₅ , V ₆ O ₁₃ , TiO ₂ , Cu ₂ V ₂ O ₃ , amorphous V ₂ O—P ₂ O ₅ , MoO ₃ , V ₂ O ₅ , V ₆ O _{13 and the} like can be mentioned. Among them, MnO, V ₂ O ₅ , V ₆ O ₁₃ and TiO ₂ are preferable from the viewpoint of cycle stability and capacity.
Examples of the transition metal sulfide include TiS ₂ , TiS ₃ , amorphous MoS ₂ , FeS, and the like.

Examples of the lithium-containing composite metal oxide include a lithium-containing composite metal oxide having a layered structure, a lithium-containing composite metal oxide having a spinel structure, and a lithium-containing composite metal oxide having an olivine structure.
Examples of the lithium-containing composite metal oxide having a layered structure include lithium-containing cobalt oxide (LiCoO ₂ ), lithium-containing nickel oxide (LiNiO ₂ ), lithium composite oxide of Co—Ni—Mn, Ni—Mn— Examples thereof include a lithium composite oxide of Al and a lithium composite oxide of Ni—Co—Al.
Examples of the lithium-containing composite metal oxide having a spinel structure include Li [Mn _3/2 M _1/2 ] O _{4 in which} lithium manganate (LiMn ₂ O ₄ ) or a part of Mn is substituted with another transition metal. (Where M is Cr, Fe, Co, Ni, Cu, etc.).
Examples of the lithium-containing composite metal oxide having an olivine type structure include Li _X MPO ₄ (wherein M is Mn, Fe, Co, Ni, Cu, Mg, Zn, V, Ca, Sr, Ba, Ti). Olivine type lithium phosphate compound represented by the formula: at least one selected from the group consisting of Al, Si, B and Mo, wherein X represents a number satisfying 0 ≦ X ≦ 2.

  Examples of the positive electrode active material made of an organic compound include conductive polymers such as polyacetylene and poly-p-phenylene.

Moreover, you may use the positive electrode active material which consists of a composite material which combined the inorganic compound and the organic compound. For example, a composite material covered with a carbon material may be produced by reducing and firing an iron-based oxide in the presence of a carbon source material, and this composite material may be used as a positive electrode active material. Iron-based oxides tend to have poor electrical conductivity, but can be used as a high-performance positive electrode active material by using a composite material as described above.
Furthermore, you may use as a positive electrode active material what carried out the element substitution of the said compound partially. Moreover, you may use the mixture of said inorganic compound and organic compound as a positive electrode active material.
In addition, a positive electrode active material may be used individually by 1 type, and may be used combining two or more types by arbitrary ratios.

  The average particle diameter of the positive electrode active material particles is usually 1 μm or more, preferably 2 μm or more, and usually 50 μm or less, preferably 30 μm or less. By making the average particle diameter of the positive electrode active material particles in the above range, the amount of the binder when preparing the positive electrode active material layer can be reduced, and the decrease in the capacity of the secondary battery can be suppressed. In order to form the positive electrode active material layer, a positive electrode slurry composition containing a positive electrode active material and a binder is usually prepared. The viscosity of the positive electrode slurry composition is adjusted to an appropriate viscosity that is easy to apply. And a uniform positive electrode can be obtained.

  The content ratio of the positive electrode active material in the positive electrode active material layer is preferably 90% by weight or more, more preferably 95% by weight or more, preferably 99.9% by weight or less, more preferably 99% by weight or less. By setting the content of the positive electrode active material in the above range, the capacity of the secondary battery can be increased, and the flexibility of the positive electrode and the binding property between the current collector and the positive electrode active material layer can be improved.

  Examples of the positive electrode binder include polyethylene, polytetrafluoroethylene (PTFE), polyvinylidene fluoride (PVDF), tetrafluoroethylene-hexafluoropropylene copolymer (FEP), polyacrylic acid derivatives, and polyacrylonitrile derivatives. Resins; Soft polymers such as acrylic soft polymers, diene soft polymers, olefin soft polymers, and vinyl soft polymers can be used. In addition, a binder may be used individually by 1 type and may be used combining two or more types by arbitrary ratios.

