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

Abstract

The present invention provides a novel secondary battery binder that can favorably contribute to the production of a battery and / or the battery characteristics, or a slurry containing the secondary battery binder. The present invention relates to a method for producing a water-based polymer. The aqueous solution obtained when the aqueous polymer is dissolved in water at a concentration of 2% by mass has a Na concentration of 0.05% by mass or more and 0.25% by mass or less, The secondary battery binder has an electrolyte absorption rate (25°C) of 8.0% or less of the aqueous polymer.

Description

[Technical Field]

[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. [Background technology]

[0002] Slurries containing binders are used in the manufacturing process of secondary batteries, particularly in the manufacturing process of electrodes. In recent years, due to concerns about the impact on the environment, interest has been 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. [Prior art documents] [Patent documents]

[0003] [Patent Document 1] Japanese Patent Application Laid-Open No. 2012-49061 Summary of the Invention [Problem to be solved by the invention]

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

[0005] The present disclosure includes the following aspects: [Section 1] Contains water-based polymers, The aqueous solution obtained when the aqueous polymer is dissolved in water at a concentration of 2% by mass has a Na concentration of 0.05% by mass or more and 0.25% by mass or less, The secondary battery binder has an electrolyte absorption rate (25°C) of 8.0% or less of the aqueous polymer. [Section 2] Item 2. The secondary battery binder according to item 1, wherein the electrolyte absorption rate (25° C.) is 2% or more and 6.5% or less. [Section 3] 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. [Section 4] The water-based polymer is formula: -[CH2-C(R 1 )(C(=O)R 2 )]- [In the formula, R 1 is a hydrogen atom or CH3, R 2 NH2, OM (M is a hydrogen atom or a counter cation), O(CH2) n OH, NH(CH2) n OH (wherein each n is independently 1 or more and 6 or less). A repeating unit (1) represented by the formula: formula: -[CH2-CH(OH)]- Repeating unit (2) 4. The secondary battery binder according to any one of items 1 to 3, comprising a repeating unit selected from the following: [Section 5] In the water-based 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 repeating units containing an acidic functional group is 0.8 mol% or more, Item 5. The secondary battery binder according to item 4, wherein the amount of nonionic repeating units is 40 mol % or more. [Section 6] Item 6. The secondary battery binder according to any one of items 1 to 5, which contains SBR. [Section 7] Item 7. A slurry comprising the secondary battery binder according to any one of Items 1 to 6 and water. [Section 8] Item 8. The slurry according to Item 7, further comprising an electrode active material. [Section 9] Item 9. A method for producing a secondary battery, comprising applying the slurry according to Item 7 or 8. [Section 10] Item 7. An electrode comprising the secondary battery binder according to any one of Items 1 to 6 or a component derived from the secondary battery binder. [Section 11] Item 7. An electrode comprising a heated and dried slurry according to item 7 or 8. [Section 12] Item 12. A secondary battery comprising the electrode according to item 10 or 11. [Effects of the Invention]

[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 battery expansion after charge-discharge cycles. DETAILED DESCRIPTION OF THE INVENTION

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

[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 in particular, is water-soluble.

[0012] [Characteristics of water-based polymers] The properties of water-based polymers are shown below.

[0013] (water soluble) 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.)

[0015] The Mw (weight average molecular weight) of the aqueous polymer measured by GPC-RI may be 100,000 or more, 300,000 or more, 500,000 or more, 750,000 or more, or 1,500,000 or more, preferably 100,000 or more, more preferably 500,000 or more, and may be 3,000,000 or less, 1,000,000 or less, 500,000 or less, or 250,000 or less, preferably 1,000,000 or less, more preferably 800,000 or less. This value is determined by the method described in the examples.

[0016] (pH) The pH (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 5.0 or more, 5.5 or more, 6.0 or more, 6.5 or more, 7.0 or more, 7.5 or more, 8.0 or more, 8.5 or more, or 9.0 or more, preferably 5.5 or more, more preferably 6.5 or more, and may be 10 or less, 9.5 or less, 9.0 or less, 8.5 or less, 8.0 or less, 7.5 or less, or 7.0 or less, preferably 9.0 or less, more preferably 8.5 or less. This value is determined by the method described in the Examples. Ion-exchanged water is usually used as the water. When the pH is equal to or higher than the lower limit (particularly 7.0 or higher (neutral to alkaline)), the flexibility of the polymer component including the aqueous polymer is increased, and the polymer component can exhibit high compliance with the expansion and contraction of the active material. Similarly, when the pH is equal to or higher than the lower limit, the dispersibility of the slurry can be improved. By keeping the pH within the above range (particularly 5.0 or more and 7.5 or less), the viscosity stability of the aqueous polymer solution is good, which is preferable from the viewpoint of productivity in battery production.

