CN111095635A - Binder for nonaqueous electrolyte secondary battery electrode, electrode mixture for nonaqueous electrolyte secondary battery, electrode for nonaqueous electrolyte secondary battery, and electrical device - Google Patents
Binder for nonaqueous electrolyte secondary battery electrode, electrode mixture for nonaqueous electrolyte secondary battery, electrode for nonaqueous electrolyte secondary battery, and electrical device Download PDFInfo
- Publication number
- CN111095635A CN111095635A CN201880060479.4A CN201880060479A CN111095635A CN 111095635 A CN111095635 A CN 111095635A CN 201880060479 A CN201880060479 A CN 201880060479A CN 111095635 A CN111095635 A CN 111095635A
- Authority
- CN
- China
- Prior art keywords
- secondary battery
- electrolyte secondary
- nonaqueous electrolyte
- electrode
- binder
- Prior art date
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- 239000011230 binding agent Substances 0.000 title claims abstract description 86
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- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/621—Binders
- H01M4/622—Binders being polymers
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L29/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal or ketal radical; Compositions of hydrolysed polymers of esters of unsaturated alcohols with saturated carboxylic acids; Compositions of derivatives of such polymers
- C08L29/02—Homopolymers or copolymers of unsaturated alcohols
- C08L29/04—Polyvinyl alcohol; Partially hydrolysed homopolymers or copolymers of esters of unsaturated alcohols with saturated carboxylic acids
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- C—CHEMISTRY; METALLURGY
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- C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
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- C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
- C08L33/04—Homopolymers or copolymers of esters
- C08L33/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, which oxygen atoms are present only as part of the carboxyl radical
- C08L33/062—Copolymers with monomers not covered by C08L33/06
- C08L33/064—Copolymers with monomers not covered by C08L33/06 containing anhydride, COOH or COOM groups, with M being metal or onium-cation
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- H01M4/00—Electrodes
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Abstract
The invention provides a binder for an electrode, which has sufficient binding power and can reduce the resistance of a nonaqueous electrolyte secondary battery. A binder for a nonaqueous electrolyte secondary battery electrode, which contains a copolymer of vinyl alcohol and an alkali metal neutralized product of an ethylenically unsaturated carboxylic acid, and polyvinyl alcohol.
Description
Technical Field
The present invention relates to a binder for a nonaqueous electrolyte secondary battery electrode, an electrode mixture for a nonaqueous electrolyte secondary battery containing the binder, an electrode for a nonaqueous electrolyte secondary battery using the electrode mixture, a nonaqueous electrolyte secondary battery including the electrode, and an electric device including the secondary battery.
Background
In recent years, with the spread of portable electronic devices such as notebook computers, smart phones, portable game machines, and PDAs, in order to make these devices lighter and usable for a long time, the secondary batteries used as power sources are required to be smaller and have higher energy density.
In particular, in recent years, the use of the power source for vehicles such as electric vehicles and electric motorcycles has been expanding. For such secondary batteries used also as power sources for vehicles, batteries capable of operating in a wide temperature range in addition to high energy density are required, and various nonaqueous electrolyte secondary batteries have been proposed.
As nonaqueous electrolyte secondary batteries, nickel-cadmium batteries, nickel-hydrogen batteries, and the like have been mainly used, but from the above-described demands for downsizing and higher energy density, the use of lithium ion secondary batteries tends to increase.
An electrode for a nonaqueous electrolyte secondary battery such as a lithium ion secondary battery is generally manufactured by: a battery electrode mixture slurry (hereinafter, sometimes simply referred to as a slurry) in which an active material (electrode active material) and a conductive additive are mixed in a binder solution in which a binder for an electrode (hereinafter, sometimes simply referred to as a binder) is dissolved in a solvent or a slurry in which a binder is dispersed in a dispersion medium is applied to a current collector, and the solvent or the dispersion medium is removed by a method such as drying.
In a lithium ion secondary battery, for example, a positive electrode is obtained by coating and drying a positive electrode mixture slurry, which is an active material of lithium cobaltate (LiCoO), on an aluminum foil current collector2) And polyvinylidene fluoride (PVDF) as a binder and carbon black as a conductive aid are dispersed in a dispersion medium.
The negative electrode is obtained by applying and drying a negative electrode mixture slurry, in which Graphite (Graphite) as an active material, any one of carboxymethyl cellulose (CMC), Styrene Butadiene Rubber (SBR), PVDF, polyimide, and the like as a binder, and carbon black as a conductive aid are dispersed in water or an organic solvent, on a copper foil current collector.
In addition, in order to increase the capacity of lithium ion secondary batteries, various graphites have been studied as negative electrode active materials. In particular, it is known that the energy capacity as a negative electrode active material changes due to changes in the crystal state of artificial graphite caused by differences in the raw material and carbonization temperature (see patent documents 1 to 3).
Documents of the prior art
Patent document
Patent document 1, Japanese patent application laid-open No. 8-264180
Patent document 2 Japanese patent application laid-open No. 4-188559
Patent document 3, Japanese patent application laid-open No. H10-284082
Patent document 4 International publication No. 2004/049475
Patent document 5 Japanese patent application laid-open No. H10-302799
Disclosure of Invention
Problems to be solved by the invention
When various types of graphite are used as the negative electrode active material, PVDF that has been conventionally used as a binder has low binding power and flexibility, and therefore a large amount of binder needs to be used. By using a large amount of the binder, the amount of the active material is relatively reduced, the battery capacity is reduced, and the resistance inside the battery is increased. Further, since PVDF is dissolved only in an organic solvent, another binder capable of reducing the environmental load has been proposed (see patent documents 4 to 5). However, in the case of using these binders, the performance as a battery is insufficient.
In addition, as an aqueous binder expected to reduce the environmental load without reducing the adhesive strength, use of Styrene Butadiene Rubber (SBR) has been studied. However, since SBR having a rubbery property as an insulator exists on the surface of the active material, sufficient rate characteristics cannot be obtained, and there is a problem that the resistance in the electrode becomes high.
In view of the above situation, a main object of the present invention is to provide a binder for an electrode which has a sufficient binding force and can reduce the resistance of a nonaqueous electrolyte secondary battery.
Means for solving the problems
The present inventors have conducted intensive studies to solve the above problems. As a result, they have found that when a binder containing a polyvinyl alcohol and a copolymer of a vinyl alcohol and an alkali metal neutralized product of an ethylenically unsaturated carboxylic acid is used for an electrode of a nonaqueous electrolyte secondary battery, a sufficient adhesive force can be exerted, and the resistance of the nonaqueous electrolyte secondary battery can be lowered.
That is, the present invention provides an invention having the following configuration.
Scheme 1. a binder for nonaqueous electrolyte secondary battery electrodes, which contains a copolymer of vinyl alcohol and an alkali metal neutralized product of an ethylenically unsaturated carboxylic acid, and polyvinyl alcohol.
The binder for a nonaqueous electrolyte secondary battery electrode according to claim 1, wherein a copolymerization composition ratio of the vinyl alcohol in the copolymer to the alkali metal neutralized product of the ethylenically unsaturated carboxylic acid is 95/5 to 5/95 in terms of a molar ratio.
The binder for a nonaqueous electrolyte secondary battery electrode according to claim 1 or 2, wherein the alkali metal neutralized product of an ethylenically unsaturated carboxylic acid is an alkali metal neutralized product of (meth) acrylic acid.