  In addition, the positive electrode active material layer may contain components other than the positive electrode active material and the binder as necessary. Examples thereof include a viscosity modifier, a conductive agent, a reinforcing material, a leveling agent, an electrolytic solution additive, and the like. Moreover, these components may be used individually by 1 type, and may be used combining two or more types by arbitrary ratios.

  The thickness of the positive electrode active material layer is usually 5 μm or more, preferably 10 μm or more, and usually 300 μm or less, preferably 250 μm or less. When the thickness of the positive electrode active material layer is in the above range, high characteristics can be realized in both load characteristics and energy density.

  The positive electrode may be manufactured, for example, in the same manner as the above-described negative electrode.

[3-2. Electrolyte]
As the electrolytic solution, for example, a solution obtained by dissolving a lithium salt as a supporting electrolyte in a non-aqueous solvent may be used. Examples of the lithium salt include LiPF ₆ , LiAsF ₆ , LiBF ₄ , LiSbF ₆ , LiAlCl ₄ , LiClO ₄ , CF ₃ SO ₃ Li, C ₄ F ₉ SO ₃ Li, CF ₃ COOLi, (CF ₃ CO) ₂ NLi , (CF ₃ SO ₂ ) ₂ NLi, (C ₂ F ₅ SO ₂ ) NLi, and other lithium salts. In particular, LiPF ₆ , LiClO ₄ , and CF ₃ SO ₃ Li that are easily soluble in a solvent and exhibit a high degree of dissociation are preferably used. One of these may be used alone, or two or more of these may be used in combination at any ratio.

  The amount of the supporting electrolyte is usually 1% by weight or more, preferably 5% by weight or more, and usually 30% by weight or less, preferably 20% by weight or less with respect to the electrolytic solution. If the amount of the supporting electrolyte is too small or too large, the ionic conductivity is lowered, and the charging characteristics and discharging characteristics of the secondary battery may be lowered.

  The solvent used in the electrolytic solution is not particularly limited as long as it can dissolve the supporting electrolyte. Examples of the solvent include alkyl carbonates such as dimethyl carbonate (DMC), ethylene carbonate (EC), diethyl carbonate (DEC), propylene carbonate (PC), butylene carbonate (BC), and methyl ethyl carbonate (MEC); Examples include esters such as butyrolactone and methyl formate; ethers such as 1,2-dimethoxyethane and tetrahydrofuran; sulfur-containing compounds such as sulfolane and dimethyl sulfoxide; and the like. In particular, dimethyl carbonate, ethylene carbonate, propylene carbonate, diethyl carbonate, and methyl ethyl carbonate are preferred because high ion conductivity is easily obtained and the use temperature range is wide. In addition, a solvent may be used individually by 1 type and may be used combining two or more types by arbitrary ratios.

  Moreover, you may make an electrolyte solution contain an additive as needed. As the additive, for example, carbonate compounds such as vinylene carbonate (VC) are preferable. In addition, an additive may be used individually by 1 type and may be used combining two or more types by arbitrary ratios.

Examples of the electrolytic solution other than the above include a gel polymer electrolyte obtained by impregnating a polymer electrolyte such as polyethylene oxide and polyacrylonitrile with an electrolytic solution; an inorganic solid electrolyte such as lithium sulfide, LiI, and Li ₃ N; Can do.

[3-3. separator]
As the separator, a porous substrate having a pore portion is usually used. Examples of separators include (a) a porous separator having pores, (b) a porous separator having a polymer coating layer formed on one or both sides, and (c) a porous resin coat containing inorganic ceramic powder. And a porous separator having a layer formed thereon. Examples of these include solid polymer electrolytes such as polypropylene, polyethylene, polyolefin, or aramid porous separators, polyvinylidene fluoride, polyethylene oxide, polyacrylonitrile, or polyvinylidene fluoride hexafluoropropylene copolymers. Or a polymer film for a gel polymer electrolyte; a separator coated with a gelled polymer coat layer; a separator coated with a porous film layer composed of an inorganic filler and an inorganic filler dispersant; and the like.