[0017] (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 5 mPa·s or more, more preferably 25 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 300 mPa·s or less, more preferably 100 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., 5 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 formed well on the active material, and expansion of the electrode (particularly the initial expansion rate) when the battery is formed can be suppressed. Similarly, by setting the viscosity within the above range, the dispersibility of the slurry can be improved.

[0018] (conductivity) The conductivity of the aqueous solution obtained when a water-based polymer is dissolved in water at a concentration of 2% by mass may be 0.5 mS / cm or more, 1.5 mS / cm or more, 2.5 mS / cm or more, 3.0 mS / cm or more, 3.5 mS / cm or more, or 4.5 mS / cm or more, preferably 2.0 mS / cm or more, more preferably 2.5 mS / cm or more, and may be 10 mS / cm or less, 7.5 mS / cm or less, or 5.0 mS / cm or less, preferably 7.5 mS / cm or less, more preferably 4.0 mS / cm or less. This value is determined by the method described in the Examples. Ion-exchanged water is usually used as the water. A relatively low conductivity (e.g., 3.3 mS / cm or less, particularly 3.0 mS / cm or less) favorably suppresses foaming during stirring of the aqueous solution. Furthermore, a conductivity within the above range is thought to prevent the concentration of ionic components from becoming too high, suppressing the surfactant properties of the ionic components and suppressing foaming. When the conductivity is relatively high (especially 3.3 mS / cm or higher), the viscosity stability of the aqueous solution is favorable. This is thought to be because, when the conductivity is high, the concentration of polar functional groups derived from the structure of the water-based polymer increases, and the ionic interactions become stronger, stabilizing the viscosity of the aqueous solution.

[0019] (Na concentration) The aqueous solution obtained by dissolving the water-based polymer in water at a concentration of 2% by mass has a sodium concentration of 0.05% by mass or more and 0.25% by mass or less. When the sodium concentration is in this range, expansion of the electrode after charge-discharge cycles can be suppressed. When the Na concentration is equal to or greater than the lower limit, uneven distribution of the aqueous polymer in the slurry is suppressed, and uneven distribution of the binder when the battery is formed can also be suppressed, which is thought to facilitate suppression of expansion of the active material. A preferred lower limit is 0.10% by mass or greater. Furthermore, when the Na concentration is equal to or less than the upper limit, adhesion to the active material is improved, which is thought to suppress expansion. In addition, it is thought that the uniformity of the slurry is improved, and an increase in battery resistance can also be suppressed. This value is determined by the method described in the Examples. Ion-exchanged water is usually used as the water.

[0020] (Electrolyte absorption rate (25℃)) The electrolyte absorption rate of the aqueous polymer (at 25°C) is 8.0% or less. When the electrolyte absorption rate is within the above range, the DC resistance of the battery after charge / discharge cycles is suitably suppressed. From the same viewpoint, it is preferably 6.5% or less, and more preferably 2% to 6.5%. Aqueous polymers with an electrolyte absorption rate (25°C) below the upper limit mentioned above tend to have relatively high rigidity and high binder film strength. As a result, it is believed that the binder film is less likely to tear or peel off when the active material swells and shrinks due to charging and discharging of the battery, and it is believed that this can maintain a high coverage of the active material, suppress the formation of a high-resistance film due to decomposition of the electrolyte upon contact with the electrolyte, and suppress an increase in the battery's DC resistance. This value can be determined by the method described in the Examples.

[0021] [Water-based polymer structure, etc.] The aqueous polymer can be obtained by polymerizing one or more types of monomers. The aqueous polymer can be a vinyl polymer. The vinyl polymer is a polymer obtained by polymerizing a vinyl monomer. The vinyl monomer can be any compound having a polymerizable carbon-carbon double bond (ethylenically unsaturated double bond) (>C=C<), and can 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 aqueous polymer can 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 carboxyl group, a sulfonic acid group, a phosphate group, and a nitrate group; cationic groups such as an amino group; a hydroxyl 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 may be partially or completely in the form of a salt.