The binder for a nonaqueous electrolyte secondary battery electrode according to any one of claims 1 to 3, wherein a mass ratio of the copolymer to the polyvinyl alcohol is 95/5 to 70/30.
An electrode mixture for nonaqueous electrolyte secondary batteries, comprising an electrode active material, a conductive auxiliary agent, and the binder for nonaqueous electrolyte secondary battery electrodes according to any one of claims 1 to 4.
The electrode mixture for a nonaqueous electrolyte secondary battery according to claim 5, wherein the content of the binder is 0.5 to 40 parts by mass with respect to 100 parts by mass of the total amount of the electrode active material, the conductive additive and the binder.
An electrode for a nonaqueous electrolyte secondary battery according to claim 7, which is produced by using the electrode mixture for a nonaqueous electrolyte secondary battery according to claim 5 or 6.
The nonaqueous electrolyte secondary battery of claim 8, which comprises the electrode for nonaqueous electrolyte secondary batteries of claim 7.
An electrical device comprising the nonaqueous electrolyte secondary battery according to claim 8.
Embodiment 10. use of a binder in an electrode of a nonaqueous electrolyte secondary battery, wherein the binder comprises a copolymer of vinyl alcohol and an alkali metal neutralized product of an ethylenically unsaturated carboxylic acid, and polyvinyl alcohol.
ADVANTAGEOUS EFFECTS OF INVENTION
According to the present invention, it is possible to provide a binder for an electrode which has a sufficient binding force and can reduce the resistance of a nonaqueous electrolyte secondary battery. Further, according to the present invention, there can be provided an electrode mixture for a nonaqueous electrolyte secondary battery containing the binder, an electrode for a nonaqueous electrolyte secondary battery using the electrode mixture, a nonaqueous electrolyte secondary battery including the electrode, and an electric device including the secondary battery.
Detailed Description
The binder for nonaqueous electrolyte secondary battery electrodes, the electrode mixture for nonaqueous electrolyte secondary batteries, the electrode for nonaqueous electrolyte secondary batteries, the nonaqueous electrolyte secondary battery, and the electrical device of the present invention will be described in detail below.
In the present invention, "(meth) acrylic acid" means "acrylic acid" and/or "methacrylic acid", and similar expressions are also applicable.
< Binder for nonaqueous electrolyte Secondary Battery electrode >
The binder for a nonaqueous electrolyte secondary battery electrode of the present invention (hereinafter, may be referred to as "the binder of the present invention") is characterized by containing a copolymer of vinyl alcohol and an alkali metal neutralized product of an ethylenically unsaturated carboxylic acid, and polyvinyl alcohol. When the binder for a nonaqueous electrolyte secondary battery electrode of the present invention is used for an electrode of a nonaqueous electrolyte secondary battery, the binder can exhibit sufficient binding power and can reduce the resistance of the nonaqueous electrolyte secondary battery.
[ copolymer of vinyl alcohol with alkali Metal neutralization product of ethylenically unsaturated carboxylic acid ]
The copolymer of vinyl alcohol and an ethylenically unsaturated carboxylic acid alkali metal neutralized product (hereinafter, may be simply referred to as "copolymer") is a copolymer obtained by copolymerizing vinyl alcohol and an ethylenically unsaturated carboxylic acid alkali metal neutralized product as monomer components. The copolymer can be obtained, for example, by saponifying a precursor obtained by copolymerizing a vinyl ester and an ethylenically unsaturated carboxylic acid ester in a mixed solvent of an aqueous organic solvent and water in the presence of an alkali containing an alkali metal. That is, vinyl alcohol itself is unstable and thus cannot be used as a monomer as it is, but a polymer obtained by using vinyl ester as a monomer is saponified to produce a copolymer in which vinyl alcohol is copolymerized as a monomer component.
Examples of the vinyl ester include vinyl acetate and vinyl propionate, and vinyl acetate is preferable from the viewpoint of facilitating the saponification reaction. The vinyl ester may be used alone in 1 kind, or may be used in combination in 2 or more kinds.
Examples of the ethylenically unsaturated carboxylic acid ester include methyl, ethyl, n-propyl, isopropyl, n-butyl, tert-butyl and the like of (meth) acrylic acid, and methyl acrylate and methyl methacrylate are preferable from the viewpoint of facilitating the saponification reaction. The ethylenically unsaturated carboxylic acid ester may be used alone in 1 kind, or may be used in combination in 2 or more kinds.
Further, in addition to the vinyl ester and the ethylenically unsaturated carboxylic acid ester, other ethylenically unsaturated monomers copolymerizable with the vinyl ester and the ethylenically unsaturated carboxylic acid ester may be used and copolymerized as necessary.
As an example of the saponification reaction, a saponification reaction in which a precursor obtained by copolymerizing vinyl acetate/methyl acrylate is 100% saponified with potassium hydroxide is shown below.
The copolymer of vinyl alcohol and an alkali metal neutralized product of an ethylenically unsaturated carboxylic acid is a compound obtained by saponifying an ester portion derived from a monomer, which is a precursor obtained by random copolymerization of a vinyl ester and an ethylenically unsaturated carboxylic acid ester, and the bond between the monomers is a C — C covalent bond. Hereinafter, the "copolymer of vinyl alcohol and an alkali metal neutralized product of an ethylenically unsaturated carboxylic acid" may be simply referred to as a copolymer. In the above formula, "/" indicates random copolymerization.
In the precursor obtained by copolymerizing a vinyl ester and an ethylenically unsaturated carboxylic acid ester, the molar ratio of the vinyl ester to the ethylenically unsaturated carboxylic acid ester is preferably 95/5 to 5/95, more preferably 90/10 to 10/90, and still more preferably 80/20 to 20/80, from the viewpoint of more sufficiently exerting the binding force of the binder of the present invention and more suitably lowering the resistance of the nonaqueous electrolyte secondary battery. By setting the molar ratio to 95/5 to 5/95, the retention of the adhesive as a copolymer obtained after saponification is further improved.
Therefore, from the viewpoint of more sufficiently exerting the adhesive force of the present invention and more suitably lowering the resistance of the nonaqueous electrolyte secondary battery, the copolymer of the vinyl alcohol and the neutralized product of the ethylenically unsaturated carboxylic acid alkali metal is preferably 95/5 to 5/95, more preferably 90/10 to 10/90, and still more preferably 80/20 to 20/80 in terms of the molar ratio of the copolymerization composition. By setting the molar ratio to 95/5 to 5/95, the holding force of the electrode mixture as a binder is further improved.
From the viewpoint of the binder of the present invention exhibiting a more sufficient binding force and more suitably lowering the resistance of the nonaqueous electrolyte secondary battery, the total proportion of the vinyl ester and the ethylenically unsaturated carboxylic acid ester is preferably 5% by mass or more, more preferably 20 to 95% by mass, and still more preferably 40 to 95% by mass, based on the total mass (100% by mass) of the monomers forming the copolymer.
The alkali metal (meth) acrylate-neutralized product of the ethylenically unsaturated carboxylic acid according to the present invention is preferably an alkali metal (meth) acrylate-neutralized product from the viewpoint of ease of handling during production. Examples of the alkali metal-neutralized product of the ethylenically unsaturated carboxylic acid include lithium, sodium, potassium, rubidium, and cesium, and potassium and sodium are preferable. Particularly preferred alkali metal ethylenically unsaturated carboxylate neutralizers are at least one member selected from the group consisting of sodium acrylate neutralizers, potassium acrylate neutralizers, sodium methacrylate neutralizers and potassium methacrylate neutralizers.