[3-4. Secondary battery manufacturing method]
The manufacturing method of the secondary battery of the present invention is not particularly limited. For example, the above-described negative electrode and positive electrode may be overlapped via a separator, and this may be wound or folded in accordance with the shape of the battery and placed in the battery container, and the electrolyte may be injected into the battery container and sealed. Furthermore, if necessary, an expanded metal; an overcurrent prevention element such as a fuse or a PTC element; a lead plate or the like may be inserted to prevent an increase in pressure inside the battery or overcharge / discharge. The shape of the battery may be any of, for example, a laminate cell type, a coin type, a button type, a sheet type, a cylindrical type, a square type, and a flat type.

  EXAMPLES Hereinafter, although an Example is shown and this invention is demonstrated concretely, this invention is not limited to the Example shown below. In the following description of Examples, “%” and “parts” representing amounts are based on weight unless otherwise specified. Further, the operations described below were performed under normal temperature and normal pressure conditions unless otherwise specified.

〔Evaluation method〕
1. Adhesive strength The negative electrodes produced in Examples and Comparative Examples were cut into rectangles having a length of 100 mm and a width of 10 mm to obtain test pieces. This test piece was affixed to the cellophane tape fixed to the test stand. In pasting, the surface on the negative electrode active material layer side was brought into contact with the adhesive surface of the cellophane tape with the surface on the negative electrode active material layer side facing down. As the cellophane tape, one specified in JIS Z1522 was used.
Then, the stress when one end of the current collector was pulled vertically upward at a pulling speed of 50 mm / min and peeled was measured. This measurement was performed 3 times, the average value was calculated | required, and the said average value was made into peel strength. The higher the peel strength, the greater the binding force of the negative electrode active material layer to the current collector, that is, the higher the adhesion strength.

2. Slurry Stability The negative electrode slurry compositions produced in the examples and comparative examples were placed in a container, and the viscosity was measured at 25 ° C. Viscosity was measured by setting the rotating part of the E-type viscometer so as to be immersed within 20% from the upper part of the slurry contained in the container, and measuring at 6 rpm.
Then, after leaving the slurry composition for negative electrodes at 5 degreeC for 72 hours, it returned to 25 degreeC and measured the viscosity again similarly to the above. Comparing the viscosities before and after standing, it was set as A if the rate of viscosity change was less than 10% increase, B if it was increased 10% to 30%, and C if it was 30% or more.

3. Coating property Apply the slurry composition for negative electrode manufactured in Examples and Comparative Examples on a 20 μm thick copper foil as a current collector so that the film thickness after drying is about 150 μm, and then dry. It was. This drying was performed by conveying the copper foil in an oven at 60 ° C. at a speed of 0.5 m / min for 2 minutes. Thereafter, heat treatment was performed at 120 ° C. for 2 minutes to obtain a negative electrode. The obtained negative electrode was cut out with a size of 10 × 10 cm, and the number of pinholes having a diameter of 0.1 mm or more was visually measured. The smaller the number of pinholes, the better the coatability.

4). Durability (1) High-temperature storage characteristics After leaving the lithium-ion secondary battery of the laminate type cell produced in Examples and Comparative Examples for 24 hours, the battery was charged and discharged at a charge / discharge rate of 4.2 V and 0.1 C. The operation was performed and the initial capacity _C0 was measured. Furthermore, after charging to 4.2 V and storing at 60 ° C. for 7 days, charge and discharge operations were performed at a charge and discharge rate of 4.2 V and 0.1 C, and the capacity C ₁ after high temperature storage was measured. The high-temperature storage characteristics were evaluated by a capacity change rate ΔC _S represented by ΔC _S = C ₁ / C ₀ × 100 (%). As the value of the capacitance change rate [Delta] C _S is high, the better the high-temperature storage characteristics.