[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 preferably 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 of the present disclosure may have a nonionic hydrophilic repeating unit, examples of which include (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: formula: -[CH2-C(R 1 )(C(=O)R 2 )]- [In the formula, R 1 is a hydrogen atom or CH3, R 2 NH2, OM (M is a hydrogen atom or a counter cation), O(CH2) n OH, NH(CH2) n OH (wherein each n is independently 1 or more and 6 or less). A repeating unit (1) represented by the formula: formula: -[CH2-CH(OH)]- Repeating unit (2) Examples of repeating units include those selected from the following:

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

[0030] In the repeating unit (1), R 2 In the formula (I), M 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 an ONa group, or R 2 The repeating unit (1) may be only an OLi group. 2 may contain ONa groups and OH groups, and R 2 may contain OLi groups and OH groups, may contain NH2 groups and OH groups, may contain NH2 groups, OH groups and ONa groups, may contain NH2 groups, OH groups, ONa groups and OLi groups, or R 2 may include those with 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) and then saponifying it, or by reacting it with a polymer having a vinyl alcohol-based repeating unit (for example, 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 water-based polymers] 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 20 mol% or more, more preferably 40 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, 60 mol% or more, 80 mol% or more, or 90 mol% or more, preferably 5 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 90 mol% or less, more preferably 60 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 20 mol% or more, more preferably 40 mol% or more, and may be 100 mol% or less, 90 mol% or less, 80 mol% or less, or 70 mol% or less, preferably 90 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 20 mol% or more, more preferably 40 mol% or more, and may be 100 mol% or less, 90 mol% or less, 80 mol% or less, or 70 mol% or less, preferably 90 mol% or less, more preferably 80 mol% or less.

[0041] The total amount of repeating units (1) and repeating units (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 90 mol% or less, more preferably 80 mol% or less.

[0042] The amount of repeating unit (1) 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 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 90 mol% or less, more preferably 80 mol% or less.

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

[0044] A repeating unit derived from (meth)acrylamide (R 2 The amount of NH2) 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, more preferably 30 mol% or more, and may be 90 mol% or less, 80 mol% or less, or 70 mol% or less, preferably 90 mol% or less, more preferably 70 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 10 mol% or more, more preferably 20 mol% or more, and may be 90 mol% or less, 80 mol% or less, or 70 mol% or less, preferably 90 mol% or less, more preferably 70 mol% or less.

[0046] [Method of manufacturing water-based polymers] The aqueous polymer can be produced by any known method for producing copolymers. Preferably, it 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 resulting mixture is stirred while undergoing a polymerization reaction at a reaction temperature of approximately 50 to 100°C (e.g., 60 to 70°C). 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 3°C to 10°C above the reaction temperature (e.g., 4°C to 8°C). 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 WO2017 / 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 polymerization initiators that combine such persulfates with reducing agents such as sodium hydrogen sulfite; and azo initiators such as 2,2'-azobis-2-amidinopropane dihydrochloride (NC-32) (V-50) and 2,2'-azobis[2-(2-imidazolin-2-yl)propane] dihydrochloride (VA-044). The amount of radical polymerization initiator used is preferably about 0.05 to 2% by mass, more preferably about 0.1 to 1.5% by mass, based on 100% by mass of the monomers that serve as raw materials 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 aqueous 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 aqueous polymer alone.

[0051] [Other binder components] The secondary battery binder of the present disclosure may contain other binder components in addition to the aqueous polymer. Examples of other 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 is preferably 10% by mass or less.

[0055] [Amount of liquid medium] The amount of the liquid medium is adjusted according to the desired slurry solids concentration. The amount of the liquid medium may be 20% by mass or more, 30% by mass or more, 40% by mass or more, 50% by mass or more, or 60% by mass or more, preferably 30% by mass or more, more preferably 50% by mass or more, based on the slurry solids (total amount of the secondary battery binder, active material, and conductive additive), and may be 80% by mass or less, 70% by mass or less, 60% by mass or less, 50% by mass or less, or 40% by mass or less, preferably 70% by mass or less, more preferably 60% by mass or less.

[0056] [Secondary battery binder] The slurry contains a secondary battery binder, the types of which are 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 may be 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 3.0% by mass or less, more preferably 1.0% by mass or less. A content equal to or greater than the above lower limit is preferred from the viewpoint of achieving a good binder effect. A content equal to or less than the above upper limit is preferred from the viewpoint of achieving a high-capacity battery.

[0058] [Active material] The active material is an electrode active material, including a negative electrode active material or a positive electrode active material. When the active material is, for example, a negative electrode active material, it can include, for example, a carbon material, and can also include at least one of silicon and silicon oxide. Specific materials of the negative electrode active material and the positive electrode active material are exemplified below.

[0059] (Negative electrode active material) The negative electrode active material may be a negative electrode active material used in the technical field.