A precursor obtained by copolymerizing a vinyl ester and an ethylenically unsaturated carboxylic acid ester (hereinafter, may be simply referred to as a precursor) is preferably obtained by a suspension polymerization method in which monomers mainly composed of a vinyl ester and an ethylenically unsaturated carboxylic acid ester are polymerized in a suspension state in an aqueous solution of a dispersant containing a polymerization catalyst to prepare polymer particles, from the viewpoint of obtaining a powdery precursor.
Examples of the polymerization catalyst include organic peroxides such as benzoyl peroxide and lauryl peroxide (laurylperoxide), and azo compounds such as azobisisobutyronitrile and azobisdimethylvaleronitrile, and among these polymerization catalysts, lauryl peroxide is preferable.
The amount of the polymerization catalyst to be added is preferably 0.01 to 5% by mass, more preferably 0.05 to 3% by mass, and still more preferably 0.1 to 3% by mass, based on the total mass (100% by mass) of the monomers. If the amount is less than 0.01% by mass, the polymerization reaction may not be completed, and if the amount exceeds 5% by mass, the adhesive effect of the finally obtained copolymer as an adhesive may be insufficient.
Examples of the dispersant used in the polymerization include polyvinyl alcohol (partially saponified polyvinyl alcohol, completely saponified polyvinyl alcohol), poly (meth) acrylic acid and salts thereof, water-soluble polymers such as polyvinyl pyrrolidone, methyl cellulose, carboxymethyl cellulose, hydroxyethyl cellulose, and hydroxypropyl cellulose, and water-insoluble inorganic compounds such as calcium phosphate and magnesium silicate. These dispersants may be used alone in 1 kind, or may be used in combination in 2 or more kinds.
The amount of the dispersant used depends on the kind of the monomer used, but is preferably 0.01 to 10% by mass, more preferably 0.05 to 5% by mass, based on the total mass (100% by mass) of the monomer.
Further, an alkali metal or alkaline earth metal water-soluble salt may be added to adjust the surface active effect of the dispersant. Examples of the water-soluble salt include sodium chloride, potassium chloride, calcium chloride, lithium chloride, sodium sulfate, potassium sulfate, disodium hydrogen phosphate, dipotassium hydrogen phosphate, trisodium phosphate, and tripotassium phosphate, and these water-soluble salts may be used alone in 1 kind or in combination of 2 or more kinds.
The amount of the water-soluble salt used is usually 0.01 to 10% by mass based on the mass of the aqueous dispersant solution.
The temperature for polymerizing the monomer is preferably-20 ℃ to +20 ℃ and more preferably-10 ℃ to +10 ℃ relative to the 10-hour half-life temperature of the polymerization catalyst. If the polymerization temperature of the monomer is lower than-20 ℃ relative to the 10-hour half-life temperature of the polymerization catalyst, the polymerization reaction may not be completed, and if it exceeds +20 ℃, the adhesion effect as an adhesive of the resulting copolymer of vinyl alcohol and the alkali metal neutralized product of an ethylenically unsaturated carboxylic acid may be insufficient.
The time for polymerizing the monomer is usually several hours to several tens of hours.
After the polymerization reaction is completed, the precursor is separated by a method such as centrifugation or filtration, and is obtained in the form of an aqueous cake. The obtained aqueous cake-like precursor may be used directly for saponification, or may be dried as necessary and used for saponification.
The number average molecular weight of the precursor can be determined by a molecular weight measuring apparatus equipped with a GFC column (OHpak, Shodex) or the like using a polar solvent such as DMF. Examples of such a molecular weight measuring apparatus include 2695 manufactured by Vortex corporation and RI detector 2414.
The number average molecular weight of the precursor is preferably 10000 to 10000000, more preferably 50000 to 5000000. When the number average molecular weight of the precursor is in the range of 10000 to 10000000, the adhesive strength is improved when the precursor is used as a binder, and particularly when the precursor is used as a water-based binder, the thickness can be easily adjusted.
The saponification reaction can be carried out, for example, in the presence of an alkali containing an alkali metal in an aqueous organic solvent alone or in a mixed solvent of an aqueous organic solvent and water. As the alkali containing an alkali metal used for the saponification reaction, a known alkali can be used. As the base, an alkali metal hydroxide is preferably used, and sodium hydroxide and potassium hydroxide are more preferably used from the viewpoint of high reactivity.
The amount of the base used is preferably 60 to 140 mol%, more preferably 80 to 120 mol%, based on the total number of moles of the monomers. If the amount of the alkali used is less than 60 mol%, the saponification may be insufficient, and even if it exceeds 140 mol%, the effect may not be more excellent and it is uneconomical. The saponification degree in the saponification reaction of the precursor is preferably 90 to 100%, more preferably 95 to 100%. By setting the saponification degree to 90% or more, the solubility in water can be improved.
In the copolymer of the present invention, free carboxylic acid groups (COOH) derived from the ethylenically unsaturated carboxylic acid ester are hardly present regardless of the amount of the base used. The absence of carboxylic acid groups allows the slurry-like electrode mixture to have an appropriate viscosity, and also allows the electrode mixture to have improved coating properties and storage stability.
As the solvent for the saponification reaction, it is preferable to use only an aqueous organic solvent or a mixed solvent of an aqueous organic solvent and water. Examples of the aqueous organic solvent include lower alcohols such as methanol, ethanol, n-propanol, isopropanol, n-butanol, and t-butanol, ketones such as acetone and methyl ethyl ketone, and mixtures thereof. Among them, lower alcohols are preferable, and methanol and ethanol are particularly preferable in terms of obtaining a copolymer having an excellent thickening effect and excellent resistance to mechanical shear. The aqueous organic solvent may be used alone in 1 kind, or may be used in combination of 2 or more kinds.
The mass ratio (aqueous organic solvent: water) when a mixed solvent of an aqueous organic solvent and water is used is preferably 2: 8-10: 0, more preferably 3: 7-8: 2. at a deviation of 2: 8-10: when the amount is in the range of 0, the solvent affinity of the precursor or the solvent affinity of the saponified copolymer may be insufficient, and the saponification reaction may not proceed sufficiently. In an aqueous organic solvent of less than 2: when the ratio of 8 is used, the copolymer tends to be thickened during the saponification reaction, and thus the copolymer is not easily obtained industrially. When the water-containing cake-like precursor is used directly in the saponification reaction, the mass ratio of the mixed solvent is the ratio of water containing the water-containing cake-like precursor.
The saponification reaction temperature of the precursor is preferably 20-80 ℃, and more preferably 20-60 ℃. When the saponification reaction is carried out at a temperature lower than 20 ℃, the reaction may not be completed, and when the saponification reaction is carried out at a temperature higher than 80 ℃, the reaction system may be thickened and may not be easily stirred.
The time for the saponification reaction is usually about several hours.
At the end of the saponification reaction, the copolymer is usually dispersed in the form of a paste or slurry. The dispersion is subjected to solid-liquid separation by a method such as centrifugation or filtration, washed with a lower alcohol such as methanol, and dried, whereby a copolymer of a vinyl alcohol and an alkali metal neutralized product of an ethylenically unsaturated carboxylic acid can be obtained as spherical single particles or aggregated particles obtained by aggregating spherical particles.
