CN112385062A - Composition for electricity storage device, slurry for electricity storage device electrode, and electricity storage device - Google Patents
Composition for electricity storage device, slurry for electricity storage device electrode, and electricity storage device Download PDFInfo
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- CN112385062A CN112385062A CN201980045781.7A CN201980045781A CN112385062A CN 112385062 A CN112385062 A CN 112385062A CN 201980045781 A CN201980045781 A CN 201980045781A CN 112385062 A CN112385062 A CN 112385062A
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- storage device
- polymer
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- slurry
- composition
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Classifications
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- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/04—Acids; Metal salts or ammonium salts thereof
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- C08F236/04—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds conjugated
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- C08L25/10—Copolymers of styrene with conjugated dienes
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- C08L27/02—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 a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L27/12—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 a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
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- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
- H01G11/32—Carbon-based
- H01G11/38—Carbon pastes or blends; Binders or additives therein
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
- H01G11/50—Electrodes characterised by their material specially adapted for lithium-ion capacitors, e.g. for lithium-doping or for intercalation
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/131—Electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/134—Electrodes based on metals, Si or alloys
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The invention provides a composition for an electric storage device, which can be used for manufacturing an electric storage device electrode having excellent flexibility and adhesiveness and good charge-discharge durability. The composition for an electricity storage device of the present invention comprises a polymer (A) and a liquid medium (B), wherein the polymer (A) comprises 5 to 50 parts by mass of a repeating unit (a1) derived from a conjugated diene compound, 5 to 90 parts by mass of a repeating unit (a2) derived from an unsaturated carboxylic acid, and 5 to 90 parts by mass of a repeating unit (a3) derived from a (meth) acrylamide, and the total amount of the repeating unit (a2) and the repeating unit (a3) is 50 parts by mass or more, when the total amount of the repeating units contained in the polymer (A) is 100 parts by mass.
Description
Technical Field
The present invention relates to a composition for an electricity storage device, a slurry for an electricity storage device electrode containing the composition and an active material, an electricity storage device electrode formed by applying the slurry to a current collector and drying the slurry, and an electricity storage device provided with the electrode.
Background
In recent years, as a power source for driving an electronic device, a power storage device having a high voltage and a high energy density has been required. As such an electric storage device, a lithium ion battery, a lithium ion capacitor, and the like have been expected.
The electrode used in such an electric storage device is manufactured by: a composition (electrode slurry) containing an active material and a polymer that functions as a binder is applied to the surface of a current collector and dried. Examples of the characteristics required for the polymer used as the binder include binding ability of the active materials to each other and adhesion ability of the active materials to the current collector; abrasion resistance in the step of winding the electrode; and a powder falling resistance that prevents fine particles of the active material from falling off from a coating film (hereinafter, also referred to as an "active material layer") of the coated and dried composition even after subsequent cutting or the like.
It is empirically clear that the performance is approximately proportional to the binding ability of the active materials to each other, the adhesion between the active materials and the current collector, and the powder fall resistance. Therefore, in the present specification, these characteristics are sometimes expressed below in terms of "adhesion".
However, in recent years, from the viewpoint of achieving a demand for higher output and higher energy density of an electric storage device, studies have been advanced for using a material having a large lithium occlusion amount as an active material. For example, as disclosed in patent document 1, a method of effectively utilizing a silicon material having a theoretical lithium occlusion amount of at most about 4200mAh/g as an active material is considered promising.
However, an active material using such a material having a large lithium occlusion amount undergoes a large volume change due to occlusion and release of lithium. Therefore, if a conventionally used binder for an electrode is applied to such a material having a large lithium absorption amount, adhesion cannot be maintained, and the active material peels off, resulting in a significant capacity decrease with charge and discharge.
As a technique for improving the adhesion of a binder for an electrode, a technique of controlling the amount of surface acid of particulate binder particles has been proposed (see patent documents 2 and 3); and techniques for improving the above properties by using an adhesive having an epoxy group and a hydroxyl group (see patent documents 4 and 5). Further, a technique has been proposed in which an active material is bound by a rigid molecular structure of polyimide to suppress a change in volume of the active material (see patent document 6). In addition, a technique using a water-soluble polymer such as polyacrylic acid has also been proposed (see patent document 7).
