Secondary battery binder, slurry, electrode, method for producing secondary battery, and secondary battery

Abstract

The present invention provides: a novel binder that is capable of suitably contributing to the production of a battery and / or battery characteristics by means of a secondary battery binder which contains an aqueous polymer, wherein the amount of moisture generated at 170-290°C in the aqueous polymer is 15% by mass or less as measured by the measurement method described below, the aqueous polymer is a vinyl polymer that has a repeating unit having an acidic functional group and a nonionic hydrophilic repeating unit, the weight average molecular weight of the aqueous polymer is 1,000,000 or less, and the pH at 25°C of an aqueous solution that is obtained by dissolving the aqueous polymer in water at a concentration of 2% by mass is 6.5 to 8.5 inclusive; and a slurry which contains this binder. [Amount of moisture generated at 170-290°C] 20 g of an aqueous polymer solution which is obtained by dissolving the aqueous polymer in water so as to have a solid content concentration of 2% by mass is added to a tray, and after drying the aqueous polymer solution at 60°C for 8 hours in a forced convection oven, additional drying is performed for 24 hours under conditions of 60°C and a degree of pressure reduction of 0.1 MPa in a vacuum dryer so as to produce a film. The thus-produced film is cut into an approximately 2-mm-square piece weighing 10 mg, and measurement is performed under the conditions described below using a Karl Fischer moisture meter and a moisture vaporizer.　Measurement conditions: After the temperature is raised to 80°C, the temperature is kept at 80°C until the weight loss rate falls to 0.1 µg / s or less (method A). Thereafter, the temperature is raised from 80°C to 300°C over 30 minutes (method B).　Method A data collection interval: 1 second; Method B data collection interval: 5 seconds; Calculation of amount of generated moisture: The ratio of the amount of generated moisture is calculated according to the formula described below, where Wa is the weight after keeping the temperature at 80°C until the weight loss rate falls to 0.1 µg / s or less, and Wb is the amount of generated moisture detected between 170°C and 290°C.　Ratio of amount of generated moisture = Wb / Wa × 100 (% by mass)

Description

Secondary battery binder, slurry, electrode, method for manufacturing secondary battery, and secondary battery

[0001] The present disclosure relates to a secondary battery binder, a slurry, an electrode, a method for manufacturing a secondary battery, and a secondary battery.

[0002] In the manufacturing process of secondary batteries, particularly in the manufacturing process of electrodes, a slurry containing a binder is used. In recent years, due to concerns about the impact on the environment, interest has been increasing in shifting from slurries using organic solvents to aqueous slurries using water as the solvent. Patent Document 1 discloses the use of an aqueous slurry containing a latex-based binder.

[0003] JP 2012-49061 A

[0004] The types and properties of the binder are not sufficiently considered in Patent Document 1. An object of the present disclosure is to provide a novel binder that can favorably contribute to battery production and / or battery properties, or a slurry containing the binder.

[0005] The present disclosure includes the following aspects: [Item 1] A secondary battery binder comprising an aqueous polymer, wherein the amount of moisture generated from the aqueous polymer at 170°C to 290°C is 15% by mass or less as measured by the following measurement method, the aqueous polymer being a vinyl polymer having a repeating unit having an acidic functional group and a nonionic hydrophilic repeating unit, the weight-average molecular weight of the aqueous polymer being 1,000,000 or less, and the pH of an aqueous solution obtained by dissolving the aqueous polymer in water to a concentration of 2% by mass is 6.5 or more and 8.5 or less at 25°C. [Amount of moisture generated at 170°C to 290°C] 20 g of an aqueous polymer solution prepared by dissolving the aqueous polymer in water to a solids concentration of 2% by mass was added to a tray, dried at 60°C for 8 hours in a constant temperature incubator with a forced air blower, and then further dried in a vacuum dryer at 60°C and a reduced pressure of 0.1 MPa for 24 hours to produce a film. The prepared film was cut into approximately 2 mm square pieces, each measuring 10 mg, and measured using a Karl Fischer moisture meter and a moisture vaporizer under the following conditions. Measurement conditions: After heating to 80°C, the film was kept at 80°C until the rate of weight loss reached 0.1 μg / s or less (Method A). The film was then heated from 80°C to 300°C over 30 minutes (Method B). Method A: Data collection interval: 1 second; Method B: Data collection interval: 5 seconds. Calculation of the amount of moisture generated: The weight after keeping the film at 80°C until the rate of weight loss reached 0.1 μg / s or less was designated Wa, and the amount of moisture generated between 170°C and 290°C was designated Wb. The percentage of the amount of moisture generated was calculated using the following formula: Percentage of amount of moisture generated = Wb / Wa × 100 [mass %]. [Item 2] The secondary battery binder according to Item 1, wherein the amount of moisture generated is 2.5 mass % or more. [Item 3] The aqueous polymer is represented by the formula: -[CH ２ -C(R １ ) (C(=O)R ２ )] - [wherein, R 1 is a hydrogen atom or CH ３ and R 2 is NH ２ , OM (M is a hydrogen atom or a counter cation), O(CH ２ ) ｎ OH, NH(CH ２ ) ｎOH (wherein n is independently 1 or more and 6 or less).] and a repeating unit (1) represented by the formula: -[CH ２ Item 4. The secondary battery binder according to Item 1 or 2, comprising a repeating unit selected from the repeating unit (2) represented by the formula: —CH(OH)]—. [Item 4] The secondary battery binder according to Item 3, wherein in the aqueous polymer, the amount of the repeating unit selected from the repeating unit (1) and the repeating unit (2) is 40 mol % or more, the amount of the acidic functional group-containing repeating unit is 0.8 mol % or more, and the amount of the nonionic repeating unit is 40 mol % or more. [Item 5] The secondary battery binder according to any one of Items 1 to 4, comprising SBR. [Item 6] A slurry comprising the secondary battery binder according to any one of Items 1 to 5 and water. [Item 7] The slurry according to Item 6, further comprising an electrode active material. [Item 8] A method for producing a secondary battery, comprising a step of applying the slurry according to Item 6 or 7. [Item 9] An electrode comprising the secondary battery binder according to Items 1 to 5 or a component derived from the secondary battery binder. [Item 10] An electrode comprising a heat-dried product of the slurry according to Item 6 or 7. [Item 11] A secondary battery comprising the electrode according to Item 9 or 10.

[0006] The secondary battery binder according to the present disclosure or a slurry containing the secondary battery binder has one or more properties suitable for batteries or the manufacture of batteries. In particular, the use of the secondary battery binder according to the present disclosure or a slurry containing the secondary battery binder can suitably suppress an increase in resistance after charge-discharge cycling of the battery.

[0007] <Definitions of Terms, etc.> In this specification, regardless of whether "each independently" or a similar expression is explicitly stated, unless otherwise stated, when a term (symbol) that may appear multiple times in a chemical structure is defined, the definition applies independently to each occurrence.

[0008] In this specification, "(meth)acrylic" means "acrylic or methacrylic", and "(meth)allyl" means "allyl or methallyl".

[0009] In this specification, when multiple lower limit values ​​and multiple upper limit values ​​are separately described, any lower limit value and any upper limit value can be selected, and a numerical range that is a combination of the lower limit value and the upper limit value can be selected.

[0010] <Secondary Battery Binder> The secondary battery binder in the present disclosure is used to enhance the binding strength between particles inside an electrode in a secondary battery and the binding strength between an active material layer and a current collector.

[0011] [Water-based polymer] The secondary battery binder in the present disclosure includes a water-based polymer. The water-based polymer in the present disclosure is a polymer that can be dispersed in water by itself, and is particularly water-soluble.

[0012] [Characteristics of Water-Based Polymer] The characteristics of the water-based polymer are shown below.

[0013] (Water Solubility) When 2.0 g of the aqueous polymer is dissolved in 100 g of water at 25°C, the insoluble content may be 20% by mass or less, or 15% by mass or less, preferably 5% by mass or less, and more preferably 1% by mass or less, relative to the aqueous polymer.

[0014] (Molecular weight, etc.) The Mw (weight average molecular weight) of the aqueous polymer measured by GPC-triple detector is 1,000,000 or less. The Mw of the aqueous polymer measured by GPC-triple detector may be 50,000 or more, 100,000 or more, 300,000 or more, 500,000 or more, or 750,000 or more, preferably 100,000 or more, more preferably 200,000 or more, and may be 800,000 or less, 500,000 or less, 250,000 or less, or 100,000 or less, preferably 700,000 or less, more preferably 600,000 or less. This value is determined by the method described in the examples. By having the Mw of the aqueous polymer measured by GPC-triple detector be in the above range (particularly 100,000 or more), the viscosity stability of the aqueous solution can be improved, which may be advantageous from the viewpoint of productivity in battery production.