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

[0061] As the negative electrode active material, materials capable of storing and releasing a large amount of lithium ions such as silicon (Si), tin (Sn), titanium (Ti), etc. may be used. These materials can be used in the form of a single substance, alloy, compound, solid solution, or a composite active material containing a silicon-containing material, a tin-containing material, or a titanium-containing material. Examples of the silicon-containing material include Si, Si / C, SiOx (0.05 < x < 1.95), or an alloy, compound, or solid solution 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 replaces a part of Si in any of these. The silicon-containing material may be a silicon oxide. Examples of the tin-containing material include Ni2Sn4, Mg2Sn, SnOx (0 < x < 2), SnO2, SnSiO3, LiSnO, etc. Examples of the titanium-containing material include Li2TiO3, Li4Ti5O 12Examples 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. Any carbon material commonly used in secondary batteries, particularly non-aqueous electrolyte secondary batteries, can be used as the carbon material. Crystalline carbon, amorphous carbon, or a combination of these may be used. Examples of crystalline carbon include those mentioned 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] (Cathode active material) The positive electrode active material is not particularly limited, and any positive electrode active material commonly used in the art may be used.

[0065] The positive electrode active material may be a lithium-containing composite oxide, such as LiMnO2, LiFeO2, LiCoO2, LiMn2O4, Li2FeSiO4, or 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 zO2 (where 0 ≤ x < 1, 0 ≤ y < 1, 0 ≤ z < 1, and 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. may be mentioned.

[0066] [Amount of active material] The amount of the active material 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, 95% by mass or more in the slurry solid content (total amount of the secondary battery binder, the active material, and the conductive assistant), preferably 55% by mass or more, more preferably 75% by mass or more, and may also be 99% by mass or less, 95% by mass or less, 90% by mass or less, or 85% by mass or less.

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

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

[0069] <00ooo359>[Dispersing agent] The slurry of the present disclosure may further contain a dispersing aid. Examples of the dispersing aid include an organic acid containing at least one substituent selected from the group consisting of a hydroxy group, an amino group, and an imino group, and a carboxy group, or humic acid. Examples of organic acids containing a hydroxy group and a carboxy 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 carboxy 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 carboxy 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 dispersing agent] The amount of the dispersion aid may be 0.1 mass% or more, 0.5 mass% or more, 1.0 mass% or more, 1.5 mass% or more, or 3.0 mass% or more, and is preferably 0.3 mass% or more, and may be 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, based on the slurry solids content (total amount of secondary battery binder, active material, and conductive aid).

[0071] [Other ingredients] The slurries of the present disclosure may also contain other ingredients, such as conventional additives.

[0072] [Amount of other ingredients] The amount of other components (individual amount or total amount) of 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, 1.0 mass% or less, 0.5 mass% or less, preferably 3.0 mass% or less, and more preferably 1.0 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 the components. For example, a binder, a liquid medium, an active material, and, if necessary, a conductive aid, a dispersing aid, etc. are mixed to form a slurry. The timing of adding the liquid medium is not particularly limited. The binder of the present disclosure may be dispersed or dissolved in the liquid medium in advance, and then the active material and other components may be mixed to form a slurry. Alternatively, the active material, the binder of the present disclosure, and, if necessary, a conductive aid, a dispersing aid, etc. may be mixed in a solid state, and then the liquid medium may be added to form a paste-like slurry.

[0074] <Electrode> The electrode of the present disclosure is an electrode for a secondary battery, and includes the aforementioned secondary battery binder (or a component derived from the secondary battery binder) of the present disclosure and an active material. That is, the electrode of the present disclosure can be produced, for example, by applying the aforementioned 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 substance 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 substances (e.g., stainless steel). The current collector may also be made of Fe plated with Cu. From the viewpoints of high electrical conductivity, stability in the electrolyte, and oxidation resistance, Cu, Ni, stainless steel, etc. are preferred as materials 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, stability in the electrolyte, and 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-like substrate, a three-dimensional substrate, etc. Using 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 aforementioned 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 fabricated 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. [Example]

[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 MAS: methallylsulfonic acid VA: vinyl alcohol CMC: Carboxymethyl cellulose SBR: Styrene butadiene rubber

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

[0087] Example 1 A sealable vial having an internal volume of 500 ml was charged with 35.3 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 (Fujifilm Wako Pure Chemical Industries, Ltd. product name "VA-044"), and 210.0 g of ion-exchanged water, and the resulting mixture was mixed to prepare an aqueous monomer solution, which was then deoxygenated. Separately, a 2 L reactor equipped with a stirrer, thermometer, N2 gas inlet, reflux condenser, and dropping funnel was charged with 858.3 g of ion-exchanged water. N2 gas was blown into the reactor to deoxygenate the system, and the internal temperature was raised to 68 °C. Subsequently, the deoxygenated monomer aqueous solution was added dropwise to the reactor over 3 hours using the dropping funnel while stirring. After the 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 48 wt% NaOH aqueous solution was added until the pH reached 5.5, yielding an aqueous solution containing a water-based polymer. The repeating unit composition of the water-based polymer was AAm / AA(H / Na) / 2-HEA / MAS(H / Na) = 35 / 35 / 29.9 / 0.1 (molar ratio).