After the saponification reaction, an inorganic acid such as hydrochloric acid, sulfuric acid, phosphoric acid, or nitric acid; after acid treatment of the copolymer with an acid such as an organic acid such as formic acid, acetic acid, oxalic acid, or citric acid, a copolymer of a vinyl alcohol of a different kind (i.e., different alkali metals) and an alkali metal neutralized product of an ethylenically unsaturated carboxylic acid is obtained by using any alkali metal such as lithium hydroxide, sodium hydroxide, potassium hydroxide, rubidium hydroxide, cesium hydroxide, or francium hydroxide.
The conditions for drying the liquid-containing copolymer are generally preferably drying at a temperature of 30 to 120 ℃ under normal pressure or reduced pressure. The drying time depends on the pressure and temperature during drying, but is usually several hours to several tens of hours.
The volume average particle diameter of the copolymer of vinyl alcohol and the neutralized product of an ethylenically unsaturated carboxylic acid alkali metal is preferably 1 to 200 μm, more preferably 10 to 100 μm, from the viewpoint of more sufficiently exerting the adhesive force of the adhesive of the present invention and more suitably lowering the resistance of the nonaqueous electrolyte secondary battery. When the particle diameter is 1 μm or more, a more preferable binding effect can be obtained, and when the particle diameter is 200 μm or less, the thickener becomes more uniform, and a more preferable binding effect can be obtained. The volume average particle diameter of the copolymer is a value measured by using 2-propanol or methanol in a dispersion solvent with a batch tank (SALD-BC, manufactured by Shimadzu corporation) provided in a laser diffraction particle size distribution measuring apparatus (SALD-710, manufactured by Shimadzu corporation).
When the liquid-containing copolymer is dried and the volume average particle size of the obtained copolymer exceeds 200 μm, the volume average particle size can be adjusted to 1 μm or more and 200 μm or less by pulverizing the copolymer by a conventionally known pulverization method such as mechanical grinding treatment.
The mechanical grinding treatment refers to a method of applying an external force such as impact, tension, friction, compression, shear, etc. to the obtained copolymer, and examples of an apparatus used for the mechanical grinding treatment include a rolling mill, a vibration mill, a planetary mill, a swing mill, a horizontal mill, a jet mill, a crusher, a homogenizer, a fluidizer, a paint mixer (paintshaker), a mixer, and the like. For example, the planetary mill crushes or mixes the copolymer by putting the copolymer and the pellets together into a container and using mechanical energy generated by simultaneous rotation and revolution. According to the method, the pulverization can be carried out to a nano level.
The thickening effect of the copolymer of vinyl alcohol and an alkali metal neutralized product of an ethylenically unsaturated carboxylic acid according to the present invention is preferably 20 to 10000mPa · s, more preferably 50 to 10000mPa · s, and even more preferably 50 to 5000mPa · s, in terms of ease of application of the electrode mixture to be produced, in an aqueous solution containing 1 mass% of the copolymer (1 mass% aqueous solution). When the viscosity is 20 mPas or more, a slurry-like electrode mixture having a preferable viscosity can be obtained, and the applicability is also easy. Further, the dispersibility of the active material and the conductive assistant in the mixture is also improved. If the viscosity is 10000 mPas or less, the viscosity of the mixture to be prepared is not too high, and it becomes easier to apply the mixture to a current collector in a thin and uniform manner. The viscosity of the 1 mass% aqueous solution was measured using a rotational viscometer (model DV-I +) manufactured by BROOKFIELD under the conditions of spindle No.5, 50rpm (spindle No.5, 50rpm) (liquid temperature 25 ℃).
From the viewpoint of the binder of the present invention exhibiting more sufficient binding power and more suitably lowering the resistance of the nonaqueous electrolyte secondary battery, the proportion of the copolymer of the vinyl alcohol and the alkali metal neutralization product of an ethylenically unsaturated carboxylic acid in the binder of the present invention is preferably 5% by mass or more, more preferably 20% by mass or more and 95% by mass or less, and still more preferably 40% by mass or more and 95% by mass or less.
[ polyvinyl alcohol ]
In the binder for a nonaqueous electrolyte secondary battery electrode of the present invention, the degree of saponification of polyvinyl alcohol is preferably 75% or more, more preferably 90% or more, from the viewpoint of solubility in water. The polyvinyl alcohol preferably used has a polymerization degree of about 100 to 3000 from the viewpoint of handling.
The number average molecular weight of the polyvinyl alcohol is preferably 1000 to 5000000 from the viewpoint of more sufficient binding power of the binder of the present invention and more suitably lowering the resistance of the nonaqueous electrolyte secondary battery, and more preferably 4000 to 1000000 from the viewpoint of forming a viscosity that is easy to handle when the electrode mixture is applied.
The number average molecular weight of the polyvinyl alcohol is the same as that of the precursor, and is measured by a molecular weight measuring apparatus equipped with a GFC column.
The polyvinyl alcohol can be produced by a known method, for example, a method of polymerizing vinyl ester in the presence of a catalyst and saponifying in the presence of a catalyst such as an acid or an alkali. Further, as the polyvinyl alcohol, for example, commercially available products such as "GOHSENOL" series (manufactured by japan synthetic chemical corporation) and "Kuraray Poval" series (manufactured by Kuraray Poval) may be used.
From the viewpoint of more sufficiently exerting the adhesive force of the binder of the present invention and more suitably lowering the resistance of the nonaqueous electrolyte secondary battery, the content of the polyvinyl alcohol in the binder of the present invention is preferably 1 mass% or more, more preferably 1 mass% or more and 60 mass% or less, and further preferably 1 mass% or more and 40 mass% or less, based on the total mass of the binder.
In the adhesive of the present invention, the mass ratio of the copolymer to the polyvinyl alcohol (copolymer/polyvinyl alcohol) is preferably 95/5 to 70/30, more preferably 95/5 to 65/35, and still more preferably 95/5 to 60/40, from the viewpoint of more sufficiently exerting the adhesive force and more suitably lowering the resistance of the nonaqueous electrolyte secondary battery. When the mass ratio is 95/5 to 70/30, the resistance in the electrode further decreases, and the deterioration of cycle life characteristics due to insufficient adhesion tends to be suppressed.
[ other ingredients ]
The binder for nonaqueous electrolyte secondary battery electrodes of the present invention may contain other components in addition to the copolymer of vinyl alcohol and an alkali metal-neutralized ethylenically unsaturated carboxylic acid and polyvinyl alcohol. Examples of the other component include a known component mixed in a binder for an electrode of a nonaqueous electrolyte secondary battery. Specific examples of the other component include carboxymethylcellulose (CMC), acrylic resins, sodium polyacrylate, sodium alginate, Polyimide (PI), polyamide, polyamideimide, polyacrylic acid, Styrene Butadiene Rubber (SBR), and ethylene-vinyl acetate copolymer (EVA). Among them, acrylic resins, sodium polyacrylate, sodium alginate, polyamide, polyamideimide, and polyimide are preferably used, and acrylic resins are particularly preferably used. The other components may be used alone in 1 kind, or may be used in combination in 2 or more kinds.
The binder for nonaqueous electrolyte secondary battery electrodes of the present invention may contain no polyalkylene oxide. That is, one embodiment of the binder for a nonaqueous electrolyte secondary battery electrode of the present invention does not contain a polyalkylene oxide (the content of polyalkylene oxide is 0 mass%). Examples of the polyalkylene oxide include polyethylene oxide, polypropylene oxide, polybutylene oxide, an ethylene oxide-propylene oxide copolymer, an ethylene oxide-butylene oxide copolymer, and a propylene oxide-butylene oxide copolymer.