[0015] The Rh (hydrodynamic radius) of the aqueous polymer measured by GPC-triple detector may be 2.5 nm or more, 5.0 nm or more, 7.5 nm or more, 10 nm or more, or 12.5 nm or more, preferably 3.0 nm or more, more preferably 5.0 nm or more, and may be 30 nm or less, 20 nm or less, 10 nm or less, 7.5 nm or less, or 5 nm or less, preferably 9.0 nm or less, more preferably 7.0 nm or less. This value is determined by the method described in the Examples.

[0016] The Rg (radius of gyration) of the aqueous polymer measured by GPC-triple detector may be 0.1 nm or more, 1.0 nm or more, 10 nm or more, 20 nm or more, 40 nm or more, or 60 nm or more, preferably 0.1 nm or more, more preferably 15 nm or more, and may be 200 nm or less, 100 nm or less, 75 nm or less, 50 nm or less, or 30 nm or less, preferably 50 nm or less, more preferably 30 nm or less. This value is determined by the method described in the Examples.

[0017] (pH) The pH (25°C) of the aqueous solution obtained when the aqueous polymer is dissolved in water at a concentration of 2% by mass is 6.5 to 8.5, and may be 7.0 to 7.5, or 8.0 or more, or 8.0 to 7.5, or 7.0 or less, preferably 7.5 or less. This value is determined by the method described in the Examples. Ion-exchanged water is typically used as the water. When the pH is above the lower limit (particularly 7.0 or more (neutral to alkaline)), the flexibility of the polymer component containing the aqueous polymer is increased and the solution can exhibit high compliance with the expansion and contraction of the active material. Similarly, when the pH is above the lower limit, the dispersibility of the slurry can be improved. When the pH is within the above range (particularly 6.5 to 7.5), the viscosity stability of the aqueous polymer solution is improved, which is preferable from the viewpoint of productivity in battery production. When the pH is below the upper limit (e.g., pH 7.5 or less), the hydrogen bonding interaction of the acidic groups is strengthened, and viscosity stability can be improved.

[0018] (Viscosity) The viscosity (25°C) of the aqueous solution obtained when a water-based polymer is dissolved in water at a concentration of 2% by mass may be 1 mPa·s or more, 5 mPa·s or more, 10 mPa·s or more, 25 mPa·s or more, or 50 mPa·s or more, preferably 3 mPa·s or more, more preferably 5 mPa·s or more, and may be 2000 mPa·s or less, 1000 mPa·s or less, 500 mPa·s or less, 100 mPa·s or less, 50 mPa·s or less, or 25 mPa·s or less, preferably 50 mPa·s or less, more preferably 30 mPa·s or less. This value is determined by the method described in the Examples. Ion-exchanged water is usually used as the water. By setting the viscosity within the above range (e.g., 3 mPa·s or more and 200 mPa·s or less), the dispersibility of the active material and binder in the slurry is improved, a binder film is well formed on the active material, and expansion of the electrode (particularly the initial expansion rate) when the slurry is used as a battery can be suppressed. Similarly, by setting the viscosity within the above range, the dispersibility of the slurry can be improved. (APHA) The APHA of the aqueous solution obtained when the aqueous polymer is dissolved in water at a concentration of 2% by mass may be 0 or more, 5 or more, 10 or more, or 20 or more, and may be 200 or less, 100 or less, 50 or less, 25 or less, 5 or less, or 1 or less, preferably 10 or less, more preferably 8 or less. This value is determined by the method described in the Examples. Ion-exchanged water is usually used as the water.

[0019] (Amount of moisture generated at 170°C to 290°C) The amount of moisture generated by the water-based polymer at 170°C to 290°C is 15% by mass or less. By ensuring that the amount of moisture generated is within the above range, the battery resistance after charge / discharge cycling can be suitably suppressed. From the same perspective, the amount of moisture generated is preferably 13% by mass or less, more preferably 12% by mass or less. Furthermore, the amount of moisture generated may be 2.5% by mass or more, 5.0% by mass or more, 7.5% by mass or more, or 10% by mass or more, preferably 2.5% by mass or more, more preferably 4.0% by mass or more. The water-based polymer used as the binder mainly generates water during thermal decomposition. It is believed that a similar dehydration reaction also occurs in the battery due to interaction with the active material during charge / discharge. When the amount of water generated during thermal decomposition at 170°C to 290°C is within the above range (for example, 15% by mass or less, particularly 2.5% by mass or more and 15% by mass or less), the effect on the decrease in conductivity associated with structural changes in the aqueous polymer due to the influence of decomposition in the dehydration reaction is small, and as a result, it is thought that an increase in battery resistance can be suppressed.

[0020] (Glass transition temperature) The glass transition temperature of the aqueous polymer may be 30°C or higher, 50°C or higher, 60°C or higher, or 80°C or higher, preferably 50°C or higher, more preferably 55°C or higher, and may be 120°C or lower, 100°C or lower, 80°C or lower, 60°C or lower, or 40°C or lower, preferably 100°C or lower, more preferably 90°C or lower. This value is determined by the method described in the Examples. A glass transition temperature within the above range (particularly 50°C or higher and 100°C or lower) is suitable from the viewpoint of suppressing battery resistance. A glass transition temperature above the lower limit (particularly 50°C or higher) is considered to improve the strength of the polymer as a binder, increase the degree of coverage of the active material by the binder, suppress the formation of a high-resistance film due to decomposition of the electrolyte upon contact with the electrolyte, and suppress an increase in battery resistance. When the glass transition temperature is below the upper limit (particularly 100°C or below), the flexibility of the polymer increases, allowing it to follow the expansion and contraction of the active material, and it is thought that an increase in battery resistance due to cracks on the electrode surface can be suppressed.

[0021] [Structure of Water-Based Polymer, etc.] Water-based polymers are obtained by polymerizing one or more types of monomers. Water-based polymers are vinyl polymers having a repeating unit with an acidic functional group and a nonionic hydrophilic repeating unit. Vinyl polymers are polymers obtained by polymerizing vinyl monomers. Here, the vinyl monomer may be any compound having a polymerizable carbon-carbon double bond (ethylenically unsaturated double bond) (>C=C<), and may be a monomer containing a vinyl group, a vinylene group, a vinylidene group, an acryloyl group, a methacryloyl group, or a derivative group thereof. The water-based polymer may particularly be a (meth)acrylic polymer containing a repeating unit derived from a monomer having an acryloyl group or a methacryloyl group.

[0022] The water-based polymer may be a random polymer or a block polymer, for example a random polymer.

[0023] (Hydrophilic Repeating Unit) The aqueous polymer has a hydrophilic repeating unit. The hydrophilic repeating unit contains a hydrophilic group. Examples of the hydrophilic group include anionic groups such as a carboxy group, a sulfonic acid group, a phosphate group, and a nitrate group, cationic groups such as an amino group, a hydroxy group, a polyoxyethylene group (e.g., having a repeating number of 2 or more, 5 or more, or 10 or more), and nonionic hydrophilic groups such as an amide group. The anionic group and the cationic group may be in a free acid / base state, or a part or all of them may be in the form of a salt. The hydrophilic repeating unit may not contain a sulfonic acid group-containing repeating unit, and the aqueous polymer may not contain a sulfonic acid group-containing repeating unit.

[0024] In this specification, when an anionic group or a cationic group or a structure containing such a group (for example, a repeating unit containing an acidic functional group) is mentioned, it is intended to encompass not only the anionic group and the cationic group but also salts thereof, unless explicitly stated otherwise.

[0025] Examples of counter cations of anionic groups include metal ions, preferably light metal ions, more preferably lithium ions, sodium ions, or potassium ions, and particularly lithium ions or sodium ions. The counter cations may be monovalent to trivalent, monovalent to divalent, or monovalent, preferably monovalent. Examples of counter anions of cationic groups include inorganic acid ions such as phosphate ions, nitrate ions, and sulfate ions, and halide ions. The aqueous polymer may be anionic, or may not have a cationic group.

[0026] The aqueous polymer of the present disclosure has a repeating unit having an acidic functional group as a hydrophilic repeating unit. The acidic functional group may be an anionic group such as a carboxy group, a sulfonic acid group, a phosphate group, or a nitrate group, preferably a carboxy group or a sulfonic acid group, and more preferably a carboxy group. These groups may exist in the form of a salt, and in this case, the above-mentioned metal ions are suitable as counter cations. Examples of repeating units having an acidic functional group include repeating units derived from (meth)acrylic acid, maleic acid, vinylsulfonic acid, or (meth)allylsulfonic acid.