(2) High-temperature cycle characteristics After the lithium-ion secondary batteries of the laminate type cells produced in Examples and Comparative Examples were allowed to stand for 24 hours, charge / discharge operations were performed at a charge / discharge rate of 4.2 V and 0.1 C. The initial capacity C ₀ was measured. Furthermore, charge / discharge was repeated under an environment of 60 ° C., and the capacity C ₂ after 100 cycles was measured. The high temperature cycle characteristics were evaluated by a capacity change rate ΔC _C represented by ΔC _C = C ₂ / C ₀ × 100 (%). It shows that it is excellent in high temperature cycle characteristics, so that the value of this capacity | capacitance change rate (DELTA) _CC is high.

(3) Electrode Swelling Characteristics After the evaluation of the “(1) High temperature storage characteristics”, the cell of the lithium ion secondary battery was disassembled, and the thickness d1 of the negative electrode plate was measured. The negative electrode plate swell ratio (d1-d0) / d0 was calculated with d0 being the thickness of the negative electrode plate before the production of the lithium ion secondary battery cell. It shows that it is excellent in the electrode plate swelling characteristic, so that this value is low.

5. Low temperature output characteristics After the lithium ion secondary batteries of the laminate type cells produced in Examples and Comparative Examples were allowed to stand for 24 hours, charge / discharge operations were performed at a charge / discharge rate of 4.2 V and 0.1 C. Then, charging / discharging operation was performed in -25 degreeC environment, and voltage V10 ₁₀ seconds after the discharge start was measured. Low-temperature output characteristics were evaluated by the voltage change [Delta] V shown by ΔV = _{4.2V-V 10.} It shows that it is excellent in low temperature output characteristics, so that the value of this voltage change (DELTA) V is small.

6). Viscosity of 1% aqueous solution of water-soluble polymer A 1% aqueous solution of a water-soluble polymer was prepared from 10% aqueous ammonia and ion-exchanged water for the water-soluble polymers produced in Examples and Comparative Examples. The viscosity of this aqueous solution was measured with an E-type viscometer.

[Example 1]
(1-1. Production of water-soluble polymer)
In a 5 MPa pressure vessel with a stirrer, 77.5 parts of butyl acrylate, 20 parts of monomethyl-2-methacryloyloxyethyl phosphate, 2.5 parts of 2-acrylamido-2-methylpropanesulfonic acid (AMPS), dodecylbenzenesulfonic acid as an emulsifier 1.0 part of sodium, 150 parts of ion-exchanged water and 0.5 part of potassium persulfate as a polymerization initiator were added and stirred sufficiently, and then heated to 60 ° C. to initiate polymerization. When the polymerization conversion reached 96%, the reaction was stopped by cooling to obtain a mixture containing a water-soluble polymer.
To this mixture, 10% aqueous ammonia was added to adjust to pH 8 to obtain an aqueous solution containing the desired water-soluble polymer.
Using the obtained aqueous solution, a 1% aqueous solution of a water-soluble polymer was prepared as described above, and the viscosity was measured. The results are shown in Table 1.

(1-2. Production of binder)
In a 5 MPa pressure vessel with a stirrer, 33 parts of 1,3-butadiene, 1.5 parts of methacrylic acid, 65.5 parts of styrene, 4 parts of sodium dodecylbenzenesulfonate as an emulsifier, 150 parts of ion-exchanged water, and as a polymerization initiator After adding 0.5 part of potassium persulfate and stirring sufficiently, the mixture was heated to 50 ° C. to initiate polymerization. When the polymerization conversion rate reached 96%, the reaction was stopped by cooling to obtain a mixture containing a binder.
A 5% aqueous sodium hydroxide solution was added to this mixture to adjust to pH 8, and then unreacted monomers were removed by heating under reduced pressure. Then, it cooled to 30 degrees C or less, and obtained the aqueous dispersion liquid containing the desired binder (SBR-1).