Documents of the prior art
Patent document
Patent document 1: japanese patent laid-open publication No. 2004-185810
Patent document 2: international publication No. 2011/096463
Patent document 3: international publication No. 2013/191080
Patent document 4: japanese patent application laid-open No. 2010-205722
Patent document 5: japanese laid-open patent application No. 2010-3703
Patent document 6: japanese patent laid-open publication No. 2011-204592
Patent document 7: japanese laid-open patent publication No. 2007-294323
Disclosure of Invention
However, the binders for electrodes disclosed in patent documents 1 to 7 cannot be said to have sufficient adhesion when new active materials represented by silicon materials having a large amount of lithium occlusion and a large volume change accompanying lithium occlusion and release are put to practical use. When such a binder for an electrode is used, the electrode is deteriorated due to, for example, the falling-off of an active material caused by repeated charge and discharge, and therefore, there is a problem that durability required for practical use cannot be sufficiently obtained.
Accordingly, some embodiments of the present invention provide a composition for an electric storage device, which can produce an electric storage device electrode having excellent flexibility and adhesion and exhibiting good charge/discharge durability characteristics. In addition, some embodiments of the present invention provide a slurry for an electrode of an electric storage device containing the composition. In addition, some embodiments of the present invention provide an electricity storage device electrode that is excellent in flexibility and adhesion and exhibits good charge and discharge durability characteristics. Further, some embodiments of the present invention provide an electric storage device having excellent charge/discharge durability characteristics.
The present invention has been made to solve at least part of the above problems, and can be realized as any of the following embodiments.
One embodiment of the composition for an electric storage device of the present invention comprises a polymer (A) and a liquid medium (B),
the polymer (A) contains 5 to 50 parts by mass of a repeating unit (a1) derived from a conjugated diene compound, 5 to 90 parts by mass of a repeating unit (a2) derived from an unsaturated carboxylic acid, and 5 to 90 parts by mass of a repeating unit (a3) derived from a (meth) acrylamide, wherein the total of the repeating units contained in the polymer (A) is 100 parts by mass,
the total amount of the repeating unit (a2) and the repeating unit (a3) is 50 parts by mass or more.
In one embodiment of the composition for an electricity storage device, the polymer (a) may be a water-soluble polymer having a solubility in water of 1g or more relative to 100g of water at 25 ℃ under 1 atmosphere.
In any embodiment of the composition for an electric storage device, the pH may be 6 to 11.
In any embodiment of the composition for an electric storage device, the ratio (V9/V3) of the viscosity (V9[ mPa · s ]) at pH9 and the viscosity (V3[ mPa · s ]) at pH3 of 5% by mass of water in the polymer (a) may be 10 or more.
In any embodiment of the composition for an electricity storage device, the polymer (a) may have a viscosity of 500 to 150000mPa · s at pH9 of 5 mass% water.
In any embodiment of the composition for an electricity storage device, the liquid medium (B) may be water.
One embodiment of the slurry for an electric storage device electrode of the present invention contains the composition for an electric storage device of any of the above-described embodiments and an active material.
In one embodiment of the above slurry for an electrode of an electric storage device, a silicon material may be contained as the active material.
In any embodiment of the above slurry for an electric storage device electrode, at least 1 polymer selected from the group consisting of a styrene-butadiene copolymer, an acrylic polymer, and a fluorine-based polymer may be further contained.
In any embodiment of the above slurry for an electric storage device electrode, a thickener may be further contained.
One embodiment of the power storage device electrode of the present invention includes a current collector and an active material layer formed by applying the slurry for a power storage device electrode of any one of the above-described embodiments on a surface of the current collector and drying the applied slurry.
One embodiment of the power storage device of the present invention includes the power storage device electrode of the above-described embodiment.
According to the composition for an electric storage device of the present invention, since flexibility and adhesion can be improved, an electric storage device electrode exhibiting good charge-discharge durability can be produced. The composition for an electric storage device of the present invention exhibits the above-described effects particularly when the electric storage device electrode contains a material having a large lithium occlusion amount, for example, a carbon material such as graphite or a silicon material as an active material. That is, since a material having a large lithium occlusion amount can be used as the active material, the battery performance is also improved.