[0088] Example 2 Into a sealable vial having an internal volume of 500 ml, 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 and mixed to prepare an aqueous monomer solution, which was then deoxygenated. Separately, 500.0 g of ion-exchanged water was charged into a 1 L reactor equipped with a stirrer, thermometer, N2 gas inlet tube, reflux condenser, and dropping funnel. N2 gas was blown into the system to deoxygenate it, and the internal temperature was raised to 75 °C. The prepared monomer aqueous solution was then added dropwise to the reactor using the dropping funnel over 3 hours while stirring. After the 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 a water-based polymer. The repeating unit composition of the water-based polymer was 2-HEA / AA (H / Na) = 48 / 52 (molar ratio).

[0089] Example 3 A monomer aqueous solution was prepared by adding 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 to a sealable vial having an internal volume of 500 ml and mixing them. Separately, a 1 L reactor equipped with a stirrer, thermometer, N2 gas inlet tube, reflux condenser, and dropping funnel was charged with 607.6 g of ion-exchanged water. N2 gas was blown into the system to deoxygenate it, and the internal temperature was raised to 75 °C. Subsequently, the prepared monomer aqueous solution was added dropwise to the reactor using the dropping funnel over 3 hours while stirring. After the addition, the mixture was maintained for 2 hours. The internal temperature was then raised to 80 °C and maintained 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 a water-based polymer. The repeating unit composition of the water-based polymer was 2-HEA / AA(H / Na) / AAm = 13 / 22 / 65 (molar ratio).

[0090] Example 4 In a 500 ml beaker and a sealable 500 ml vial, 46.5 g (0.54 mol) of methyl acrylate and 211.8 g (2.46 mol) of vinyl acetate were added and mixed to prepare an aqueous monomer solution. Separately, a 2 L reactor equipped with a stirrer, thermometer, N2 gas inlet tube, reflux condenser, and dropping funnel was charged with 768 g of ion-exchanged water and 12 g of anhydrous sodium sulfate, and N2 gas was blown in to deoxygenate the system. 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 reactor over 4 hours using the 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 obtained solid, 450 g of methanol, 420 g of ion-exchanged water, 140 g of sodium hydroxide, and 0.52 g of hydrazine were charged to the same reactor as above, 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 content was filtered off. The solid content was washed with methanol and dried under reduced pressure at 60°C for 8 hours to obtain an aqueous polymer. The composition of the repeating units of the aqueous polymer was VA / AA (H / Na) = 82 / 18 (molar ratio).

[0091] Comparative Example 1 A 2 L reactor equipped with a stirrer, thermometer, N2 gas inlet, reflux condenser, and dropping funnel was charged with 831.0 g of ion-exchanged water. N2 gas was blown in to deoxygenate the system, and the internal temperature was raised to 68 °C. A previously prepared mixture of 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 (Fujifilm Wako Pure Chemical Industries, Ltd. product name "VA-044"), and 250.0 g of ion-exchanged water was added dropwise via the dropping funnel over 3 hours. After the 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, and then at 73°C for 1 hour to obtain an aqueous solution containing a water-based polymer. The repeating unit composition of the water-based polymer was AAm / MAS(H / Na) = 99 / 1 (molar ratio).

[0092] Comparative Example 2 A 1 L reaction vessel equipped with a stirrer, thermometer, N2 gas inlet tube, reflux condenser, and dropping funnel was charged with 485.3 g of ion-exchanged water and 100.0 g of terminally thiol-modified polyvinyl alcohol (degree of polymerization: 375, degree of saponification: 98.7 mol%). N2 gas was blown in to deoxygenate the system, and the internal temperature was raised to 95°C and then cooled to room temperature. The pH was then adjusted to 3.0 with 0.5 N sulfuric acid. The internal temperature was then raised to 62°C, and with stirring, 9.9 g (0.14 mol) of acrylic acid, 1.70 g of ammonium persulfate, and 75.2 g of ion-exchanged water were added dropwise via the dropping funnel over 1.5 hours. After the dropwise addition, the internal temperature was maintained at 62°C for 0.5 hours, followed by stirring at 67°C for 1 hour. The internal temperature was then cooled to 30°C, and 5.72 g (0.69 mol) of 48% by mass aqueous sodium hydroxide solution was added to obtain an aqueous solution containing a water-based polymer. The composition of the repeating units of the water-based polymer was VA / AA (H / Na) = 94 / 6 (molar ratio).

[0093] Comparative Example 3 A mixture of carboxymethyl cellulose and styrene-butadiene rubber (CMC / SBR=1 / 2 (solid weight ratio)) was used.