(1-3. Production of slurry composition for negative electrode)
The aqueous solution containing the water-soluble polymer obtained in the above (1-1) was diluted with water to adjust the concentration to 5%.
In a planetary mixer with a disper, 90 parts of artificial graphite (volume average particle diameter: 24.5 μm) having a specific surface area of 4 m ² / g and 10 parts of SiOC (volume average particle diameter: 12 μm) as a negative electrode active material, A 1% portion of a 5% aqueous solution of a polymer was added in an amount corresponding to the solid content, adjusted to a solid content concentration of 55% with ion-exchanged water, and then mixed at 25 ° C for 60 minutes. Next, after adjusting the solid content concentration to 52% with ion-exchanged water, the mixture was further mixed at 25 ° C. for 15 minutes to obtain a mixed solution.

Into the mixed solution, 1 part of the aqueous dispersion containing the binder obtained in (1-2) above is added in an amount corresponding to the solid content, and ion-exchanged water, and adjusted so as to have a final solid content concentration of 42%. Mix for 10 minutes. This was defoamed under reduced pressure to obtain a negative electrode slurry composition having good fluidity.
About the obtained slurry composition for negative electrodes, the applicability | paintability and slurry stability were evaluated in the way mentioned above. The results are shown in Table 1.

(1-4. Production of negative electrode)
The slurry composition for negative electrode obtained in (1-3) above was applied on a copper foil having a thickness of 20 μm, which is a current collector, with a comma coater so that the film thickness after drying was about 150 μm. , Dried. This drying was performed by conveying the copper foil in an oven at 60 ° C. at a speed of 0.5 m / min for 2 minutes. Then, the negative electrode original fabric was obtained by heat-processing at 120 degreeC for 2 minute (s). This negative electrode original fabric was rolled with a roll press to obtain a negative electrode having a negative electrode active material layer thickness of 80 μm.
About the obtained negative electrode, the adhesive strength was evaluated in the way mentioned above. The results are shown in Table 1.

(1-5. Production of positive electrode)
As a binder for the positive electrode, a 40% aqueous dispersion of an acrylate polymer having a glass transition temperature Tg of −40 ° C. and a number average particle size of 0.20 μm was prepared. The acrylate polymer is a copolymer obtained by emulsion polymerization of a monomer mixture containing 78% by weight of 2-ethylhexyl acrylate, 20% by weight of acrylonitrile, and 2% by weight of methacrylic acid.

100 parts of LiFePO ₄ having a volume average particle size of 0.5 μm and an olivine crystal structure as a positive electrode active material, and a 1% aqueous solution of carboxymethyl cellulose (“BSH-12” manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) as a solid component as a solid content 1 part at a time and a 40% aqueous dispersion of the above acrylate polymer as a binder are mixed with 5 parts at a solid content, and ion-exchanged water is added to this so that the total solid content concentration is 40%. The slurry composition for positive electrodes was prepared by mixing with a planetary mixer.

  The slurry composition for positive electrode was applied on a copper foil having a thickness of 20 μm, which is a current collector, with a comma coater so that the film thickness after drying was about 200 μm and dried. This drying was performed by conveying the copper foil in an oven at 60 ° C. at a speed of 0.5 m / min for 2 minutes. Then, it heat-processed for 2 minutes at 120 degreeC, and obtained the positive electrode.

(1-6. Preparation of separator)
A single-layer polypropylene separator (width 65 mm, length 500 mm, thickness 25 μm, manufactured by dry method, porosity 55%) was cut into a square of 5 × 5 cm ² .

(1-7. Lithium ion secondary battery)
An aluminum packaging exterior was prepared as the battery exterior. The positive electrode obtained in the above (1-5) was cut into a square of 4 × 4 cm ² and arranged so that the current collector-side surface was in contact with the aluminum packaging exterior. On the surface of the positive electrode active material layer of the positive electrode, the square separator obtained in (1-6) above was disposed. Furthermore, the negative electrode obtained in the above (1-4) was cut into a square of 4.2 × 4.2 cm ² and arranged on the separator so that the surface on the negative electrode active material layer side faces the separator. And electrolyte solution was inject | poured in the aluminum packaging material so that air might not remain. Furthermore, in order to seal the opening of the aluminum packaging material, heat sealing at 150 ° C. was performed to close the aluminum exterior, and a lithium ion secondary battery was manufactured. In addition, as an electrolytic solution, LiPF ₆ was added at 1 mol / liter in a mixed solvent obtained by mixing ethylene carbonate (EC) and diethyl carbonate (DEC) at EC: DEC = 1: 2 (volume ratio at 20 ° C.). A solution dissolved at a concentration was used.
About the obtained lithium ion secondary battery, durability was evaluated by the high temperature storage characteristic, the high temperature cycling characteristic, and the electrode plate swelling characteristic in the above-mentioned way, and also the low temperature output characteristic was evaluated. The results are shown in Table 1.