Detailed Description
Hereinafter, preferred embodiments of the present invention will be described in detail. The present invention is not limited to the embodiments described below, and it should be understood that the present invention also includes various modifications that can be implemented within a range not changing the gist of the present invention. In the present specification, "(meth) acrylic acid" is a concept including both "acrylic acid" and "methacrylic acid". Similarly, "- (meth) acrylate" is a concept including both of "-acrylate" and "-methacrylate". Likewise, "(meth) acrylamide" is a concept including both "acrylamide" and "methacrylamide".
In the present specification, the numerical range described by "to" is used to include numerical values described before and after "to" as the lower limit value and the upper limit value.
1. Composition for electricity storage device
The composition for an electricity storage device of the present embodiment contains a polymer (a) and a liquid medium (B). The composition for an electricity storage device of the present embodiment can be used as a material for producing an electricity storage device electrode (active material layer) for improving the binding ability between active materials, the adhesion ability between the active materials and a current collector, and the powder dropping resistance, and can also be used as a material for forming a protective film for suppressing short-circuiting due to dendrites generated during charge and discharge. Hereinafter, each component contained in the composition for an electric storage device of the present embodiment will be described in detail.
1.1. Polymer (A)
The composition for an electricity storage device of the present embodiment contains a polymer (a). The polymer (a) contains 5 to 50 parts by mass of a repeating unit (a1) derived from a conjugated diene compound (hereinafter, also simply referred to as "repeating unit (a 1)"), 5 to 90 parts by mass of a repeating unit (a2) derived from an unsaturated carboxylic acid (hereinafter, also simply referred to as "repeating unit (a 2)") and 5 to 90 parts by mass of a repeating unit (a3) derived from a (meth) acrylamide (hereinafter, also simply referred to as "repeating unit (a 3)") when the total of the repeating units contained in the polymer (a) is 100 parts by mass, and the total amount of the repeating unit (a2) and the repeating unit (a3) is 50 parts by mass or more. The polymer (a) may contain, in addition to the above-mentioned repeating units, repeating units derived from another monomer copolymerizable therewith. Examples of the other monomer include an unsaturated carboxylic acid ester having a hydroxyl group, an unsaturated carboxylic acid ester (excluding the above-mentioned unsaturated carboxylic acid ester having a hydroxyl group), an α, β -unsaturated nitrile compound, a cationic monomer, an aromatic vinyl compound, and a compound having a sulfonic acid group.
The polymer (a) contained in the composition for an electricity storage device of the present embodiment may be in the form of a latex dispersed in the liquid medium (B), or may be dissolved in the liquid medium (B), and is preferably dissolved in the liquid medium (B). In the case where the polymer (a) is dissolved in the liquid medium (B), the slurry for an electrode of an electric storage device (hereinafter, also simply referred to as "slurry") prepared by mixing with the active material is preferable because the slurry has good stability and good coatability on the current collector.
The following description will be made in order of the respective repeating units constituting the polymer (a), the physical properties of the polymer (a), and the production method.
1.1.1. Each repeating unit constituting the polymer (A)
< repeating Unit (a1) > < from the conjugated diene Compound
The content of the repeating unit (a1) derived from the conjugated diene compound is 5 to 50 parts by mass, based on 100 parts by mass of the total of the repeating units contained in the polymer (A). The lower limit of the content of the repeating unit (a1) is preferably 7 parts by mass, and more preferably 10 parts by mass. The upper limit of the content of the repeating unit (a1) is preferably 48 parts by mass, and more preferably 45 parts by mass. By containing the repeating unit (a1) in the above range, the polymer (a) having a low glass transition temperature can exist in the state of an aqueous solution, and therefore the dispersibility of the active material and the filler is good. Further, since the polymer (a) has flexibility, even if the polymer (a) is coated with an active material, the polymer (a) expands and contracts, and thereby the occurrence of structural defects in the electrode plate can be suppressed, and excellent charge and discharge durability characteristics can be exhibited.
The conjugated diene compound is not particularly limited, and includes 1, 3-butadiene, 2-methyl-1, 3-butadiene, 2, 3-dimethyl-1, 3-butadiene, 2-chloro-1, 3-butadiene and the like, and may be 1 or more selected from them. Among these, 1, 3-butadiene is particularly preferable.