[0027] The aqueous polymer in the present disclosure has a nonionic hydrophilic repeating unit, examples of which include repeating units derived from (meth)acrylamide, hydroxyalkyl (meth)acrylate, hydroxyalkyl (meth)acrylamide, polyoxyalkylene (meth)acrylate, polyoxyalkylene (meth)acrylamide, and vinyl alcohol.

[0028] Examples of suitable hydrophilic repeating units include those of the formula: —[CH ２ -C(R １ ) (C(=O)R ２ )] - [wherein, R 1 is a hydrogen atom or CH ３ and R 2 is NH ２ , OM (M is a hydrogen atom or a counter cation), O(CH ２ ) ｎ OH, NH(CH２ ) ｎ OH (wherein n is independently 1 or more and 6 or less).] and a repeating unit (1) represented by the formula: -[CH ２ -CH(OH)]- (2)

[0029] In the repeating unit (1), R 1 is preferably a hydrogen atom.

[0030] In the repeating unit (1), R ２ M in the formula (I) may be a metal cation, preferably a light metal cation, more preferably a lithium ion, a sodium ion, or a potassium ion, and particularly preferably a lithium ion or a sodium ion. M may be monovalent to trivalent, monovalent to divalent, or monovalent, and is preferably monovalent.

[0031] In the repeating unit (1), R ２ In the formula, n may be 6 or less, 5 or less, 4 or less, 3 or less, or 2 or less, preferably 3 or less, and especially 2 or less.

[0032] The repeating unit (1) is R 2 It is preferable that the repeating unit (1) contains at least one of an NH group, an OH group, an ONa group, and an OLi group. 2 is only NH2 group, R 2 is only OH group, R 2 is only an ONa group, or R 2 The repeating unit (1) may be an OLi group only. 2 may contain ONa groups and OH groups, and R 2 may contain an OLi group and an OH group, may contain an NH group and an OH group, may contain an NH group, an OH group and an ONa group, may contain an NH group, an OH group, an ONa group and an OLi group, or R 2 may contain OH groups, OLi groups and NH2 groups.

[0033] The repeating unit (2) can be introduced, for example, by polymerizing a vinyl ester (vinyl acetate, vinyl propionate, etc., particularly vinyl acetate) followed by saponification, or by reacting a polymer having a vinyl alcohol-based repeating unit (e.g., polyvinyl alcohol).

[0034] The aqueous polymer preferably contains a repeating unit derived from (meth)acrylic acid (particularly a sodium salt or lithium salt).

[0035] (Non-hydrophilic repeating unit) The aqueous polymer may have a non-hydrophilic repeating unit. The non-hydrophilic repeating unit does not have a hydrophilic group (e.g., an ionic group). Examples of the non-hydrophilic repeating unit include repeating units derived from (meth)acrylonitrile, (meth)acrylic acid alkyl ester, vinyl chloride, etc.

[0036] [Composition of aqueous polymer, etc.] The amount of hydrophilic repeating units in the aqueous polymer may be 20 mol% or more, 40 mol% or more, 60 mol% or more, 80 mol% or more, or 90 mol% or more, preferably 80 mol% or more, more preferably 90 mol% or more, and may be 100 mol% or less, 90 mol% or less, 80 mol% or less, or 70 mol% or less.

[0037] The amount of the acidic functional group-containing repeating unit in the aqueous polymer may be 0.8 mol% or more, 3 mol% or more, 5 mol% or more, 10 mol% or more, 20 mol% or more, 40 mol% or more, or 60 mol% or more, preferably 0.8 mol% or more, more preferably 10 mol% or more, and may be 90 mol% or less, 80 mol% or less, or 70 mol% or less, preferably 60 mol% or less, more preferably 50 mol% or less.

[0038] The amount of nonionic hydrophilic repeating units in the aqueous polymer may be 20 mol% or more, 40 mol% or more, 60 mol% or more, 80 mol% or more, or 90 mol% or more, preferably 40 mol% or more, more preferably 60 mol% or more, and may be 100 mol% or less, 90 mol% or less, 80 mol% or less, or 70 mol% or less, preferably 99 mol% or less, more preferably 80 mol% or less.

[0039] The amount of non-hydrophilic repeating units in the aqueous polymer may be 0 mol% or more, 1 mol% or more, 3 mol% or more, 5 mol% or more, 20 mol% or more, 40 mol% or more, or 50 mol% or more, or may be 70 mol% or less, 50 mol% or less, 40 mol% or less, 30 mol% or less, 20 mol% or less, 10 mol% or less, 5 mol% or less, or 3 mol% or less, and the aqueous polymer may not contain non-hydrophilic repeating units.

[0040] The amount of nonionic repeating units in the aqueous polymer may be 20 mol% or more, 40 mol% or more, 60 mol% or more, 80 mol% or more, or 90 mol% or more, preferably 40 mol% or more, more preferably 60 mol% or more, and may be 100 mol% or less, 90 mol% or less, 80 mol% or less, or 70 mol% or less, preferably 99 mol% or less, more preferably 90 mol% or less.

[0041] The total amount of the repeating unit (1) and the repeating unit (2) in the aqueous polymer may be 40 mol% or more, 60 mol% or more, 80 mol% or more, or 90 mol% or more, preferably 40 mol% or more, more preferably 50 mol% or more, and may be 100 mol% or less, 90 mol% or less, 80 mol% or less, or 70 mol% or less, preferably 100 mol% or less, more preferably 90 mol% or less.

[0042] The amount of the repeating unit (1) in the aqueous polymer may be 40 mol% or more, 60 mol% or more, 80 mol% or more, or 90 mol% or more, preferably 40 mol% or more, more preferably 50 mol% or more, and may be 100 mol% or less, 90 mol% or less, 80 mol% or less, or 70 mol% or less, preferably 100 mol% or less, more preferably 90 mol% or less.

[0043] The amount of the repeating unit (2) in the aqueous polymer may be 40 mol% or more, 60 mol% or more, 80 mol% or more, or 90 mol% or more, and may be 100 mol% or less, 90 mol% or less, 80 mol% or less, or 70 mol% or less, preferably 50 mol% or less, more preferably 10 mol% or less. The aqueous polymer may not contain the repeating unit (2).

[0044] A repeating unit derived from (meth)acrylamide (R ２ NH ２ The amount of the hydroxybenzoate (H2O3) in the aqueous polymer may be 20 mol% or more, 40 mol% or more, 60 mol% or more, 80 mol% or more, or 90 mol% or more, preferably 30 mol% or more, more preferably 50 mol% or more, and may be 99 mol% or less, 90 mol% or less, 80 mol% or less, or 70 mol% or less, preferably 99 mol% or less, more preferably 80 mol% or less.

[0045] A repeating unit derived from (meth)acrylic acid or a salt thereof (R ２ The amount of OM) in the aqueous polymer may be 20 mol% or more, 40 mol% or more, 60 mol% or more, 80 mol% or more, or 90 mol% or more, preferably 20 mol% or more, and may be 90 mol% or less, 80 mol% or less, or 70 mol% or less, preferably 60 mol% or less.

[0046] [Method for Producing Aqueous Polymers] The method for producing the aqueous polymer is not particularly limited, and can be produced using known copolymer production methods. Preferably, the polymer can be synthesized by aqueous radical polymerization. Specifically, a radical polymerization initiator and, if necessary, a chain transfer agent are added to a monomer mixture, and the polymerization reaction is carried out at a reaction temperature of approximately 50 to 100°C (e.g., 60 to 70°C) while stirring. The reaction time is not particularly limited, and may be approximately 1 to 10 hours. After the reaction time has elapsed, the mixture may be further aged for 15 minutes to 2 hours (e.g., 30 minutes to 1.5 hours) at a temperature of +3°C to +10°C (e.g., +4°C to +8°C) above the reaction temperature. Aging can reduce the amount of unreacted monomer. When the aqueous polymer contains vinyl alcohol units, the saponification conditions may be set with reference to, for example, the method for producing a copolymer of vinyl alcohol and an alkali metal neutralized product of an ethylenically unsaturated carboxylic acid, as described in WO 2017 / 168947.

[0047] The monomer concentration at the start of polymerization may be 5% by mass or more, 10% by mass or more, 15% by mass or more, 20% by mass or more, or 25% by mass or more, and may be 30% by mass or less, 25% by mass or less, 20% by mass or less, 15% by mass or less, or 10% by mass or less, and in one aspect, is 10% by mass or more and 11% by mass or less, 15% by mass or more and 17% by mass or less, or 11% by mass or more and 13% by mass or less.