From the viewpoint of the binder of the present invention exhibiting a more sufficient binding force and more suitably lowering the resistance of the nonaqueous electrolyte secondary battery, the proportion of the other component in the binder of the present invention is preferably less than 80% by mass, more preferably 50% by mass or less, and still more preferably 20% by mass or less.
In the binder of the present invention, the content ratio of the copolymer of vinyl alcohol and the neutralized product of an ethylenically unsaturated carboxylic acid alkali metal and polyvinyl alcohol is preferably 20 to 100% by mass in total relative to the total mass of the binder, from the viewpoint of more sufficiently exerting the binding force and more suitably lowering the resistance of the nonaqueous electrolyte secondary battery.
The binder for a nonaqueous electrolyte secondary battery electrode of the present invention can be suitably used as an aqueous binder (that is, a nonaqueous binder for a nonaqueous electrolyte secondary battery electrode).
< electrode mixture for nonaqueous electrolyte secondary battery >
The electrode mixture for a nonaqueous electrolyte secondary battery of the present invention is an electrode mixture for producing an electrode for a nonaqueous electrolyte secondary battery, which contains the binder for a nonaqueous electrolyte secondary battery electrode of the present invention, an electrode active material (a positive electrode active material and a negative electrode active material), and a conductive additive as essential components.
The binder content of the present invention is preferably 0.5 to 40 parts by mass, more preferably 1 to 25 parts by mass, and even more preferably 1.5 to 10 parts by mass, based on 100 parts by mass of the total amount of the electrode active material, the conductive assistant and the binder, from the viewpoint of more sufficiently exerting the binding force and more suitably lowering the resistance of the nonaqueous electrolyte secondary battery. From the same viewpoint, the content of the binder of the present invention in the electrode mixture of the present invention is preferably 0.5 to 40% by mass, more preferably 1 to 25% by mass, and still more preferably 1.5 to 10% by mass. When the content is 0.5 mass% or more, the deterioration of cycle life characteristics due to insufficient cohesive force and the aggregation due to insufficient viscosity of the slurry tend to be suppressed. On the other hand, when the content is 40 mass% or less, a high capacity tends to be obtained during charge and discharge of the battery.
The electrode mixture of the present invention can be produced by a known method using the binder of the present invention, and for example, can be produced by adding a conductive additive, the binder of the present invention, a dispersion additive (if necessary), and water to an electrode active material to prepare a paste-like slurry. The timing of adding water is not particularly limited, and the binder of the present invention may be dissolved in water in advance to be added, or the electrode active material, the conductive aid, the dispersion aid (if necessary), and the binder of the present invention may be mixed in a solid state and then added with water.
The amount of water used is, for example, preferably 40 to 2000 parts by mass, and more preferably 50 to 1000 parts by mass, based on 100 parts by mass of the total of the electrode active material, the conductive assistant and the binder of the present invention. By setting the amount of water used to the above range, the operability of the electrode mixture (slurry) of the present invention tends to be further improved.
[ Positive electrode active Material ]
As the positive electrode active material, positive electrode active materials used in the art can be used. For example, lithium iron phosphate (LiFePO) is preferably used4) Lithium manganese phosphate (LiMnPO)4) Lithium cobalt phosphate (LiCoPO)4) Iron pyrophosphate (Li)2FeP2O7) Lithium cobaltate (LiCoO)2) Spinel-type lithium manganate composite oxide (LiMn)2O4) Lithium manganate composite oxide (LiMnO)2) Lithium nickelate composite oxidationSubstance (LiNiO)2) Lithium niobate composite oxide (LiNbO)2) Lithium ferrite composite oxide (LiFeO)2) Lithium magnesium oxide composite oxide (LiMgO)2) Lithium calcium oxide composite oxide (LiCaO)2) Lithium cuprate composite oxide (LiCuO)2) Lithium zincate composite oxide (LiZnO)2) Lithium molybdate composite oxide (LiMoO)2) Lithium tantalate composite oxide (LiTaO)2) Lithium tungstate composite oxide (LiWO)2) Lithium-nickel-cobalt-aluminum composite oxide (LiNi)0.8Co0.15Al0.05O2) Lithium-nickel-cobalt-manganese composite oxide ((LiNi)xCoyMn1-x-yO2) X is more than 0 and less than 1, y is more than 0 and less than 1, and x + y is less than 1), Li excess system nickel-cobalt-manganese composite oxide and manganese nickel oxide (LiNi)0.5Mn1.5O4) Manganese oxide (MnO)2) Vanadium-based oxides, sulfur-based oxides, silicate-based oxides, and the like. These can be used alone in 1 or a combination of 2 or more.
[ negative electrode active Material ]
As the negative electrode active material, negative electrode active materials used in the art can be used. For example, a material capable of absorbing and releasing a large amount of lithium ions such as a carbon material, silicon (Si), tin (Sn), lithium titanate, or the like can be used. In the case of such a material, any of a simple substance, an alloy, a compound, a solid solution, and a composite active material containing a silicon-containing material or a tin-containing material can exhibit the effects of the present embodiment. As the carbon material, crystalline carbon, amorphous carbon, or the like can be used. Examples of the crystalline carbon include amorphous, tabular and flaky (flake). Natural graphite or artificial graphite in the form of spheres or fibers. Examples of the amorphous carbon include soft carbon (graphite which is easily carbonized), hard carbon (graphite which is hardly carbonized), mesophase pitch carbide, and calcined coke. As the silicon-containing material, Si or SiO can be usedx(0.05 < x < 1.95), or an alloy, compound or solid solution in which a part of Si is substituted with at least one element selected from B, Mg, Ni, Ti, Mo, Co, Ca, Cr, Cu, Fe, Mn, Nb, Ta, V, W, Zn, C, N and SnAnd the like. They may be referred to as silicon or silicon compounds. As the tin-containing material, Ni can be applied2Sn4、Mg2Sn、SnOx(0＜x＜2)、SnO2、SnSiO3And LiSnO.
These materials may be used alone in 1 kind, or may be used in combination in 2 or more kinds. Among them, graphite is preferable as the negative electrode active material. By using the binder of the present invention, even when graphite is used as the negative electrode active material, the binder can exhibit sufficient binding power, and the nonaqueous electrolyte secondary battery can be reduced in resistance as appropriate.
A composite obtained by mixing silicon or a silicon compound as the first negative electrode active material, a carbon material as the second negative electrode active material, and the first and second negative electrode active materials may be used as the negative electrode active material. In this case, the mixing ratio of the first and second negative electrode active materials is preferably 5/95 to 95/5 in terms of mass ratio. The carbon material may be any carbon material used in the art, and typical examples thereof include the crystalline carbon and the amorphous carbon.
The method for producing the negative electrode active material may be any method as long as both are uniformly dispersed when producing an active material composite in which the first negative electrode active material and the second negative electrode active material are mixed. As a specific method for producing the negative electrode active material, a method of mixing the first negative electrode active material and the second negative electrode active material using a ball mill may be mentioned. For example, a method of supporting the second negative electrode active material precursor on the surface of the particles of the first negative electrode active material and carbonizing the particles by a heat treatment method is exemplified. The second negative electrode active material precursor may be any carbon precursor that can form a carbon material by heat treatment, and examples thereof include glucose, citric acid, pitch, tar, binder materials (for example, polyvinylidene fluoride, carboxymethyl cellulose, acrylic resin, sodium polyacrylate, sodium alginate, polyimide, polytetrafluoroethylene, polyamide, polyamideimide, polyacrylic acid, styrene butadiene rubber, polyvinyl alcohol, ethylene-vinyl acetate copolymer, and the like). Commercial products of these negative electrode active materials can be easily obtained.