< repeating Unit (a2) >, derived from unsaturated carboxylic acid
The content of the repeating unit (a2) derived from an unsaturated carboxylic acid is 5 to 90 parts by mass, based on 100 parts by mass of the total of the repeating units contained in the polymer (A). The lower limit of the content of the repeating unit (a2) is preferably 7 parts by mass, and more preferably 10 parts by mass. The upper limit of the content ratio of the repeating unit (a2) is preferably 85 parts by mass, and more preferably 80 parts by mass. By containing the repeating unit (a2) within the above range, the dispersibility of the active material and the filler is good. Further, the affinity with the silicon material as an active material is improved, swelling of the silicon material is suppressed, and favorable charge and discharge durability characteristics are exhibited.
The unsaturated carboxylic acid is not particularly limited, and may be a mono-or dicarboxylic acid such as acrylic acid, methacrylic acid, crotonic acid, maleic acid, fumaric acid, itaconic acid, and the like, and may be one or more selected from these.
< repeating unit (a3) > (meth) acrylamide-derived
The content of the (meth) acrylamide-derived repeating unit (a3) is 5 to 90 parts by mass, based on 100 parts by mass of the total of the repeating units contained in the polymer (A). The lower limit of the content of the repeating unit (a3) is preferably 7 parts by mass, and more preferably 10 parts by mass. The upper limit of the content ratio of the repeating unit (a3) is preferably 85 parts by mass, and more preferably 80 parts by mass. When the content ratio of the repeating unit (a3) is within the above range, the glass transition temperature (Tg) of the polymer (A) is appropriate. As a result, the dispersibility of the active material and the filler is good. The obtained active material layer has appropriate flexibility, and the current collector and the active material layer have good adhesion capability. Further, since the binding ability between the active materials containing the carbon material such as graphite and the silicon material can be improved, the flexibility of the obtained active material layer and the adhesion ability to the current collector can be further improved.
The (meth) acrylamide is not particularly limited, and may include acrylamide, methacrylamide, N-isopropylacrylamide, N-dimethylacrylamide, N-dimethylmethacrylamide, N-diethylacrylamide, N-diethylmethacrylamide, N-dimethylaminopropylacrylamide, N-dimethylaminopropylmethacrylamide, N-methylolmethacrylamide, N-methylolacrylamide, diacetoneacrylamide, maleic amide, acrylamide-t-butylsulfonic acid, and the like. These (meth) acrylamides may be used alone in 1 kind, or may be used in combination in 2 or more kinds.
The total amount of the repeating unit (a2) and the repeating unit (a3) is 50 parts by mass or more, preferably 55 parts by mass or more, and more preferably 60 parts by mass or more, assuming that the total amount of the repeating units contained in the polymer (a) is 100 parts by mass. When the total amount of the repeating unit (a2) and the repeating unit (a3) is in the above range, the dispersibility of the active material and the filler is good, and the flexibility and the adhesion are improved, thereby exhibiting good charge and discharge durability characteristics.
< other repeating Unit >
The polymer (a) may contain, in addition to the above-mentioned repeating units (a1) to (a3), repeating units derived from another monomer copolymerizable with these. Examples of such a repeating unit include a repeating unit (a4) derived from an unsaturated carboxylic acid ester having a hydroxyl group (hereinafter, also simply referred to as "repeating unit (a 4)"), a repeating unit (a5) derived from an unsaturated carboxylic acid ester (not including the unsaturated carboxylic acid ester having a hydroxyl group) (hereinafter, also simply referred to as "repeating unit (a 5)"), a repeating unit (a6) derived from an α, β -unsaturated nitrile compound (hereinafter, also simply referred to as "repeating unit (a 6)"), a repeating unit (a7) derived from an aromatic vinyl compound (hereinafter, also simply referred to as "repeating unit (a 7)"), a repeating unit (a8) derived from a compound having a sulfonic acid group (hereinafter, also simply referred to as "repeating unit (a 8)"), a repeating unit derived from a cationic monomer, and the like.
Specific examples of the unsaturated carboxylic acid ester having a hydroxyl group include, but are not particularly limited to, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 5-hydroxypentyl (meth) acrylate, 6-hydroxyhexyl (meth) acrylate, glycerol mono (meth) acrylate, and glycerol di (meth) acrylate. Among these, 2-hydroxyethyl (meth) acrylate and glycerol mono (meth) acrylate are preferable. These monomers may be used alone in 1 kind, or may be used in combination in 2 or more kinds.