[0048] Various known initiators can be used without particular limitation. Examples of radical polymerization initiators include persulfates such as potassium persulfate and ammonium persulfate; redox-based polymerization initiators that combine such persulfates with a reducing agent such as sodium hydrogen sulfite; and azo-based initiators such as 2,2'-azobis-2-amidinopropane dihydrochloride (V-50, manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.), 2,2'-azobis[2-(2-imidazolin-2-yl)propane]dihydrochloride (VA-044, manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.), and 2,2'-azobis(2,4-dimethylvaleronitrile) (V-65, manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.). The amount of radical polymerization initiator used is preferably about 0.05 to 2% by mass, and more preferably about 0.1 to 1.5% by mass, relative to 100% by mass of the monomer group that serves as the raw material for the aqueous polymer of the present disclosure.

[0049] The polymerization conditions can be appropriately set in accordance with the structure of the target compound.

[0050] [Amount of Water-Based Polymer] The amount of the water-based polymer in the secondary battery binder may be 25% by mass or more, 50% by mass or more, 75% by mass or more, 95% by mass or more, or 99% by mass or more, preferably 50% by mass or more, more preferably 75% by mass or more, and may be 99% by mass or less, 90% by mass or less, 80% by mass or less, or 70% by mass or less. The secondary battery binder may be the water-based polymer alone.

[0051] [Other Binder Components] The secondary battery binder according to the present disclosure may contain other binder components in addition to the aqueous polymer. Examples of the other binder components include known binder resins, such as styrene-butadiene rubber (SBR), styrene-ethylene-butylene-styrene copolymer (SEBS), polyimide (PI), polyamide, and ethylene-vinyl acetate copolymer (EVA).

[0052] The amount of other binder components in the secondary battery binder may be 0% by mass or more, 0.5% by mass or more, 5% by mass or more, 10% by mass or more, or 25% by mass or more, and may be 50% by mass or less, 40% by mass or less, 30% by mass or less, 20% by mass or less, 10% by mass or less, or 5% by mass or less, for example, 3% by mass or less.

[0053] <Slurry> The slurry of the present disclosure contains the secondary battery binder and water, and may further contain an electrode active material. The slurry may also contain battery particles such as a conductive additive and other liquid media, and is typically an electrode slurry containing an electrode active material. The slurry may be a positive electrode slurry containing a positive electrode active material or a negative electrode slurry containing a negative electrode active material.

[0054] [Liquid Medium] The slurry contains a liquid medium (aqueous medium) containing water. The liquid medium is preferably water alone from the viewpoint of environmental concerns, but may also contain an organic solvent, such as alcohol (ethanol, methanol, isopropyl alcohol, etc.). The amount of the organic solvent in the liquid medium may be 30% by mass or less, 20% by mass or less, 10% by mass or less, 5% by mass or less, or 3% by mass or less, and preferably 10% by mass or less.

[0055] [Amount of liquid medium] The amount of the liquid medium may be 20% by mass or more, 40% by mass or more, 60% by mass or more, 80% by mass or more, or 100% by mass or more, and is preferably 30% by mass or more, relative to 100% by mass of the slurry solids content (total amount of secondary battery binder, active material, and conductive additive), and may be 200% by mass or less, 100% by mass or less, 80% by mass or less, 60% by mass or less, 50% by mass or less, or 40% by mass or less, and is preferably 160% by mass or less, and more preferably 150% by mass or less.

[0056] [Secondary Battery Binder] The slurry contains a secondary battery binder, the types of which are as described above.

[0057] [Amount of Secondary Battery Binder] The amount of the secondary battery binder in the slurry solids (total amount of the secondary battery binder, active material, and conductive additive) may be 0.1% by mass or more, 0.3% by mass or more, 0.5% by mass or more, 1.0% by mass or more, 1.5% by mass or more, 3.0% by mass or more, or 5.0% by mass or more, preferably 0.3% by mass or more, and 10% by mass or less, 7.5% by mass or less, 5.0% by mass or less, 3.0% by mass or less, 1.0% by mass or less, 0.5% by mass or less, preferably 5.0% by mass or less, more preferably 4.0% by mass or less. Being equal to or greater than the lower limit is preferable from the viewpoint of exhibiting the effect of the secondary battery binder well. Being equal to or less than the upper limit is preferable from the viewpoint of achieving a high capacity battery.

[0058] [Active Material] The active material is an electrode active material, and may be a negative electrode active material or a positive electrode active material. When the active material is a negative electrode active material, it may contain, for example, a carbon material, and may also contain, for example, at least one of silicon and silicon oxide. Specific examples of the negative electrode active material and the positive electrode active material are shown below.

[0059] (Negative Electrode Active Material) The negative electrode active material is not particularly limited, and any negative electrode active material used in the technical field may be used.

[0060] Carbon materials such as crystalline carbon and amorphous carbon may be used as the negative electrode active material. Examples of crystalline carbon include graphite, such as natural graphite or artificial graphite, which may be amorphous, plate-like, flake-like, spherical, or fibrous. Examples of amorphous carbon include soft carbon (easily graphitizable carbon) or hard carbon (non-graphitizable carbon), mesophase pitch carbide, and calcined coke.

[0061] Materials capable of absorbing and releasing large amounts of lithium ions, such as silicon (Si), tin (Sn), and titanium (Ti), may be used as the negative electrode active material. These materials may be used in the form of simple substances, alloys, compounds, solid solutions, or composite active materials containing silicon-containing materials, tin-containing materials, and titanium-containing materials. Examples of silicon-containing materials include Si, Si / C, SiOx (0.05<x<1.95), or alloys, compounds, or solid solutions in which at least one element selected from the group consisting of B, Mg, Ni, Ti, Mo, Co, Ca, Cr, Cu, Fe, Mn, Nb, Ta, V, W, Zn, C, N, and Sn is substituted for a portion of the Si. The silicon-containing material may be a silicon oxide. Examples of tin-containing materials include Ni2Sn4, Mg2Sn, SnOx (0<x<2), SnO2, SnSiO3, LiSnO, etc. Examples of titanium-containing materials include Li2TiO3 and Li4Ti5O 12 Examples of the material include lithium titanates such as those mentioned above, and titanium-niobium composite compounds. These materials can be used singly or in combination of two or more. Among these, silicon or silicon oxide is preferred, and may be, for example, simple silicon or silicon oxide.

[0062] As the negative electrode active material, it is more preferable to use a composite obtained by mixing silicon or silicon oxide as the first negative electrode active material and a carbon material as the second negative electrode active material. As the carbon material, any carbon material generally used in secondary batteries, particularly non-aqueous electrolyte secondary batteries, can be used, and crystalline carbon, amorphous carbon, or a combination of these may be used. Examples of crystalline carbon include those described above.

[0063] The method for producing the negative electrode active material is not particularly limited. When producing an active material composite by mixing the first negative electrode active material and the second negative electrode active material, a method in which both materials are uniformly dispersed may be employed, such as a method in which the first negative electrode active material and the second negative electrode active material are mixed in a ball mill.

[0064] (Positive Electrode Active Material) The positive electrode active material is not particularly limited, and any positive electrode active material used in the art may be used.

[0065] The positive electrode active material may be a lithium-containing composite oxide. Examples of the lithium-containing composite oxide include LiMnO, LiFeO, LiCoO, LiMnO, LiFeSiO, and LiNi. 1 / 3 Co 1 / 3 Mn 1 / 3 O2, LiNi 0.5 Co 0.2 Mn 0.3 O2, LiNi 0.6 Co 0.2 Mn 0.2 O2, LiNi 0.8 Co 0.1 Mn 0.1 O2, LiNi x Co y M z O2 (wherein 0≦x<1, 0≦y<1, 0≦z<1, x+y+z=1, and M is at least one element selected from the group consisting of Mn, V, Mg, Mo, Nb, Fe, Cu, and Al), LiMn （１－ｗ） Fe ｗ PO4 (where 0<w<1), LiFePO4, etc.

[0066] [Amount of Active Material] The amount of the active material in the slurry solids (total amount of secondary battery binder, active material, and conductive additive) may be 35% by mass or more, 45% by mass or more, 55% by mass or more, 65% by mass or more, 75% by mass or more, or 95% by mass or more, preferably 55% by mass or more, more preferably 75% by mass or more, and is 99% by mass or less, 95% by mass or less, 90% by mass or less, or 85% by mass or less.