The heat treatment method is a method of obtaining conductivity by carbonizing a carbon precursor by heat treatment in a non-oxidizing atmosphere (an atmosphere which is not easily oxidized such as a reducing atmosphere, an inert atmosphere, a reduced pressure atmosphere, or the like) at 600 to 4000 ℃.
[ conductive auxiliary agent ]
The conductive aid may be one used in the art, and is preferably carbon powder. Examples of the carbon powder include 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 (CNT).
The amount of the conductive aid used is preferably 0.1 to 30% by mass, more preferably 0.5 to 10% by mass, and still more preferably 2 to 5% by mass, based on 100 parts by mass of the total of the electrode active material, the conductive aid, and the binder. If the amount of the conductive aid used is less than 0.1 mass%, the conductivity of the electrode may not be sufficiently improved. If the amount of the conductive aid used exceeds 30 mass%, the proportion of the electrode active material is relatively reduced, and therefore, a high capacity is not easily obtained during charge and discharge of the battery, and the surface area is increased because the amount is smaller than that of the electrode active material, and the amount of the binder used may be increased.
[ dispersing auxiliary ]
The electrode mixture of the present invention may further contain a dispersion aid. By containing the dispersion aid, the dispersibility of the electrode active material and the conductive aid in the electrode mixture is improved. The dispersing aid is preferably an organic acid having a molecular weight of 100000 or less, which is soluble in an aqueous solution having a pH of 7 to 13. Among these organic acids, at least one of a carboxyl group, a hydroxyl group, an amino group, and an imino group is preferably contained. Specific examples thereof include compounds having a carboxyl group and a hydroxyl group such as lactic acid, tartaric acid, citric acid, malic acid, glycolic acid, hydroxymalonic acid, glucuronic acid, humic acid, etc.; compounds having a carboxyl group and an amino group such as glycine, alanine, phenylalanine, 4-aminobutyric acid, leucine, isoleucine, and lysine; compounds having a plurality of carboxyl groups and amino groups such as glutamic acid and aspartic acid; compounds having a carboxyl group and an imino group such as proline, 3-hydroxyproline, 4-hydroxyproline, Pipecolic acid (Pipecolic acid); compounds having a carboxyl group and a functional group other than a hydroxyl group and an amino group, such as glutamine, asparagine, cysteine, histidine, and tryptophan. Among them, glucuronic acid, humic acid, glycine, aspartic acid, and glutamic acid are preferable from the viewpoint of ease of obtaining.
The molecular weight of the dispersion aid is preferably 100000 or less in terms of solubility in water in the case of an aqueous binder. If the molecular weight exceeds 100000, the hydrophobicity of the molecule becomes strong, and the uniformity of the slurry may be impaired.
< electrode for nonaqueous electrolyte secondary battery >
The electrode for a nonaqueous electrolyte secondary battery of the present invention can be produced by applying the method used in the art to the electrode mixture of the present invention (that is, the electrode for a nonaqueous electrolyte secondary battery of the present invention). For example, the electrode can be produced by providing an electrode mixture on the current collector. More specifically, the electrode mixture can be produced, for example, by applying (and if necessary drying) the electrode mixture to a current collector.
When the electrode of the present invention is a positive electrode, as a material constituting the current collector, for example, a conductive material such as C, Cu, Ni, Fe, V, Nb, Ti, Cr, Mo, Ru, Rh, Ta, W, Os, Ir, Pt, Au, Al, or an alloy (for example, stainless steel) containing 2 or more of these conductive materials can be used. The current collector may be formed by plating a conductive material with a different conductive material (for example, by plating Fe with Cu). From the viewpoint of high conductivity and excellent stability and oxidation resistance in the electrolytic solution, Cu, Ni, stainless steel, and the like are preferable as the material constituting the current collector, and from the viewpoint of material cost, Cu and Ni are preferable.
When the electrode of the present invention is a negative electrode, as a material constituting the current collector, for example, a conductive material such as C, Ti, Cr, Mo, Ru, Rh, Ta, W, Os, Ir, Pt, Au, Al, or an alloy (for example, stainless steel) containing 2 or more of these conductive materials can be used. From the viewpoint of high conductivity and excellent stability and oxidation resistance in the electrolytic solution, C, Al, stainless steel, and the like are preferable as the material constituting the current collector, and Al is preferable from the viewpoint of material cost.
As the shape of the current collector, for example, a foil-like substrate, a three-dimensional substrate, or the like can be used. However, if a three-dimensional substrate (metal foam, mesh, woven fabric, nonwoven fabric, expanded body (expanded), or the like) is used, an electrode having a higher capacity density can be obtained, and high-rate charge and discharge characteristics are also good.
< nonaqueous electrolyte Secondary Battery >
The nonaqueous electrolyte secondary battery of the present invention (a nonaqueous electrolyte secondary battery including at least the electrode for a nonaqueous electrolyte secondary battery of the present invention) can be manufactured using the electrode for a nonaqueous electrolyte secondary battery of the present invention. The nonaqueous electrolyte secondary battery of the present invention may include the electrode for nonaqueous electrolyte secondary batteries of the present invention as either or both of the positive electrode and the negative electrode. The nonaqueous electrolyte secondary battery is preferably a lithium ion secondary battery. As the method for manufacturing the nonaqueous electrolyte secondary battery of the present invention, a common method used in the art can be used.
In the nonaqueous electrolyte secondary battery of the present invention, since the lithium ion secondary battery also contains lithium ions, a lithium salt is preferably used as the electrolyte. Examples of the lithium salt include lithium hexafluorophosphate, lithium perchlorate, lithium tetrafluoroborate, lithium trifluoromethanesulfonate imide and the like. The electrolyte may be used alone in 1 kind, or may be used in combination in 2 or more kinds.
As the electrolyte of the battery, for example, propylene carbonate, ethylene carbonate, dimethyl carbonate, diethyl carbonate, γ -butyrolactone, or the like can be used. The electrolyte may be used alone in 1 kind, or may be used in combination in 2 or more kinds. Particularly preferred is a propylene carbonate single component, a mixture of ethylene carbonate and diethyl carbonate, or a gamma-butyrolactone single component. The mixing ratio of the mixture of ethylene carbonate and diethyl carbonate can be arbitrarily adjusted within a range of 10 to 90 vol% of one component.
< Electrical apparatus >
The electric device of the present invention is an electric device including at least the nonaqueous electrolyte secondary battery of the present invention. That is, the electric device according to the present invention is an electric device using at least the nonaqueous electrolyte secondary battery of the present invention as a power source.
Examples of the electric device of the present invention include an air conditioner, a washing machine, a television, a refrigerator, a computer, a tablet computer, a smartphone, a computer keyboard, a monitor, a printer, a mouse, a hard disk, a computer peripheral device, an iron, a clothes dryer, a walkie talkie, a blower, a music recorder, a music player, an oven, a stove, a warm air heater, a car navigation device, a flashlight, a humidifier, a portable karaoke machine, a dry battery, an air cleaner, a game machine, a sphygmomanometer, a coffee grinder, a coffee maker, a quilt, a copier, a disc changer, a radio, an electric razor, a juicer, a shredder, a water purifier, a lighting device, a tableware dryer, a rice cooker, a trouser-wire hot press, a dust collector, a scale, an electric blanket, an electric pot, an electronic dictionary, an electronic notepad, an electromagnetic oven, a calculator, an electric cart, an electric wheelchair, an, Electric tools, electric toothbrushes, foot cookers, clocks, interphones, air circulators, electric shock killers, hot plates, toasters, hot water heaters, shredders, soldering irons, cameras, video recorders ("ビデオデッキ" in japanese text of "video cassette recorder"), facsimile machines, bedding dryers, blenders, sewing machines, rice cake makers, drinking water coolers, electronic musical instruments, motorcycles, toys, lawn mowers, bicycles, automobiles, hybrid cars, plug-in hybrid cars, railways, ships, airplanes, emergency batteries, and the like.