The unsaturated carboxylic acid ester is not particularly limited, but is preferably a (meth) acrylate. Specific examples of the (meth) acrylic acid ester include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, n-pentyl (meth) acrylate, isoamyl (meth) acrylate, hexyl (meth) acrylate, cyclohexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, n-octyl (meth) acrylate, nonyl (meth) acrylate, decyl (meth) acrylate, ethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, allyl (meth) acrylate, and the like, and 1 or more selected from them may be used. Among these, 1 or more selected from methyl (meth) acrylate, ethyl (meth) acrylate and 2-ethylhexyl (meth) acrylate are preferable, and methyl (meth) acrylate is particularly preferable.
Specific examples of the α, β -unsaturated nitrile compound are not particularly limited, and acrylonitrile, methacrylonitrile, α -chloroacrylonitrile, α -ethylacrylonitrile, vinyl cyanide and the like can be mentioned, and 1 or more selected from them can be used. Among these, 1 or more selected from acrylonitrile and methacrylonitrile are preferable, and acrylonitrile is particularly preferable.
Specific examples of the aromatic vinyl compound are not particularly limited, and include styrene, α -methylstyrene, p-methylstyrene, vinyltoluene, chlorostyrene, divinylbenzene and the like, and 1 or more selected from them may be used. Among these, styrene is particularly preferable.
Specific examples of the compound having a sulfonic acid group include, but are not particularly limited to, compounds having a sulfonic acid group such as vinylsulfonic acid, styrenesulfonic acid, allylsulfonic acid, sulfoethyl (meth) acrylate, sulfopropyl (meth) acrylate, sulfobutyl (meth) acrylate, 2-acrylamido-2-methylpropanesulfonic acid, 2-hydroxy-3-acrylamidopropanesulfonic acid, and 3-allyloxy-2-hydroxypropanesulfonic acid, and basic salts thereof.
The cationic monomer is not particularly limited, and preferably at least 1 monomer selected from a secondary amine (salt), a tertiary amine (salt), and a quaternary ammonium salt. Specific examples of the cationic monomer are not particularly limited, and include 2- (dimethylamino) ethyl (meth) acrylate, dimethylaminoethyl (meth) acrylate chloromethane salt, 2- (diethylamino) ethyl (meth) acrylate, 3- (dimethylamino) propyl (meth) acrylate, 3- (diethylamino) propyl (meth) acrylate, 4- (dimethylamino) phenyl (meth) acrylate, 2- [ (3, 5-dimethylpyrazolyl) carbonylamino ] ethyl (meth) acrylate, 2- (0- [ 1' -methylpropyleneamino ] carboxy) ethyl (meth) acrylate, 2- (1-aziridinyl) ethyl (meth) acrylate, methacryloylcholine chloride, tris (2-acryloyloxyethyl) isocyanurate, 2-vinylpyridine, and mixtures thereof, Quinaldine red, 1, 2-bis (2-pyridyl) ethylene, 4' -hydrazino-2-stilbazole dihydrochloride hydrate, 4- (4-dimethylaminostyryl) quinoline, 1-vinylimidazole, diallylamine hydrochloride, triallylamine, diallyldimethylammonium chloride, dichloropropylamine, N-allylbenzylamine, N-allylaniline, 2, 4-diamino-6-diallylamino-1, 3, 5-triazine, N-trans-cinnamyl-N-methyl- (1-naphthylmethyl) amine hydrochloride, trans-N- (6, 6-dimethyl-2-hepten-4-ynyl) -N-methyl-1-naphthylmethyl amine hydrochloride, and the like. These monomers may be used alone in 1 kind, or may be used in combination in 2 or more kinds.
The total amount of 1 or more selected from the group consisting of the repeating unit (a5), the repeating unit (a6), and the repeating unit (a7), and the repeating unit (a2) in the polymer (a) is preferably 5 to 50 parts by mass, based on 100 parts by mass of the total of the repeating units contained in the polymer (a). When the polymer (a) contains the repeating units in the above-described ratio, the dispersibility of the active material and the filler becomes good, and the flexibility and the adhesion are further improved, so that the polymer (a) exhibits good charge/discharge durability characteristics.
The total amount of the repeating unit (a2), the repeating unit (a3), the repeating unit (a4) and the repeating unit (a8) in the polymer (a) is preferably 50 to 95 parts by mass, more preferably 52 to 92 parts by mass, and particularly preferably 55 to 90 parts by mass, based on 100 parts by mass of the total of the repeating units contained in the polymer (a). When the polymer (a) contains the repeating units in the above-described ratio, the dispersibility of the active material and the filler is good, and the flexibility and the adhesion are further improved, so that the polymer (a) exhibits good charge/discharge durability characteristics.