[0094] <Measurement of polymer properties> The properties of the water-based polymers obtained in the above examples and comparative examples were measured using the following test methods.

[0095] [Molecular weight, etc.] The weight average molecular weight (Mw) of the aqueous polymers obtained in the above examples and comparative examples was measured using GPC-RI in terms of standard polyethylene glycol / polyethylene oxide. Detailed conditions are as follows: [GPC-RI] GPC equipment: HLC-8320GPC (Tosoh Corporation) Column: TSK GMPW XL (Tosoh Corporation) Carrier: 0.1M sodium nitrate Column temperature: 40℃ Flow rate: 1.0mL / min Injection volume: 200μL Concentration: 0.5mg / mL

[0096] [pH] A polymer aqueous solution was prepared by dissolving a water-based polymer in water to a solids concentration of 2% by mass, and the 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.

[0097] 〔viscosity〕 A polymer aqueous solution was prepared by dissolving a water-based polymer in water to a solids concentration of 2% by mass, and the solution was kept at 25°C. The viscosity of the polymer aqueous solution was then measured using a Brookfield type viscometer (model DV1MLVTJ0). The spindle and rotation speed corresponding to the viscosity were used during the measurement, as follows: LV-2, 12 rpm: 250 to 2500 mPa·s LV-1, 30 rpm: 20 to 200 mPa·s

[0098] 〔conductivity〕 A polymer aqueous solution was prepared by dissolving a water-based polymer in water to a solids concentration of 2% by mass, and after keeping the temperature at 25°C, the conductivity was measured using a conductivity meter (manufactured by AS ONE, model "AS710") The conductivity was calculated by rounding the measured value to one decimal place.

[0099] [Na concentration] A water-based polymer was dissolved in water to a solids concentration of 2% by mass to prepare a polymer aqueous solution. 60% by mass nitric acid was added to the solution, and the solution was heated and dissolved to prepare a measurement solution. The mass of Na contained in the measurement solution was measured by analysis using an inductively coupled plasma atomic emission spectrometer (manufactured by Thermo Fisher Scientific). The Na concentration of the 2% by mass aqueous polymer solution was calculated using the following formula: Na concentration = mass of Na in the measurement solution / mass of the aqueous polymer solution added × 100 [%]

[0100] [Electrolyte absorption rate (25℃)] A polymer aqueous solution was prepared by dissolving a water-based polymer in water to a solids concentration of 2% by mass. 20 g of this solution was added to a polypropylene tray (manufactured by AS ONE, model "DT-1") and dried at 60°C for 15 hours in a constant temperature incubator (manufactured by Yamato Scientific, model "DKM300"), followed by additional drying for 24 hours in a vacuum dryer (manufactured by AS ONE, model "AVO-310N") at 60°C and a reduced pressure of 0.1 MPa to produce a film. The film prepared by the above method was cut into 40 mg pieces (approximately 2 cm square) in a dry oven with a dew point of -70°C, and the weight of the film before immersion in the electrolyte was measured. The cut film was then placed in a 50 mL screw cap vial, and 20 g of electrolyte (ethylene carbonate / dimethyl carbonate = 1 / 1 v / v%, Kishida Chemical) was added to immerse the film. The screw cap vial was then sealed and stored for 22 hours in a safety tester (ESPEC, model "CSH112") set at 25°C. After storage, the film was removed from the electrolyte in the dry oven, sandwiched between Kimwipes and a load of approximately 700 g was applied from above for 2 seconds to wipe off the electrolyte. After immersion in the electrolyte, the weight was measured and the electrolyte absorption rate was calculated using the following formula. Electrolyte absorption rate = (Weight after immersion in electrolyte - Weight before immersion in electrolyte) / Weight before immersion in electrolyte x 100[%] <Characteristics of batteries / slurries / binder liquids, etc.> Using the aqueous polymers obtained in the above examples and comparative examples, batteries, slurries, and binder solutions were prepared and their properties were measured. The test methods were 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 0.9 parts by mass of a polymer aqueous solution (solid content equivalent) were kneaded together. Water was then added to the mixture to achieve 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 with a thickness of 18 μm and dried. The rolled copper foil and the coating were then intimately bonded together using a roll press (manufactured by Ohno Roll Co., Ltd.), followed by heat treatment (reduced pressure, 100°C, 12 hours or more) to prepare a negative electrode. The thickness of the active material layer in the resulting negative electrode was 36 μm, and the capacity density of the negative electrode was 3.5 mAh / cm. 2 It was.