Examples
The present invention will be described in more detail with reference to the following examples, but the present invention is not limited to these examples.
< preparation of copolymer A >
A copolymer A was produced by the following steps 1 to 3.
(Process 1: Synthesis of precursor (precursor) obtained by copolymerizing vinyl ester and ethylenically unsaturated Carboxylic acid ester)
A2-liter reaction vessel equipped with a stirrer, a thermometer, a nitrogen inlet, a reflux condenser and a dropping funnel was charged with 768g of water and 12g of anhydrous sodium sulfate, and the system was deoxygenated by blowing nitrogen gas. Then, 1g of partially saponified polyvinyl alcohol (degree of saponification: 88%) and 1g of lauryl peroxide were charged, and after the internal temperature was raised to 60 ℃, 104g (1.209mol) of methyl acrylate and 155g (1.802mol) of vinyl acetate were added dropwise over 4 hours from the dropping funnel. Thereafter, the internal temperature was maintained at 65 ℃ for 2 hours. Then, the solid content was separated by filtration to obtain 288g (water content: 10.4 mass%) of a precursor. The obtained precursor was dissolved in DMF, and then filtered through a filter, and the molecular weight of the precursor in the filtrate was measured using a molecular weight measuring apparatus (2695, RI detector 2414, manufactured by wattes corporation). The number average molecular weight calculated by conversion to standard polystyrene was 1880000.
(step 2: Synthesis of copolymer (copolymer) of vinyl alcohol and alkali Metal neutralization product of ethylenically unsaturated carboxylic acid)
A reaction vessel identical to that of step 1 was charged with 450g of methanol, 420g of water, 132g (3.3mol) of sodium hydroxide and 288g (10.4 mass% water) of the precursor obtained in step 1, and then the saponification reaction was carried out at 30 ℃ for 3 hours with stirring. After completion of the saponification reaction, the obtained copolymer was washed with methanol, filtered, and dried at 70 ℃ for 6 hours to obtain 193g of a vinyl ester/ethylenically unsaturated carboxylic acid ester copolymer (a copolymer of vinyl alcohol and a neutralized product of an ethylenically unsaturated carboxylic acid alkali metal, the alkali metal being sodium, and the degree of saponification being 98.8%). The volume average particle diameter of the obtained copolymer was 180. mu.m.
(step 3: pulverization of copolymer (copolymer) of vinyl alcohol and alkali metal neutralization product of ethylenically unsaturated carboxylic acid)
193g of the copolymer obtained in step 2 was pulverized by a jet mill (LJ, manufactured by Nippon Pneumatic industries, Ltd.) to obtain 173g of a copolymer (copolymer A) in a fine powder form. The particle size of the copolymer A obtained was measured by a laser diffraction particle size distribution measuring apparatus (SALD-7100, manufactured by Shimadzu corporation), and as a result, the volume average particle size was 39 μm.
< production of Binder, electrode mixture, and electrode >
(example 1)
An aqueous solution of an adhesive (adhesive composition) was obtained by dissolving 2.7 parts by mass of the copolymer a obtained above and 0.3 part by mass of polyvinyl alcohol (Kuraray Poval 105, number average molecular weight 22000, manufactured by komari corporation) in 50 parts by mass of water. Then, 96.5 parts by mass of artificial graphite (MAG-D, manufactured by hitachi chemical corporation) as an electrode active material and 0.5 part by mass of Acetylene BLACK (AB) (DENKA BLACK (registered trademark), manufactured by electrochemical industry) as a conductive additive were added to the above binder aqueous solution and kneaded. Further, 70 parts by mass of viscosity adjusting water was added and kneaded to prepare a slurry-like negative electrode mixture. The obtained negative electrode mixture was applied onto an electrolytic copper foil having a thickness of 10 μm and dried, and then the electrolytic copper foil was bonded to the coating film by a roll press (manufactured by OONOROLL corporation), followed by heat treatment (under reduced pressure, 140 ℃, 3 hours or more) to prepare a negative electrode. The thickness of the active material layer in the obtained negative electrode was 100 μm, and the capacity density of the negative electrode was 3.0mAh/cm2。
(example 2)
A negative electrode was produced in the same manner as in example 1, except that 2.4 parts by mass of the copolymer a was used and 0.6 part by mass of polyvinyl alcohol (Kuraray Poval 105, number average molecular weight 22000, manufactured by kokurari corporation) was used in example 1. The thickness of the active material layer in the obtained negative electrode was 101 μm, and the capacity density of the negative electrode was 3.0mAh/cm2。
Comparative example 1
A negative electrode was produced in the same manner as in example 1, except that 3.0 parts by mass of the copolymer a was used in example 1 and polyvinyl alcohol was not used. The thickness of the active material layer in the obtained negative electrode was 99 μm, and the capacity density of the negative electrode was 3.0mAh/cm2。
Comparative example 2
The procedure of example 1 was repeated, except that 3.0 parts by mass of polyvinyl alcohol (Kuraray Poval 105, number average molecular weight 22000, manufactured by Korea corporation) was used in example 1, and copolymer A was not usedAnd (6) manufacturing a negative electrode. The thickness of the active material layer in the obtained negative electrode was 102 μm, and the capacity density of the negative electrode was 3.0mAh/cm2。
(peeling test)
The coating films (negative electrode active material layers) of the negative electrodes obtained in examples 1 and 2 and comparative examples 1 and 2 were tested for peel strength to the current collector. The negative electrode was cut to a width of 80mm × 15mm, and an adhesive tape was attached to the surface (negative electrode active material layer side), and then the attached negative electrode (current collector side) was fixed to a stainless steel plate with a double-sided tape, and this was used as a sample for evaluation. The evaluation sample was subjected to a 180-degree peel Test of the negative electrode with respect to a stainless steel plate (180-degree peel Test of an adhesive tape with respect to the negative electrode fixed to the stainless steel plate) using a tensile tester (EZ-Test, a small bench scale tester manufactured by shimadzu corporation), and the peel strength between the active material layer and the current collector in the negative electrode was measured. Table 1 shows the evaluation results of the peel test (peel strength).
(electrode Strength)
The strength of the electrode (referred to as "electrode strength") was evaluated based on the presence or absence of peeling, and chipping of the active material layer when the electrode obtained in examples 1 and 2 and comparative examples 1 and 2 was die-cut into a size of 11mm phi by a die cutter. Table 2 shows the evaluation results of the electrode strength.
○ (Excellent strength), wherein the number of electrodes was 2 or less, and it was confirmed by visual observation that the active material layer was peeled, or chipped after punching 10 pieces of electrodes randomly.
△ (strength is slightly excellent). after punching 10 pieces of electrodes randomly, the number of the electrodes is 3-5, and any one of peeling, falling off and defect of the active material layer is confirmed by visual judgment.