The total amount of the repeating unit (a1), the repeating unit (a5), the repeating unit (a6) and the repeating unit (a7) in the polymer (a) is preferably 50 parts by mass or less, more preferably 5 to 48 parts by mass, and particularly preferably 8 to 45 parts by mass, based on 100 parts by mass of the total of the repeating units contained in the polymer (a). When the polymer (a) contains the repeating units in the above-described ratio, the dispersibility of the active material and the filler is good, and the flexibility and the adhesion are further improved, so that the polymer (a) exhibits good charge/discharge durability characteristics.
1.1.2. Physical Properties of Polymer (A)
< solubility in Water >
The polymer (a) is preferably a water-soluble polymer. The "water-soluble polymer" in the present invention is a polymer having a solubility in water of 1g or more relative to 100g of water at 25 ℃ under 1 atmosphere. When the polymer (a) is a water-soluble polymer, the polymer (a) having excellent flexibility and adhesion can easily coat the surface of the active material, and therefore, the falling-off of the active material due to expansion and contraction of the active material during charge and discharge can be effectively suppressed, and an electric storage device exhibiting good charge and discharge durability characteristics can be easily obtained. Further, the slurry is preferable because the stability of the slurry is good and the applicability of the slurry to the current collector is also good.
< glass transition temperature >
The polymer (a) preferably has only one endothermic peak in a temperature range of 60 to 160 ℃ as measured by Differential Scanning Calorimetry (DSC) according to JIS K7121. More preferably, the temperature of the endothermic peak (i.e., glass transition temperature (Tg)) is in the range of 70 ℃ to 150 ℃. When the polymer (a) has only one endothermic peak in DSC analysis and the peak temperature is in the above range, the polymer (a) preferably exhibits good adhesion and can impart more good flexibility and adhesiveness to the active material layer.
1.1.3. Method for producing polymer (A)
The method for producing the polymer (a) is not particularly limited, and for example, polymerization is preferably carried out in a solvent mainly containing water in the presence of a known chain transfer agent, polymerization initiator, or the like. The polymer (a) may be synthesized by one-step polymerization, two-step polymerization or multi-step polymerization, and in each polymerization, the synthesis may be performed in the presence of a known polymerization initiator, a molecular weight regulator, an emulsifier (surfactant), or the like. The amounts and types of the polymerization initiator, the molecular weight modifier, the emulsifier (surfactant), and the like, and the synthesis method may be those described in Japanese patent No. 5477610, for example.
The pH can be adjusted to 6 to 11 by adding a neutralizing agent to the polymerization mixture obtained by the above synthesis method. The neutralizing agent used herein is not particularly limited, and examples thereof include metal hydroxides such as sodium hydroxide and potassium hydroxide; ammonia, and the like. By adjusting the pH to the above range, the polymer (a) can be dissolved in the liquid medium (B) to thicken the polymer (a). In addition, by concentrating the polymerization mixture after the neutralization treatment is performed, it is possible to maintain good stability of the polymer (a) and to increase the solid content concentration.
The slurry for an electrical storage device may be prepared using the composition for an electrical storage device in the state as it is without adding a neutralizing agent to the polymerization mixture obtained by the above synthesis method, and then the slurry for an electrical storage device may be thickened by adding a neutralizing agent thereto to adjust the pH to 6 to 11. In this case, the composition for an electricity storage device does not thicken, and therefore, the preparation of the slurry for an electricity storage device may be facilitated.
1.2. Liquid medium (B)
The composition for an electricity storage device of the present embodiment contains a liquid medium (B). The liquid medium (B) is preferably an aqueous medium containing water, and more preferably water. The aqueous medium may contain a nonaqueous medium other than water. Examples of the nonaqueous medium include amide compounds, hydrocarbons, alcohols, ketones, esters, amine compounds, lactones, sulfoxides, sulfone compounds, and the like, and 1 or more selected from them can be used. The composition for an electricity storage device of the present embodiment uses an aqueous medium as the liquid medium (B), and thus the degree of adverse effect on the environment is reduced and the safety of the operator is also improved.