[0102] [Coin cell assembly] A coin cell (CR2032) was prepared comprising the negative electrode prepared above, the following positive electrode, separator, and electrolyte. ·Positive electrode: LiNi 0.5 Co 0.2 Mn 0.3 O2 (manufactured by Hachisansha Co., Ltd.) Separator: Glass filter (Advantech Co., Ltd., product name GA-100) Electrolyte: A solution in which LiPF6 is dissolved at a concentration of 1 mol / L in a solvent made by mixing ethylene carbonate (EC) and diethyl carbonate (DEC) in a volume ratio of 1:1, and 1 mass% of vinylene carbonate (VC) and 1 mass% of fluoroethylene carbonate (FEC), which are electrolyte additives, are added.

[0103] [Capacity retention rate measurement] Each coin cell prepared as described above was charged to 4.2 V at 30°C with a current equivalent to 0.1 C, discharged to 2.5 V at a current equivalent to 0.1 C, charged to 4.2 V at a current equivalent to 0.5 C, and discharged to 2.5 V at a current equivalent to 0.5 C for three cycles 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, discharged at a constant current for 12 seconds at a current equivalent to 0.2 C, then charged at a current equivalent to 0.1 C for 24 seconds, discharged at a constant current for 12 seconds at a current equivalent to 0.5 C, then charged at a current equivalent to 0.1 C for 1 minute, discharged at a constant current for 12 seconds at a current equivalent to 1 C, then charged at a current equivalent to 0.1 C for 2 minutes, discharged at a constant current for 12 seconds at a current equivalent to 2 C, and then discharged to 2.5 V at a current equivalent 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, and this cycle was repeated for 97 cycles (4th to 100th cycles). Thereafter, the same operation as that used to measure the initial discharge capacity was carried out to measure the discharge capacity after 100 cycles. 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] In the above test for [Capacity retention rate after 100 cycles], the discharge capacity after 100 cycles was measured.

[0105] [Expansion rate after 100 cycles] The expansion rate after 100 cycles was determined according to the following procedure. [Electrode preparation] An electrode was prepared in the same manner as described above in [Capacity retention rate after 100 cycles].

[0106] [Coin cell assembly] As described above in [Capacity retention rate after 100 cycles], a coin cell (CR2032) was prepared, which included a negative electrode, the following positive electrode, a separator, and an electrolyte solution.

[0107] [Expansion rate measurement] Each coin cell prepared as described above was charged to 4.2 V at 30°C with a current equivalent to 0.1 C, discharged to 2.5 V at a current equivalent to 0.1 C, charged to 4.2 V at a current equivalent to 0.5 C, and discharged to 2.5 V at a current equivalent to 0.5 C for three cycles 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, discharged at a constant current for 12 seconds at a current equivalent to 0.2 C, then charged at a current equivalent to 0.1 C for 24 seconds, discharged at a constant current for 12 seconds at a current equivalent to 0.5 C, then charged at a current equivalent to 0.1 C for 1 minute, discharged at a constant current for 12 seconds at a current equivalent to 1 C, then charged at a current equivalent to 0.1 C for 2 minutes, discharged at a constant current for 12 seconds at a current equivalent to 2 C, and 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 discharged to 2.5 V at a current equivalent to 1 C, and this cycle was repeated for 97 cycles (4th to 100th cycles). The secondary battery was then disassembled in the dry oven, and the negative electrode was removed. After washing with dimethyl carbonate and drying under reduced pressure at 23°C for 1 hour, the electrode thickness was measured with a micrometer. The active material layer thickness was calculated by subtracting the copper foil thickness from the electrode thickness, and the expansion coefficient was calculated using the following formula. Expansion rate after 100 cycles = (active material layer thickness after disassembly after 100 cycles) / (active material layer thickness at the time of battery fabrication) × 100 [%]

[0108] [DC resistance (DCR) after 100 cycles] [Electrode preparation] An electrode was prepared in the same manner as described above in [Capacity retention rate after 100 cycles]. [Coin cell assembly] In the same manner as described above in [Capacity retention rate after 100 cycles], a coin cell (CR2032) was prepared, which included a negative electrode, the following positive electrode, a separator, and an electrolyte solution.

[0109] [Measurement of DC resistance after 100 cycles] Each coin cell prepared as described above was charged to 4.2 V at 30°C with a current equivalent to 0.1 C, discharged to 2.5 V at a current equivalent to 0.1 C, charged to 4.2 V at a current equivalent to 0.5 C, and discharged to 2.5 V at a current equivalent to 0.5 C for three cycles 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, discharged at a constant current for 12 seconds at a current equivalent to 0.2 C, then charged at a current equivalent to 0.1 C for 24 seconds, discharged at a constant current for 12 seconds at a current equivalent to 0.5 C, then charged at a current equivalent to 0.1 C for 1 minute, discharged at a constant current for 12 seconds at a current equivalent to 1 C, then charged at a current equivalent to 0.1 C for 2 minutes, discharged at a constant current for 12 seconds at a current equivalent to 2 C, and 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 discharged to 2.5 V at a current equivalent to 1 C, and this cycle was repeated for 97 cycles (4th to 100th cycles). Thereafter, the same operation as the initial discharge operation was carried out. The DC resistance of each coin cell was calculated from the discharge current and voltage values ​​at 10.0 seconds of C-rate, and this was taken as the DC resistance after 100 cycles.