[Examples 2 to 4]
In the production of the slurry for negative electrode in the step (1-3), a water-soluble polymer is contained in the same manner as in Example 1 except that the ratio of artificial graphite and SiOC as the negative electrode active material is changed as shown in Table 1. An aqueous solution, a negative electrode slurry composition, a negative electrode and a lithium ion secondary battery were prepared and evaluated. The results are shown in Table 1.

[Examples 5 to 14 and Comparative Examples 1 to 6]
In manufacture of the water-soluble polymer of a process (1-1), except having changed the kind and ratio of each monomer as shown in Tables 1-4, it contains a water-soluble polymer like Example 1. An aqueous solution, a negative electrode slurry composition, a negative electrode and a lithium ion secondary battery were prepared and evaluated. The results are shown in Tables 1-4.

Examples 15 and 16
In the production of the slurry for negative electrode in the step (1-3), the addition amount (corresponding to the solid content) of the 5% aqueous solution of the water-soluble polymer was changed as shown in Table 3 in the same manner as in Example 1, An aqueous solution containing a water-soluble polymer, a slurry composition for negative electrode, a negative electrode and a lithium ion secondary battery were prepared and evaluated. The results are shown in Table 3.

Example 17
In the step of mixing the negative electrode active material and the 5% aqueous solution of the water-soluble polymer in the production process of the negative electrode slurry in the step (1-3), in addition to these, a 1% aqueous solution of carboxymethyl cellulose (Daiichi Kogyo) “BSH-12” manufactured by Pharmaceutical Co., Ltd.) was added in the same manner as in Example 1 except that 0.5 part corresponding to the solid content was added, an aqueous solution containing a water-soluble polymer, a slurry composition for negative electrode, a negative electrode, and lithium An ion secondary battery was created and evaluated. The results are shown in Table 3.

Example 18
(18-1. Production of Binder)
In a 5 MPa pressure vessel with a stirrer, 57.0 parts of 1,3-butadiene, 1.5 parts of methacrylic acid, 41.5 parts of styrene, 4 parts of sodium dodecylbenzenesulfonate as an emulsifier, 150 parts of ion-exchanged water and a polymerization initiator After adding 0.5 part of potassium persulfate and stirring sufficiently, the mixture was heated to 50 ° C. to initiate polymerization. When the polymerization conversion rate reached 96%, the reaction was stopped by cooling to obtain a mixture containing a binder.
A 5% aqueous sodium hydroxide solution was added to this mixture to adjust to pH 8, and then unreacted monomers were removed by heating under reduced pressure. Then, it cooled to 30 degrees C or less, and obtained the aqueous dispersion containing a desired binder (SBR-2).

(18-2. Manufacture of lithium ion secondary batteries, etc.)
As the aqueous dispersion containing the binder, instead of the one obtained in (1-2), the one obtained in (18-1) above was used, except that (1-1) and (1- In the same manner as 3) to (1-7), an aqueous solution containing a water-soluble polymer, a negative electrode slurry composition, a negative electrode, and a lithium ion secondary battery were prepared and evaluated. The results are shown in Table 3.