The content of the nonaqueous medium contained in the aqueous medium is preferably 10 parts by mass or less, more preferably 5 parts by mass or less, and particularly preferably substantially not contained in 100 parts by mass of the aqueous medium. Here, "substantially not contained" means that the nonaqueous medium is not intentionally added as a liquid medium, and may contain a nonaqueous medium that is inevitably mixed in when the composition for an electricity storage device is prepared.
1.3. Other additives
The composition for an electricity storage device of the present embodiment may contain additives other than the above-described components as necessary. Examples of such additives include polymers other than the polymer (a), preservatives, and thickeners.
< polymers other than Polymer (A) >
The composition for an electricity storage device of the present embodiment may contain a polymer other than the polymer (a). Such a polymer is not particularly limited, and examples thereof include SBR (styrene butadiene rubber) polymers, acrylic polymers containing unsaturated carboxylic acid esters or derivatives thereof as constituent units, and fluorine polymers such as PVDF (polyvinylidene fluoride). These polymers may be used alone in 1 kind, or may be used in combination in 2 or more kinds. By containing a polymer other than the polymer (a), flexibility and adhesiveness may be further improved.
The content of the polymer (a) in the composition for an electricity storage device of the present embodiment is preferably 10 to 90 parts by mass, more preferably 20 to 80 parts by mass, and particularly preferably 25 to 75 parts by mass, based on 100 parts by mass of the total of the polymer (a), the polymer other than the polymer (a), and the thickener, which are contained as needed.
< preservatives >
The composition for an electricity storage device of the present embodiment may contain a preservative. By containing the preservative, the composition for an electric storage device can suppress the generation of foreign matter due to the propagation of bacteria, mold, or the like when stored. Specific examples of the preservative include compounds described in japanese patent No. 5477610 and the like.
< thickening agent >
The composition for an electricity storage device of the present embodiment may contain a thickener. By containing the thickener, the coating properties, the charge/discharge characteristics of the resulting power storage device, and the like may be further improved.
Specific examples of the thickener include cellulose compounds such as carboxymethyl cellulose, methyl cellulose, and hydroxypropyl cellulose; poly (meth) acrylic acid; an ammonium salt or an alkali metal salt of the above cellulose compound or the above poly (meth) acrylic acid; polyvinyl alcohol (co) polymers such as polyvinyl alcohol, modified polyvinyl alcohol, and ethylene-vinyl alcohol copolymers; and water-soluble polymers such as saponified copolymers of vinyl esters and unsaturated carboxylic acids such as (meth) acrylic acid, maleic acid, and fumaric acid. Among these, alkali metal salts of carboxymethyl cellulose, alkali metal salts of poly (meth) acrylic acid, and the like are preferable.
Commercially available products of these thickeners include alkali metal salts of carboxymethyl cellulose such as CMC1120, CMC1150, CMC2200, CMC2280, and CMC2450 (manufactured by Daicel corporation).
When the composition for an electricity storage device of the present embodiment contains a thickener, the content of the thickener is preferably 5 parts by mass or less, and more preferably 0.1 to 3 parts by mass, based on 100 parts by mass of the total solid content of the composition for an electricity storage device.
1.4. Physical Properties of composition for Electrical storage device
1.4.1.pH
The pH of the composition for an electric storage device of the present embodiment is preferably 6 to 11, more preferably 7 to 11, and particularly preferably 7 to 10.5. When the pH is within the above range, the viscosity of the composition for an electricity storage device can be increased by dissolving the polymer (a) in the liquid medium (B). This makes it possible to suppress the occurrence of problems such as insufficient leveling property and liquid dripping during slurry application, and to easily manufacture an electrode for an electric storage device having both excellent electric characteristics and excellent adhesion. In addition, the stability of the slurry is also improved.
The "pH" in the present specification refers to the physical properties measured as follows. Is a pH meter using a glass electrode calibrated using a neutral phosphate standard solution and a borate standard solution as pH standard solutions at 25 ℃, according to JIS Z8802: 2011 measured value. Examples of such a pH meter include "HM-7J" manufactured by DKK, Tokya and "D-51" manufactured by horiba, Ltd.
It should be noted that although it is not denied that the pH of the composition for an electric storage device is affected by the monomer components constituting the polymer (a), supplementary explanation is made not only by the monomer components. That is, it is generally known that the pH of the composition for an electric storage device varies depending on polymerization conditions and the like even with the same monomer components, and examples in the present specification merely show one example thereof.