[0067] [Conductive Aid] As the conductive aid, a conductive aid used in the present technical field can be used. The conductive aid is not particularly limited as long as it has conductivity, but carbon powder is preferred. Examples of carbon powder include commonly used carbon materials such as acetylene black (AB), ketjen black (KB), graphite, carbon fiber, carbon tube, graphene, amorphous carbon, hard carbon, soft carbon, glassy carbon, carbon nanofiber, and carbon nanotube. These may be used alone or in combination of two or more.

[0068] [Amount of conductive additive] The amount of conductive additive in the slurry solids (total amount of secondary battery binder, active material, and conductive additive) may be 0.1 mass% or more, 0.5 mass% or more, 1.0 mass% or more, 3.0 mass% or more, or 5.0 mass% or more, and is preferably 0.3 mass% or more, and may be 10 mass% or less, 5.0 mass% or less, 3.0 mass% or less, or 1.0 mass% or less, and is preferably 3.0 mass% or less, and more preferably 1.0 mass% or less.

[0069] [Dispersing Aid] The slurry of the present disclosure may further contain a dispersing aid. Examples of the dispersing aid include an organic acid containing a carboxyl group and at least one substituent selected from the group consisting of a hydroxyl group, an amino group, and an imino group, or humic acid. Examples of organic acids containing a hydroxyl group and a carboxyl group include lactic acid, tartaric acid, citric acid, malic acid, glycolic acid, tartronic acid, glucuronic acid, and humic acid. Examples of organic acids containing an amino group and a carboxyl group include glycine, alanine, phenylalanine, 4-aminobutyric acid, leucine, isoleucine, lysine, glutamic acid, aspartic acid, glutamine, asparagine, histidine, tryptophan, cysteine, and polymers thereof. Examples of organic acids containing an imino group and a carboxyl group include proline, 3-hydroxyproline, 4-hydroxyproline, and pipecolic acid. Among these, glucuronic acid, humic acid, glycine, polyglycine, aspartic acid, and glutamic acid are preferred from the viewpoint of availability.

[0070] [Amount of Dispersion Aid] The amount of the dispersion aid may be 0.1 parts by mass or more, 0.5 parts by mass or more, 1.0 parts by mass or more, 1.5 parts by mass or more, or 3.0 parts by mass or more, and is preferably 0.3 parts by mass or more, and may be 5.0 parts by mass or less, 3.0 parts by mass or less, or 1.0 part by mass or less, and is preferably 3.0 parts by mass or less, and more preferably 1.0 part by mass or less, relative to 100 parts by mass of the slurry solids (total amount of the secondary battery binder, active material, and conductive aid).

[0071] Other Components The slurry of the present disclosure may contain other components, such as conventional additives.

[0072] [Amount of Other Components] The amount of other components (individual amount or total amount) may be 0.1 parts by mass or more, 0.5 parts by mass or more, 1.0 parts by mass or more, 3.0 parts by mass or more, or 5.0 parts by mass or more, and preferably 0.3 parts by mass or more, relative to 100 parts by mass of the slurry solids content (total amount of secondary battery binder, active material, and conductive additive), and may be 10 parts by mass or less, 5.0 parts by mass or less, 3.0 parts by mass or less, 1.0 part by mass or less, 0.5 parts by mass or less, and preferably 3.0 parts by mass or less, and more preferably 1.0 part by mass or less.

[0073] [Method for Producing Slurry] The method for producing the slurry of the present disclosure is not particularly limited, and the slurry is produced by mixing components. For example, a secondary battery binder, a liquid medium, an active material, and optionally, a conductive additive, a dispersing aid, and the like are mixed to produce a slurry. The timing of adding the liquid medium is not particularly limited. The secondary battery binder of the present disclosure may be dispersed or dissolved in the liquid medium in advance, and then the active material and the like may be mixed to produce a slurry. Alternatively, the active material, the secondary battery binder of the present disclosure, and optionally, a conductive additive, a dispersing aid, and the like may be mixed in a solid state, and then the liquid medium may be added to produce a paste-like slurry.

[0074] <Electrode> The electrode of the present disclosure is an electrode for a secondary battery, and includes the secondary battery binder (or a component derived from the secondary battery binder) and an active material according to the present disclosure. That is, the electrode of the present disclosure can be produced, for example, by applying the slurry of the present disclosure to a current collector and drying it. Therefore, the electrode may include a heat-dried product of the slurry. The secondary battery binder may be decomposed or reacted by heat drying and converted into a component derived from the secondary battery binder.

[0075] The temperature during heat drying may be 50°C or higher, 70°C or higher, 90°C or higher, 110°C or higher, or 130°C or higher, preferably 70°C or higher, and 300°C or lower, 250°C or lower, 200°C or lower, 175°C or lower, 150°C or lower, or 125°C or lower, preferably 150°C or lower. Heat drying may be carried out under reduced pressure (for example, 0.05 MPa or lower, 0.03 MPa or lower, or 0.01 MPa or lower). The heat drying time may be 1 hour or longer, 3 hours or longer, 6 hours or longer, 10 hours or longer, or 15 hours or longer, preferably 6 hours or longer, and may be 72 hours or shorter, 48 hours or shorter, 36 hours or shorter, 24 hours or shorter, or 18 hours or shorter, preferably 24 hours or shorter.

[0076] When the electrode of the present disclosure is a negative electrode, the material constituting the current collector may be, for example, a conductive material such as C, Cu, Ni, Fe, V, Nb, Ti, Cr, Mo, Ru, Rh, Ta, W, Os, Ir, Pt, Au, or Al, or an alloy containing two or more of these conductive materials (e.g., stainless steel). The current collector may also be made of Fe plated with Cu. From the viewpoints of high electrical conductivity, excellent stability in the electrolyte, and excellent oxidation resistance, Cu, Ni, stainless steel, etc. are preferred as the material for the negative electrode current collector, and Cu or Ni is more preferred from the viewpoint of material cost.

[0077] When the electrode of the present disclosure is a positive electrode, the material constituting the current collector may be, for example, a conductive substance such as C, Ti, Cr, Mo, Ru, Rh, Ta, W, Os, Ir, Pt, Au, or Al, or an alloy containing two or more of these conductive substances (for example, stainless steel). From the viewpoints of high electrical conductivity, excellent stability in the electrolyte, and excellent oxidation resistance, C, Al, stainless steel, etc. are preferred as the material for the positive electrode current collector, and Al is more preferred from the viewpoint of material cost.

[0078] The shape of the current collector is not particularly limited, and for example, a foil substrate, a three-dimensional substrate, etc. Use of a three-dimensional substrate (foam metal, mesh, woven fabric, nonwoven fabric, expanded fabric, etc.) tends to improve high-rate charge / discharge characteristics.

[0079] <Battery> The secondary battery of the present disclosure includes the secondary battery electrode of the present disclosure. The secondary battery of the present disclosure may include the secondary battery electrode of the present disclosure as either one or both of the positive electrode and the negative electrode. The secondary battery of the present disclosure is produced using the secondary battery electrode of the present disclosure (i.e., using the secondary battery binder of the present disclosure) by a method used in the technical field.

[0080] The secondary battery of the present disclosure is preferably a nonaqueous electrolyte secondary battery, and particularly preferably a lithium ion secondary battery. Because lithium ion secondary batteries must contain lithium ions, a lithium salt is preferred as the electrolyte. Examples of the lithium salt include lithium hexafluorophosphate, lithium perchlorate, lithium tetrafluoroborate, lithium trifluoromethanesulfonate, and lithium trifluoromethanesulfonyl imide. The electrolyte may be used alone or in combination of two or more.

[0081] Examples of the electrolyte solution that can be used include propylene carbonate, ethylene carbonate, dimethyl carbonate, diethyl carbonate, and γ-butyrolactone. The electrolyte solution can be used alone or in combination of two or more. Propylene carbonate alone, a mixture of ethylene carbonate and diethyl carbonate, or γ-butyrolactone alone are particularly preferred. The mixing ratio of the above-mentioned mixture of ethylene carbonate and diethyl carbonate can be adjusted as long as one of the components accounts for 10 to 90% by volume.

[0082] Other configurations of the secondary battery may also be the same as those of known secondary batteries.

[0083] Although the embodiments have been described above, it will be understood that various changes in form and details can be made without departing from the spirit and scope of the claims.

[0084] The present disclosure will be described in detail below with reference to examples, but the present disclosure is not limited to these examples.