Example 19
(19-1. Production of binder)
In a 5 MPa pressure vessel with a stirrer, 33.2 parts of 1,3-butadiene, 3.8 parts of itaconic acid, 63 parts of styrene, 4 parts of sodium dodecylbenzenesulfonate as an emulsifier, 150 parts of ion-exchanged water and persulfuric acid as a polymerization initiator After adding 0.5 part of potassium and stirring sufficiently, it heated to 50 degreeC and superposition | polymerization was started. When the polymerization conversion rate reached 96%, the reaction was stopped by cooling to obtain a mixture containing a binder.
A 5% aqueous sodium hydroxide solution was added to this mixture to adjust to pH 8, and then unreacted monomers were removed by heating under reduced pressure. Then, it cooled to 30 degrees C or less, and obtained the aqueous dispersion liquid containing the desired binder (SBR-3).

(19-2. Manufacture of lithium ion secondary batteries, etc.)
As an aqueous dispersion containing a binder, instead of the one obtained in (1-2), the one obtained in (19-1) above was used, except that (1-1) and (1- In the same manner as 3) to (1-7), an aqueous solution containing a water-soluble polymer, a negative electrode slurry composition, a negative electrode, and a lithium ion secondary battery were prepared and evaluated. The results are shown in Table 3.

Example 20
(20-1. Production of binder)
70 parts of ion-exchanged water and 0.3 part of sodium dodecylbenzenesulfonate were respectively supplied to a reactor equipped with a stirrer and mixed sufficiently, and the gas phase part was replaced with nitrogen gas, and the temperature was raised to 70 ° C. .
On the other hand, in another container, 50 parts of ion-exchanged water, 0.5 part of sodium dodecylbenzenesulfonate, and 76 parts of 2-ethylhexyl acrylate, 20 parts of acrylonitrile, and 4 parts of methacrylic acid were mixed as a polymerizable monomer. A monomer mixture was obtained. This monomer mixture was continuously added to the reactor over 4 hours to conduct polymerization. The reaction was started by adding 0.5 part of potassium persulfate as a 3% aqueous solution of potassium persulfate to the reactor when the addition of the monomer mixture was started. Moreover, reaction was performed at 60 degreeC during addition of a monomer mixture. After the addition of the monomer mixture was completed, the reaction was further terminated by stirring at 80 ° C. for 3 hours to obtain an aqueous dispersion containing an acrylate polymer binder (ACR). The polymerization conversion rate was 98.5%.

(20-2. Manufacture of lithium ion secondary batteries, etc.)
As the aqueous dispersion containing the binder, instead of the one obtained in (1-2), the one obtained in (20-1) above was used, except that (1-1) and (1- In the same manner as 3) to (1-7), an aqueous solution containing a water-soluble polymer, a negative electrode slurry composition, a negative electrode, and a lithium ion secondary battery were prepared and evaluated. The results are shown in Table 3.

[Comparative Example 7]
In the production of the slurry composition for negative electrode in the step (1-3), except that the aqueous solution containing the water-soluble polymer obtained in (1-1) was not added, (1-2) to In the same manner as (1-7), a slurry composition for negative electrode, a negative electrode and a lithium ion secondary battery were prepared and evaluated. The results are shown in Table 4.

[Comparative Example 8]
(C8-1. Production of binder)
In a 5 MPa pressure vessel with a stirrer, 16.5 parts of 1,3-butadiene, 0.75 parts of methacrylic acid, 32.8 parts of styrene, 38.7 parts of butyl acrylate, 10 parts of monomethyl-2-methacryloyloxyethyl phosphate, 2 -1.25 parts of acrylamido-2-methylpropanesulfonic acid, 4 parts of sodium dodecylbenzenesulfonate as an emulsifier, 150 parts of ion-exchanged water, and 0.5 part of potassium persulfate as a polymerization initiator were sufficiently stirred. Thereafter, the polymerization was started by heating to 50 ° C. When the polymerization conversion rate reached 96%, the reaction was stopped by cooling to obtain a mixture containing a binder.
A 5% aqueous sodium hydroxide solution was added to this mixture to adjust to pH 8, and then unreacted monomers were removed by heating under reduced pressure. Then, it cooled to 30 degrees C or less, and obtained the aqueous dispersion containing the desired binder (SBR-4).