X (strength difference): after punching 10 pieces of electrodes randomly, it was confirmed by visual judgment that the number of the electrodes was 6 or more, which were any of peeling, and chipping of the active material layer.
(the far infrared ray of the battery)
A coin cell (CR2032) including the negative electrodes obtained in examples 1 and 2 and comparative examples 1 and 2, the counter electrode, the separator, and the electrolyte solution described below was prepared, and a sample (coin cell) was prepared by aging treatment at 0.1C for 3 cycles in an environment of 30 ℃.
Counter electrode: metallic lithium
A spacer: glass filter (GA-100, manufactured by ADVANTEC corporation)
Electrolyte solution: make LiPF6Dissolving Ethylene Carbonate (EC) and diethyl carbonate (DEC) in a concentration of 1mol/L in a solvent prepared by mixing Ethylene Carbonate (EC) and diethyl carbonate (DEC) in a volume ratio of 1: 1, and a solution in which 1 mass% of Vinylene Carbonate (VC) as an additive for an electrolyte solution is added
(method of evaluating DC resistance)
Each of the coin cells having the negative electrodes obtained in examples 1 and 2 and comparative example 1 and manufactured as described above was charged at 0.2C in a 30 ℃ environment and discharged at rates of 0.2C, 0.5C, 1C, 3C, and 5C, respectively. In the button cell, the cut-off potential was set to 0 to 1.0V (vs. Li +/Li). The direct current resistance (DC-IR) of the battery was calculated from the obtained I-V characteristics. Table 1 shows dc resistances of examples and comparative examples. The negative electrode obtained in comparative example 2 was not evaluated for direct current resistance because the electrode strength was too low to be suitable for forming an electrode.
[ Table 1]
Claims (10)
1. A binder for a non-aqueous electrolyte secondary battery electrode, characterized in that,
a copolymer of vinyl alcohol and an alkali metal neutralized product of an ethylenically unsaturated carboxylic acid, and polyvinyl alcohol.
2. The binder for a nonaqueous electrolyte secondary battery electrode according to claim 1,
wherein the copolymerization composition ratio of the vinyl alcohol in the copolymer to the ethylenically unsaturated carboxylic acid alkali metal neutralization product is 95/5-5/95 in terms of molar ratio.
3. The binder for a nonaqueous electrolyte secondary battery electrode according to claim 1 or 2,
wherein the ethylenically unsaturated carboxylic acid alkali metal neutralizer is a (meth) acrylic acid alkali metal neutralizer.
4. The binder for a nonaqueous electrolyte secondary battery electrode according to any one of claims 1 to 3, wherein a mass ratio of the copolymer to the polyvinyl alcohol is 95/5 to 70/30.
5. An electrode mixture for a nonaqueous electrolyte secondary battery, characterized in that,
a binder for a nonaqueous electrolyte secondary battery electrode, which comprises an electrode active material, a conductive auxiliary and the binder for a nonaqueous electrolyte secondary battery electrode according to any one of claims 1 to 4.
6. The electrode mix for a nonaqueous electrolyte secondary battery according to claim 5,
wherein the content of the binder is 0.5 to 40 parts by mass per 100 parts by mass of the total amount of the electrode active material, the conductive auxiliary agent, and the binder.
7. An electrode for a nonaqueous electrolyte secondary battery, characterized in that,
the electrode for a nonaqueous electrolyte secondary battery is produced by using the electrode mixture for a nonaqueous electrolyte secondary battery according to claim 5 or 6.
8. A nonaqueous electrolyte secondary battery characterized in that,
the nonaqueous electrolyte secondary battery includes the electrode for nonaqueous electrolyte secondary battery according to claim 7.
9. An electrical apparatus, characterized in that,
the electrical device is provided with the nonaqueous electrolyte secondary battery according to claim 8.
10. Use of a binder in an electrode for a non-aqueous electrolyte secondary battery,
the adhesive contains a copolymer of vinyl alcohol and an alkali metal neutralization of an ethylenically unsaturated carboxylic acid, and polyvinyl alcohol.
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| PCT/JP2018/035610 WO2019065705A1 (en) | 2017-09-29 | 2018-09-26 | Binder for nonaqueous electrolyte secondary battery electrode, electrode mixture for nonaqueous electrolyte secondary battery, electrode for nonaqueous electrolyte secondary battery, nonaqueous electrolyte secondary battery, and electric apparatus |
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| JPH08264180A (en) | 1995-03-24 | 1996-10-11 | Central Glass Co Ltd | Lithium secondary battery negative electrode material and lithium secondary battery using it |
| JP4003276B2 (en) | 1997-02-10 | 2007-11-07 | 東レ株式会社 | Battery electrode and secondary battery using the same |
| JP3601250B2 (en) | 1997-04-25 | 2004-12-15 | Ｊｓｒ株式会社 | Binder for non-aqueous battery electrode |
| KR20040049475A (en) | 2002-12-06 | 2004-06-12 | 삼성전자주식회사 | Wafer sawing method |
| CN108886148B (en) * | 2016-03-30 | 2022-06-17 | 住友精化株式会社 | Binder for nonaqueous electrolyte secondary battery electrode, and electrode and nonaqueous electrolyte secondary battery using same |
| JP7110170B2 (en) | 2017-03-16 | 2022-08-01 | 株式会社クラレ | Binder composition for nonaqueous electrolyte battery, binder aqueous solution for nonaqueous electrolyte battery using the same, slurry composition for nonaqueous electrolyte battery, electrode for nonaqueous electrolyte battery, and nonaqueous electrolyte battery |
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2018
- 2018-09-26 CN CN201880060479.4A patent/CN111095635A/en active Pending
- 2018-09-26 WO PCT/JP2018/035610 patent/WO2019065705A1/en active Application Filing
- 2018-09-26 KR KR1020207008046A patent/KR20200062197A/en not_active Application Discontinuation
- 2018-09-26 JP JP2019545548A patent/JP7223700B2/en active Active
- 2018-09-27 TW TW107134079A patent/TWI771498B/en active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104704662A (en) * | 2012-10-12 | 2015-06-10 | 独立行政法人产业技术综合研究所 | Binder for use in positive electrode for lithium ion secondary battery, positive electrode for lithium ion secondary battery containing said binder, lithium ion secondary battery using said positive electrode, and electrical machinery and apparatus |
| CN105340110A (en) * | 2013-06-28 | 2016-02-17 | 住友精化株式会社 | Negative-electrode mixture for non-aqueous electrolyte secondary cell, negative electrode for non-aqueous electrolyte secondary cell containing said mixture, non-aqueous electrolyte secondary cell provided with said negative electrode, and electrical device |
| CN106133863A (en) * | 2014-04-01 | 2016-11-16 | 住友精化株式会社 | Electrical double layer capacitor electrodes adhesive, the electrical double layer capacitor electrodes containing this adhesive, the double layer capacitor employing this electrode and electrical equipment |
| JP2015201267A (en) * | 2014-04-04 | 2015-11-12 | 住友精化株式会社 | Mixture for lithium ion secondary battery electrode, electrode for lithium ion secondary battery containing mixture, lithium ion secondary battery including electrode, and electric equipment |
Also Published As
| Publication number | Publication date |
|---|---|
| WO2019065705A1 (en) | 2019-04-04 |
| JP7223700B2 (en) | 2023-02-16 |
| JPWO2019065705A1 (en) | 2020-11-05 |
| TWI771498B (en) | 2022-07-21 |
| TW201921789A (en) | 2019-06-01 |
| KR20200062197A (en) | 2020-06-03 |
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