[0085] The abbreviations have the following meanings: AA: acrylic acid AAm: acrylamide 2-HEA: 2-hydroxyethyl acrylate SMAS: sodium methallylsulfonate VA: vinyl alcohol

[0086] <Preparation of Polymer> The polymer was prepared according to the procedure described below.

[0087] Reference Example 1 A sealable vial having an internal volume of 500 ml was charged with 34.9 g (0.49 mol) of acrylamide, 0.2 g (0.001 mol) of sodium methallylsulfonate, 35.3 g (0.49 mol) of acrylic acid, 48.6 g (0.42 mol) of 2-hydroxyethyl acrylate, 1.36 g of 2,2'-azobis[2-(2-imidazolin-2-yl)propane]dihydrochloride (product name "VA-044" manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.), and 210.0 g of ion-exchanged water, and the charged solution was mixed to prepare an aqueous monomer solution, which was then deoxygenated. Separately, a stirrer, a thermometer, and N ２ A 2 L reaction vessel equipped with a gas inlet tube, a reflux condenser, and a dropping funnel was charged with 858.3 g of ion-exchanged water, and N ２ After deoxygenating the system by blowing in gas, the internal temperature was raised to 68°C. Subsequently, the deoxygenated aqueous monomer solution was added dropwise to the reaction vessel over 3 hours using a dropping funnel while stirring. After the dropwise addition, the internal temperature was maintained at 68°C for 2 hours. The mixture was further stirred at 73°C for 1 hour, cooled to 30°C, and 30.3 g of a 48% by mass aqueous NaOH solution was added until the pH reached 5.5, yielding an aqueous solution containing an aqueous polymer. The repeating unit composition of the aqueous polymer was AAm / AA(H / Na) / 2-HEA / SMAS = 35 / 35 / 29.9 / 0.1 (molar ratio).

[0088] Example 1 A sealable vial having an internal volume of 500 ml was charged with 126.6 g (1.78 mol) of acrylamide, 2.9 g (0.02 mol) of sodium methallylsulfonate, 1.45 g of 2,2'-azobis[2-(2-imidazolin-2-yl)propane] dihydrochloride (product name: VA-044, manufactured by Fujifilm Wako Pure Chemical Industries), and 250.0 g of ion-exchanged water, and the charged solution was mixed to prepare an aqueous monomer solution, which was then deoxygenated. ２A 2 L reaction vessel equipped with a gas inlet tube, a reflux condenser, and a dropping funnel was charged with 831.0 g of ion-exchanged water, and N ２ After deoxygenating the system by blowing in gas, the internal temperature was raised to 68°C. Next, the prepared aqueous monomer solution was added dropwise to the reaction vessel using a dropping funnel over a period of 3 hours while stirring. After the dropwise addition, the mixture was maintained at the same temperature for 1.5 hours. Next, 1.45 g of VA-044 and 20 g of ion-exchanged water were added, and the mixture was stirred at the same temperature for 1 hour. The mixture was further stirred at 73°C for 1 hour, yielding an aqueous solution containing a water-based polymer. The repeating unit composition of the water-based polymer was AAm / SMAS = 99 / 1 (molar ratio).

[0089] Example 2 40.0 g (0.56 mol) of acrylic acid, 60.0 g (0.52 mol) of 2-hydroxyethyl acrylate, 0.367 g of ammonium persulfate, and 50.0 g of ion-exchanged water were added to a sealable vial with an internal volume of 500 ml and mixed to prepare an aqueous monomer solution, which was then deoxygenated. ２ A 1 L reaction vessel equipped with a gas inlet tube, a reflux condenser, and a dropping funnel was charged with 500.0 g of ion-exchanged water, and N ２ After deoxygenating the system by blowing in gas, the internal temperature was raised to 75°C. Subsequently, the prepared aqueous monomer solution was added dropwise to the reaction vessel over a period of 3 hours using a dropping funnel while stirring. After the dropwise addition, the temperature was maintained for 2 hours. The internal temperature was then raised to 80°C and maintained for 1 hour. The internal temperature was then cooled to 40°C, and 124.9 g (0.53 mol) of a 5 mol / L aqueous sodium hydroxide solution was added to adjust the pH to 6.5, yielding an aqueous solution containing an aqueous polymer. The repeating unit composition of the aqueous polymer was 2-HEA / AA (H / Na) = 48 / 52 (molar ratio).

[0090] Example 3 23.8 g (0.33 mol) of acrylic acid, 22.6 g (0.19 mol) of 2-hydroxyethyl acrylate, 69.3 g (0.97 mol) of acrylamide, 0.608 g of ammonium persulfate, and 225.0 g of ion-exchanged water were added to a sealable vial with an internal volume of 500 ml and mixed to prepare an aqueous monomer solution. ２A 1 L reaction vessel equipped with a gas inlet tube, a reflux condenser, and a dropping funnel was charged with 607.6 g of ion-exchanged water, and N ２ After deoxygenating the system by blowing in gas, the internal temperature was raised to 75°C. Subsequently, the prepared aqueous monomer solution was added dropwise to the reaction vessel over a period of 3 hours using a dropping funnel while stirring. After the dropwise addition, the reaction vessel was maintained at this temperature for 2 hours. The internal temperature was then raised to 80°C and maintained at this temperature for 1 hour. The internal temperature was cooled to 30°C, and 70.57 g (0.30 mol) of a 5 mol / L aqueous sodium hydroxide solution was added to adjust the pH to 6.5, yielding an aqueous solution containing an aqueous polymer. The repeating unit composition of the aqueous polymer was 2-HEA / AA(H / Na) / AAm = 13 / 22 / 65 (molar ratio).

[0091] Comparative Example 1 46.5 g (0.54 mol) of methyl acrylate and 211.8 g (2.46 mol) of vinyl acetate were added to a sealable vial with an internal volume of 500 ml and mixed to prepare an aqueous monomer solution. ２ A 2-L reaction vessel equipped with a gas inlet tube, a reflux condenser, and a dropping funnel was charged with 768 g of ion-exchanged water and 12 g of anhydrous sodium sulfate, and N ２ Gas was blown into the system to deoxygenate it. Subsequently, 1 g of partially saponified polyvinyl alcohol (saponification degree 88%) and 1.2 g of lauryl peroxide were added, and the internal temperature was raised to 60°C. Subsequently, the prepared monomer aqueous solution was added dropwise to the reaction vessel over 4 hours using a dropping funnel while stirring. After the addition, the internal temperature was maintained at 65°C for 2 hours, and the precipitated solid was filtered. The same reaction vessel as above was charged with the obtained solid, 450 g of methanol, 420 g of ion-exchanged water, 140 g of sodium hydroxide, and 0.52 g of hydrazine, and the mixture was stirred at 35°C for 3 hours. Subsequently, the internal temperature was cooled to 30°C, acetic acid was added to adjust the pH to 7.5, and the solid was filtered. The solid was then washed with methanol and dried under reduced pressure at 60°C for 8 hours to obtain an aqueous polymer. The repeating unit composition of the aqueous polymer was VA / AA (H / Na) = 82 / 18 (molar ratio).

[0092] Comparative Example 2 103.6 g (1.20 mol) of methyl acrylate and 156.0 g (1.81 mol) of vinyl acetate were added to a 500 ml beaker and mixed to prepare an aqueous monomer solution. ２ A 2-L reaction vessel equipped with a gas inlet tube, a reflux condenser, and a dropping funnel was charged with 768 g of ion-exchanged water and 12 g of anhydrous sodium sulfate, and N ２ Gas was blown into the system to deoxygenate it. Subsequently, 1 g of partially saponified polyvinyl alcohol (saponification degree 88%) and 1.2 g of lauryl peroxide were added, and the internal temperature was raised to 60°C. Subsequently, the prepared monomer aqueous solution was added dropwise to the reaction vessel over 4 hours using a dropping funnel while stirring. After the addition, the internal temperature was maintained at 65°C for 2 hours, and the precipitated solid was filtered. The same reaction vessel as above was charged with the obtained solid, 450 g of methanol, 420 g of ion-exchanged water, 140 g of sodium hydroxide, and 0.52 g of hydrazine, and the mixture was stirred at 35°C for 3 hours. Subsequently, the internal temperature was cooled to 30°C, acetic acid was added to adjust the pH to 7.5, and the solid was filtered. The solid was then washed with methanol and dried under reduced pressure at 60°C for 8 hours to obtain an aqueous polymer. The repeating unit composition of the aqueous polymer was VA / AA (H / Na) = 60 / 40 (molar ratio).