[0110] [Peel strength] The peel strength 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 0.9 parts by mass of a polymer aqueous solution (solid content equivalent) were kneaded together. Water was then added to the mixture to achieve 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 with a thickness of 18 μm and dried. The rolled copper foil and the coating were then intimately bonded together using a roll press (manufactured by Ohno Roll Co., Ltd.). A heat treatment (reduced pressure, 100°C, 12 hours or more) was then performed to prepare a negative electrode. The thickness of the active material layer in the resulting negative electrode was 36 μm, and the capacity density of the negative electrode was 3.5 mAh / cm. 2 It was. [Peel strength measurement] The peel strength (N / 15 mm) of each electrode obtained was measured when the active material layer was peeled from the current collector foil. Specifically, the electrode was cut into a piece 80 mm wide x 15 mm long, adhesive tape was attached to the surface (the electrode active material layer side), and the electrode (the current collector foil side) was then attached to a stainless steel plate with double-sided tape. This was used as an evaluation sample. A 90-degree peel test of the electrode from the stainless steel plate (a 90-degree peel test of adhesive tape from a negative electrode fixed to a stainless steel plate) was performed using a tensile tester (Shimadzu Corporation, small benchtop tester EZ-SX) to measure the peel strength between the active material layer of the electrode and the current collector foil.

[0111] [Mandrel test] The mandrel test was carried out according to the following procedure. [Electrode preparation] An electrode was prepared in the same manner as described above in [Peel strength]. [Mandrel test] In accordance with JIS K 5600-5-1, a bending test was performed on four electrodes, with the active material side of the electrode facing outward and a mandrel with a diameter of 3 mm, so that the active material layer was facing outward, and the number of electrodes with cracks or breaks on the electrode surface was recorded.

[0112] [Viscosity change rate after 1 week at 20°C] A polymer aqueous solution was prepared by dissolving a water-based polymer in water to a solids concentration of 2% by mass, and the solution was kept at 25°C, after which the viscosity before storage was measured using a Brookfield type viscometer (model DV1MLVTJ0, manufactured by Brookfield).The 2% by mass aqueous solution was then left to stand at 20°C for one week, and after keeping the temperature at 25°C, the viscosity after storage was measured using a Brookfield type viscometer (model DV1MLVTJ0, manufactured by Brookfield). The viscosity change rate was calculated using the following formula. Viscosity change rate = (viscosity after storage - viscosity before storage) / viscosity before storage x 100 [%] The spindle and rotation speed corresponding to the viscosity were used as follows: LV-2, 12 rpm: 250 to 2500 mPa·s LV-1, 30 rpm: 20 to 200 mPa·s

[0113] The test results are summarized in the table below. TIFF2026035050000001.tif87164 [Industrial Applicability]

[0114] 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.

Claims

1. Contains water-based polymers, The aqueous solution obtained when the aqueous polymer is dissolved in water at a concentration of 2% by mass has a Na concentration of 0.05% by mass or more and 0.25% by mass or less, The secondary battery binder, wherein the aqueous polymer has an electrolyte absorption rate (25°C) of 8.0% or less.

2. The secondary battery binder according to claim 1 , wherein the electrolyte absorption rate (25° C.) is 2% or more and 6.5% or less.

3. 3. The secondary battery binder according to claim 1, wherein the aqueous polymer is a vinyl polymer having a repeating unit containing an acidic functional group.

4. The water-based polymer is formula: -[CH ２ -C(R １ )(C(=O)R ２ )]- [In the formula, 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 each n is independently 1 or more and 6 or less). A repeating unit (1) represented by the formula: formula: -[CH ２ -CH(OH)]- Repeating unit (2) represented by 3. The secondary battery binder according to claim 1, comprising a repeating unit selected from:

5. In the water-based 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 repeating units containing an acidic functional group is 0.8 mol% or more; 5. The secondary battery binder of claim 4, wherein the amount of nonionic repeating units is 40 mol % or more.

6. 3. The secondary battery binder of claim 1 or 2, comprising SBR.

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

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

9. A method for producing a secondary battery, comprising the step of applying the slurry according to claim 7 .

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

11. An electrode comprising the heat-dried slurry according to claim 8.

12. A secondary battery comprising the electrode according to claim 10.

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