(C8-2. Manufacture of lithium ion secondary batteries, etc.)
In the production of the slurry composition for negative electrode in the step (1-3), the aqueous solution containing the water-soluble polymer obtained in (1-1) was not added, and the binder was obtained in (1-2) as a binder. Instead of the above, a slurry composition for a negative electrode, a negative electrode and lithium were used in the same manner as in (1-3) to (1-7) of Example 1 except that the product obtained in (C8-1) was used. An ion secondary battery was created and evaluated. The results are shown in Table 4.

The items indicated by the abbreviations in the table are as follows.
S unit amount: sulfonic acid group-containing monomer unit amount P unit amount: phosphoric acid group-containing monomer unit amount AMPS: 2-acrylamido-2-methylpropanesulfonic acid SSA: styrene sulfonic acid 4SBMA; 4-sulfobutyl methacrylate MAA: methacrylic acid MM2MAOEPA: monomethyl-2-methacryloyloxyethyl phosphate DO2MAOEPA: dioctyl-2-methacryloyloxyethyl phosphate DP2MAOEPA: diphenyl-2-methacryloyloxyethyl phosphate AA: acrylic acid BA: butyl acrylate MMA: methyl methacrylate SBR -1: Binder, prepared in (1-2) of Example 1 SBR-2: Binder, prepared in (18-1) of Example 18 SBR-3: Binder, Example 19 (19-1) as prepared in ACR: Binder, Example 20 (20-1) as prepared in SBR-4: binders, as prepared in the Comparative Example Example 8 (C8-1)

As can be seen from Tables 1 to 4, in the examples, the swelling of the negative electrode accompanying charging and discharging can be suppressed, and a secondary battery can be realized in which the capacity is not easily lowered even when stored in either a high temperature environment or a low temperature environment. Since the high-temperature cycle characteristics and the low-temperature output characteristics can be improved, a secondary battery having excellent durability can be realized. Furthermore, since the amount of pinholes generated during the production of the negative electrode is small, the adhesiveness between the current collector and the negative electrode active material layer is high, and the stability of the slurry is also high, it can be easily produced while satisfying the above performance.
Furthermore, compared with Comparative Example 8 in which the binder is not a water-soluble polymer but a binder having a sulfonic acid group-containing monomer unit and a phosphoric acid group-containing monomer unit, the present embodiment has a remarkably good effect. showed that.
Therefore, the secondary battery obtained by the present invention is a secondary battery that exhibits practically excellent performance.

Claims (7)

A negative electrode for a secondary battery comprising a negative electrode active material, a binder and a water-soluble polymer,
A secondary battery in which the water-soluble polymer is a copolymer containing 0.5 to 13 % by weight of a sulfonic acid group-containing monomer unit and 5 to 30% by weight of a phosphate group-containing monomer unit. Negative electrode.   The negative electrode for secondary batteries according to claim 1, wherein the phosphate group-containing monomer is a phosphate group-containing (meth) acrylic ester.   The sulfonic acid group-containing monomer is a monomer containing an amide group, a sulfonic acid group, and a polymerizable group, or a monomer having a sulfonic acid group and a polymerizable group and having no other functional group. The negative electrode for secondary batteries of Claim 1 or 2 which is a body.   The negative electrode for secondary batteries according to any one of claims 1 to 3, wherein the 1% aqueous solution viscosity of the water-soluble polymer is 0.1 to 20000 mPa · s. A secondary battery comprising a positive electrode, a negative electrode, an electrolyte, and a separator,
The secondary battery whose said negative electrode is a negative electrode for secondary batteries of any one of Claims 1-4. A negative electrode slurry composition comprising a negative electrode active material, a binder, a water-soluble polymer and water,
Slurry for negative electrode, wherein the water-soluble polymer is a copolymer containing 0.5% by weight to 13 % by weight of sulfonic acid group-containing monomer units and 5-30% by weight of phosphoric acid group-containing monomer units. Composition. The manufacturing method of the negative electrode for secondary batteries including apply | coating the slurry composition for negative electrodes of Claim 6 on the surface of a collector, and making it dry.