[0093] <Measurement of polymer properties> The properties of the aqueous polymers obtained in the above-mentioned Reference Examples, Examples, and Comparative Examples were measured. The test methods are as follows. Note that all aqueous polymer solutions used in each test method were prepared by dissolving an aqueous polymer in ion-exchanged water.

[0094] [Molecular Weight, etc.] The Mw (weight average molecular weight), Rh (hydrodynamic radius), and Rg (radius of gyration) of the aqueous polymers obtained in the above Reference Examples, Examples, and Comparative Examples were measured using a GPC triple detector in terms of standard polyethylene glycol / polyethylene oxide. [GPC triple detector] GPC light scattering device: CHR6000 (manufactured by Malvern OMNISEC REVERAL) Column: TSK GMPW XL (Tosoh Corporation) Carrier: 0.1 M sodium nitrate Column temperature: 35°C Flow rate: 1.0 mL / min Injection volume: 150 μL Concentration: 2.0 mg / mL

[0095] [pH] An aqueous polymer was dissolved in water to a solids concentration of 2% by mass, and the aqueous solution was kept at 25°C. Then, the pH was measured using a pH meter (manufactured by Horiba, Ltd., model "D-71", glass pH electrode: model "9681S-10D") The pH was calculated by rounding the measured value to one decimal place.

[0096] [Viscosity] An aqueous polymer was dissolved in water to a solids concentration of 2% by mass, and the aqueous solution was kept at 25°C. The viscosity of the aqueous polymer solution was then measured using a Brookfield type viscometer (model DV1MLVTJ0, manufactured by Brookfield). The spindle and rotation speed corresponding to the viscosity were used during measurement as follows: LV-2, 12 rpm: 200 mPa·s or more and 2500 mPa·s or less LV-1, 30 rpm: 20 mPa·s or more and less than 200 mPa·s

[0097] [APHA] 30 ml of a polymer aqueous solution prepared by dissolving a water-based polymer in water to a solids concentration of 2% by mass was placed in a screw cap bottle, and the Hazen color number of the measurement sample was measured using a Hazen meter Type: HM-IV (X Electronics Design Co., Ltd.) in an environment of 25°C.

[0098] [Moisture Generation Amount at 170 to 290°C] 20 g of a polymer aqueous solution prepared by dissolving a water-based polymer in water to a solids concentration of 2% by mass was placed in a polypropylene tray (manufactured by AS ONE, model "DT-1") and dried at 60°C for 8 hours in a constant temperature incubator (manufactured by Yamato Scientific, model "DKM300"), followed by additional drying for 24 hours at 60°C and a reduced pressure of 0.1 MPa in a vacuum dryer (manufactured by AS ONE, model "AVO-310N") to produce a film. The film produced by the above method was cut into approximately 2 mm square pieces, and several pieces were used so that the weight of each piece was 10 mg. Measurement was performed under the following conditions using a Karl Fischer moisture meter (manufactured by Kyoto Electronics Manufacturing Co., Ltd., model "MCU-710") and a moisture evaporator (manufactured by Kyoto Electronics Manufacturing Co., Ltd., model "ADP-611"): Measurement mode: Moisture measurement. Measurement conditions: After heating to 80°C, the sample was kept at 80°C until the rate of weight loss reached 0.1 μg / s or less (Method A). The sample was then heated from 80°C to 300°C over 30 minutes (Method B). Method A: Data collection interval: 1 second. Method B: Data collection interval: 5 seconds. End-point potential: 200 mV. Measurement sample weight: 10 mg. Anolyte: Chem-Aqua anolyte AGE (Kyoto Electronics Manufacturing Co., Ltd.). Catholyte: Chem-Aqua catholyte CGE (Kyoto Electronics Manufacturing Co., Ltd.). Calculation of moisture generation: The weight after heating at 80°C until the rate of weight loss reached 0.1 μg / s or less was designated Wa, and the amount of moisture generated between 170°C and 290°C was designated Wb. The moisture generation rate was calculated using the following formula: Moisture generation rate = Wb / Wa x 100 [mass %].

[0099] [Glass Transition Temperature] 20 g of a polymer aqueous solution prepared by dissolving a water-based polymer in water to a solids concentration of 2% by mass was added to a polypropylene tray (manufactured by AS ONE, model "DT-1") and dried at 60°C for 8 hours in a constant temperature incubator (manufactured by Yamato Scientific, model "DKM300"), followed by additional drying for 24 hours at 60°C and a reduced pressure of 0.1 MPa in a vacuum dryer (manufactured by AS ONE, model "AVO-310N") to produce a film. The film produced by the above method was cut into 5 mg pieces (approximately 2 mm square) and measured using a differential scanning calorimeter (manufactured by Hitachi High-Tech Science, model "DSC600") under the following conditions. Measurement conditions: The temperature was increased from -30°C to 150°C at a rate of 10°C / min, cooled to -30°C at 10°C / min, and then increased to 400°C at 10°C / min. The glass transition temperature observed during the second heating was used. Sample pan: SUS bread Mass of measurement sample: 4 mg Calculation of glass transition temperature: The glass transition temperature was calculated by rounding off the decimal point of the temperature at the intersection of the tangent line at the start of the descent and the tangent line at the end of the descent on the chart measured during the second heating run using a differential scanning calorimeter.

[0100] <Characteristics of Battery / Slurry / Binder Liquid> Battery / slurry / binder liquid was prepared using the aqueous polymers obtained in the above-mentioned Reference Examples / Examples / Comparative Examples, and the characteristics thereof were measured. The test methods are as follows.

[0101] [Capacity Retention Rate After 100 Cycles] The capacity retention rate after 100 cycles was determined according to the following procedure. [Electrode Preparation] As electrode active materials, 23.3 parts by mass of artificial graphite (G-49, manufactured by Jiangxi Zichen Technology), 5.8 parts by mass of silicon monoxide (KSC-1265, manufactured by Shin-Etsu Chemical Co., Ltd.), and a polymer aqueous solution were kneaded together to a solid content of 0.9 parts by mass. Water was then added to the mixture to a solid content of 58% by mass, followed by kneading to prepare a negative electrode slurry. The resulting negative electrode slurry was applied to a rolled copper foil having a thickness of 18 μm and dried. The rolled copper foil and the coating were then bonded together using a roll press (manufactured by Ohno Roll Co., Ltd.), and then heat-treated (reduced pressure, 100°C, 12 hours or more) to prepare a negative electrode. The thickness of the active material layer in the obtained negative electrode was 36 μm, and the capacity density of the negative electrode was 3.5 mAh / cm ２ It was.

[0102] [Assembly of Coin Cell] A coin cell (CR2032) was fabricated comprising the negative electrode prepared above, the following positive electrode, separator, and electrolyte. Positive electrode: LiNi ０．５ Co ０．２ Mn ０．３ O ２ (Manufactured by Hachisansha Co., Ltd.) Separator: Glass filter (product name GA-100 manufactured by Advantec Co., Ltd.) Electrolyte: LiPF in a solvent made by mixing ethylene carbonate (EC) and diethyl carbonate (DEC) in a volume ratio of 1:1 ６ A solution obtained by dissolving the above at a concentration of 1 mol / L and adding 1 mass % of vinylene carbonate (VC) and 1 mass % of fluoroethylene carbonate (FEC), which are additives for electrolytes.

[0103] [Measurement of Capacity Retention Rate] Each coin cell prepared as described above was subjected to three cycles of charging at 30° C. to 4.2 V at a current corresponding to 0.1 C, discharging to 2.5 V at a current corresponding to 0.1 C, charging to 4.2 V at a current corresponding to 0.5 C, and discharging to 2.5 V at a current corresponding to 0.5 C, to perform battery aging. Subsequently, the coin cell was charged to 4.2 V at a current corresponding to 0.5 C, discharged to SOC 50 at a current corresponding to 0.5 C, discharged at a constant current for 12 seconds at a current corresponding to 0.2 C, charged for 24 seconds at a current corresponding to 0.1 C, discharged at a constant current for 12 seconds at a current corresponding to 0.5 C, charged for 1 minute at a current corresponding to 0.1 C, discharged at a constant current for 12 seconds at a current corresponding to 1 C, charged for 2 minutes at a current corresponding to 0.1 C, discharged at a constant current for 12 seconds at a current corresponding to 2 C, and then discharged to 2.5 V at a current corresponding to 0.2 C, and the initial discharge capacity was measured. Subsequently, the battery was charged to 4.2 V at a current equivalent to 1 C and discharged to 2.5 V at a current equivalent to 1 C for 97 cycles (4th to 100th cycles). The discharge capacity after 100 cycles was then measured using the same procedure as in measuring the initial discharge capacity. The capacity retention rate was calculated using the following formula: Capacity retention rate after 100 cycles = [Discharge capacity after 100 cycles (mAh / g)] / [Initial discharge capacity after aging (mAh / g)] × 100 [%]

[0104] [Discharge Capacity After 100 Cycles] The discharge capacity after 100 cycles in the above test for [Capacity Maintenance Rate After 100 Cycles] was measured.

[0105] [Direct Current Resistance (DCR) after 100 Cycles] [Electrode Fabrication] An electrode was fabricated in the same manner as described above in [Capacity Retention Rate after 100 Cycles]. [Coin Cell Assembly] A coin cell (CR2032) was fabricated in the same manner as described above in [Capacity Retention Rate after 100 Cycles], including a negative electrode, the following positive electrode, a separator, and an electrolyte.

[0106] [Measurement of DC Resistance After 100 Cycles] Each coin cell prepared as described above was subjected to three cycles of charging at 30°C to 4.2 V at a current corresponding to 0.1 C, discharging to 2.5 V at a current corresponding to 0.1 C, charging to 4.2 V at a current corresponding to 0.5 C, and discharging to 2.5 V at a current corresponding to 0.5 C, to age the battery. Subsequently, the battery was charged to 4.2 V at a current equivalent to 0.5 C, then discharged to SOC50 at a current equivalent to 0.5 C, and then subjected to a constant current discharge for 12 seconds at a current equivalent to 0.2 C. After that, the battery was charged for 24 seconds at a current equivalent to 0.1 C, and then subjected to a constant current discharge for 12 seconds at a current equivalent to 0.5 C. After that, the battery was charged for 1 minute at a current equivalent to 0.1 C, and then subjected to a constant current discharge for 12 seconds at a current equivalent to 1 C. After that, the battery was charged for 2 minutes at a current equivalent to 0.1 C, and then subjected to a constant current discharge for 12 seconds at a current equivalent to 2 C. The battery was then discharged to 2.5 V at a current equivalent to 0.2 C (initial discharge operation). Subsequently, the battery was charged to 4.2 V at a current equivalent to 1 C, and then subjected to a discharge operation to 2.5 V at a current equivalent to 1 C for 97 cycles (4th to 100th cycles). Thereafter, the same operation as the initial discharge operation was performed. The DC resistance of each coin cell was calculated from the discharge current and voltage values ​​at 10.0 seconds of C-rate, and was taken as the DC resistance after 100 cycles.

[0107] [Foaming (Low Foaming After 15 Minutes)] A polymer aqueous solution prepared by dissolving a water-based polymer in water to a solids concentration of 2% by mass was poured into a glass bottle (diameter 45 mm, height 110 mm) to a height of 5.5 cm, and a 35 mm diameter disper (manufactured by PRIMIX, model "Homo Disper 2.5") was added to a height of 3.5 cm, followed by stirring for 2 minutes at 2500 rpm in an environment of 23° C. The state of foaming after 15 minutes of stirring was visually confirmed, and a solution with almost no bubbles (approximately 20 or less bubbles in the solution) was rated as ◯, and a solution with many bubbles visible throughout was rated as ×.

[0108] The test results are summarized in the table below.

[0109] The present disclosure is suitable for use as a power source for mobile communication devices, portable electronic devices, electric bicycles, electric motorcycles, electric vehicles, and the like.

[0110] Furthermore, the present disclosure also includes the following aspects: [Item 1] A secondary battery binder comprising an aqueous polymer, wherein the amount of moisture generated by the aqueous polymer at 170°C to 290°C is 15% by mass or less. [Item 2] The secondary battery binder according to Item 1, wherein the amount of moisture generated is 2.5% by mass or more. [Item 3] The secondary battery binder according to Item 1 or 2, wherein the aqueous polymer is a vinyl polymer having an acidic functional group-containing repeating unit. [Item 4] The aqueous polymer is a compound represented by the formula: -[CH ２ -C(R １ ) (C(=O)R ２ )] - [wherein, R 1 is a hydrogen atom or CH ３ and R 2 is NH ２ , OM (M is a hydrogen atom or a counter cation), O(CH ２ ) ｎ OH, NH(CH ２ ) ｎ OH (wherein n is independently 1 or more and 6 or less).] and a repeating unit (1) represented by the formula: -[CH ２ The secondary battery binder according to any one of Items 1 to 3, comprising a repeating unit selected from the repeating unit (2) represented by the formula: -CH(OH)]-. [Item 5] The secondary battery binder according to Item 4, wherein in the aqueous polymer, the amount of the repeating unit selected from the repeating unit (1) and the repeating unit (2) is 40 mol % or more, the amount of the acidic functional group-containing repeating unit is 0.8 mol % or more, and the amount of the nonionic repeating unit is 40 mol % or more. [Item 6] The secondary battery binder according to any one of Items 1 to 5, comprising SBR. [Item 7] A slurry comprising the secondary battery binder according to any one of Items 1 to 6 and water. [Item 8] The slurry according to Item 7, further comprising an electrode active material. [Item 9] A method for producing a secondary battery, comprising a step of applying the slurry according to Item 7 or 8. [Item 10] An electrode comprising the secondary battery binder according to Items 1 to 6 or a component derived from the secondary battery binder. [Item 11] An electrode comprising a heat-dried product of the slurry according to Item 7 or 8. [Item 12] A secondary battery comprising the electrode according to Item 10 or 11.

Claims

1. A secondary battery binder comprising a water-based polymer, the amount of moisture generated by the water-based polymer at 170°C to 290°C being 15% by mass or less as measured by the following measurement method, the water-based polymer being a vinyl polymer having a repeating unit having an acidic functional group and a nonionic hydrophilic repeating unit, the weight-average molecular weight of the water-based polymer being 1,000,000 or less, and the pH of the aqueous solution obtained by dissolving the water-based polymer in water to a concentration of 2% by mass at 25°C being 6.5 or more and 8.5 or less. [Amount of moisture generated at 170°C to 290°C] 20 g of an aqueous polymer solution prepared by dissolving the water-based polymer in water to a solids concentration of 2% by mass was added to a tray, dried at 60°C for 8 hours in a constant temperature incubator with a forced air blower, and then further dried in a vacuum dryer at 60°C and a reduced pressure of 0.1 MPa for 24 hours to produce a film. The prepared film was cut into approximately 2 mm square pieces, each measuring 10 mg, and measured using a Karl Fischer moisture meter and moisture vaporizer under the following conditions. Measurement conditions: After heating to 80°C, the film was kept at 80°C until the rate of weight loss reached 0.1 μg / s or less (Method A). The film was then heated from 80°C to 300°C over 30 minutes (Method B). Method A data collection interval: 1 second; Method B data collection interval: 5 seconds. Calculation of moisture content: The weight after keeping the film at 80°C until the rate of weight loss reached 0.1 μg / s or less was designated Wa, and the amount of moisture generated detected between 170°C and 290°C was designated Wb. The moisture content was calculated using the following formula: Moisture content = Wb / Wa x 100 [% by mass] 2. The secondary battery binder according to claim 1, wherein the amount of moisture generated is 2.5 mass % or more.

3. The water-based polymer has the formula: -[CH ２ -C(R １ ) (C(=O)R ２ )] - [wherein, R 1 is a hydrogen atom or CH ３ and R 2 is NH ２ , OM (M is a hydrogen atom or a counter cation), O(CH ２ ) ｎ OH, NH(CH ２ ) ｎ OH (wherein n is independently 1 or more and 6 or less).] and a repeating unit (1) represented by the formula: -[CH ２ 3. The secondary battery binder according to claim 1, comprising a repeating unit selected from the repeating unit (2) represented by the formula:

4. The secondary battery binder according to claim 3, wherein in the aqueous polymer, the amount of the repeating unit selected from the repeating unit (1) and the repeating unit (2) is 40 mol % or more, the amount of the repeating unit containing an acidic functional group is 0.8 mol % or more, and the amount of the nonionic repeating unit is 40 mol % or more.

5. The secondary battery binder according to claim 1 or 2, which contains SBR.

6. A slurry comprising the secondary battery binder according to claim 1 or 2 and water.

7. The slurry of claim 6, further comprising an electrode active material.

8. A method for producing a secondary battery, comprising the step of applying the slurry according to claim 6.

9. An electrode comprising the secondary battery binder according to claim 1 or 2 or a component derived from said secondary battery binder.

10. An electrode comprising the heat-dried slurry of claim 6.

11. A secondary battery comprising the electrode according to claim 9.

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