For example, even if the same monomer components are used, the amount of carboxyl groups derived from unsaturated carboxylic acids exposed on the surface of the resulting polymer differs between the case where all unsaturated carboxylic acids are added to the polymerization reaction solution from the beginning, and then other monomers are sequentially added, and the case where monomers other than unsaturated carboxylic acids are added to the polymerization reaction solution and the case where unsaturated carboxylic acids are added at the end. It is considered that the pH of the composition for an electric storage device is greatly different even if the order of adding the monomers in the polymerization method is changed in this way.
1.4.2. Viscosity of the oil
The ratio (V9/V3) of the viscosity (V9[ mPas ]) at pH9 and the viscosity (V3[ mPas ]) at pH3 of 5% by mass of water in the polymer (A) is preferably 10 or more, more preferably 20 or more, and particularly preferably 50 or more. When the viscosity ratio (V9/V3) is not less than the above value, the dispersibility of the active material and the filler is good, and homogeneous active material layers and protective films can be easily produced. As a result, an electrode or the like free from structural defects can be obtained, and favorable charge and discharge characteristics are exhibited, which is preferable.
The viscosity of 5 mass% water of the polymer (A) was measured at a temperature of 25.0 ℃ using a type B viscometer according to JIS Z8803. As the type B viscometer, "RB-80L" and "TVB-10" manufactured by Toyobo industries, Inc. can be used, for example.
The viscosity of the polymer (A) at a pH of 9 of 5% by mass of water is preferably 500 to 150000 mPas, more preferably 1000 to 150000 mPas, and particularly preferably 2000 to 150000 mPas. When the viscosity at pH9 is in the above range, the dispersibility of the active material and the filler is good, and a uniform active material layer and protective film are easily formed. As a result, an electrode or the like free from structural defects can be obtained, and favorable charge and discharge characteristics are exhibited, which is preferable.
2. Slurry for electricity storage device
The slurry for an electricity storage device of the present embodiment contains the above-described composition for an electricity storage device. As described above, the composition for an electricity storage device according to the present embodiment can be used as a material for forming a protective film for suppressing short-circuiting due to dendrites generated by charge and discharge, and can also be used as a material for producing an electricity storage device electrode (active material layer) for improving the binding ability between active materials, the adhesion ability between the active materials and a current collector, and the powder dropping resistance. Therefore, the description will be divided into a slurry for an electric storage device for forming a protective film (hereinafter, also referred to as "slurry for forming a protective film") and a slurry for an electric storage device for forming an active material layer of an electric storage device electrode (hereinafter, also referred to as "slurry for an electric storage device electrode").
2.1. Slurry for forming protective film
The "slurry for forming a protective film" in the present specification means a dispersion liquid for forming a protective film on the surface of an electrode or a separator or both of them by applying the slurry to the surface of the electrode or the separator or both of them and then drying the applied slurry. The protective film forming slurry of the present embodiment may be composed of only the above-described composition for an electricity storage device, or may further contain an inorganic filler. Hereinafter, each component contained in the protective film forming slurry of the present embodiment will be described in detail. The composition for an electric storage device is as described above, and therefore, the description thereof is omitted.
2.1.1. Inorganic filler
When the protective film forming slurry of the present embodiment contains an inorganic filler, the toughness of the formed protective film can be improved. As the inorganic filler, particles of at least 1 kind selected from silica, titania (titanium dioxide), alumina (aluminum oxide), zirconia (zirconium dioxide), and magnesia (magnesia) are preferably used. Among these, titanium oxide and aluminum oxide are preferable from the viewpoint of further improving the toughness of the protective film. Further, as the titanium oxide, rutile type titanium oxide is more preferable.
The average particle diameter of the inorganic filler is preferably 1 μm or less, and more preferably in the range of 0.1 to 0.8. mu.m. The average particle diameter of the inorganic filler is preferably larger than the average pore diameter of the separator as the porous film. This can reduce damage to the separator and prevent the inorganic filler from blocking the micropores of the separator.
The slurry for forming a protective film according to the present embodiment preferably contains the above-described composition for an electricity storage device in an amount of 0.1 to 20 parts by mass, more preferably 1 to 10 parts by mass, in terms of solid content, based on 100 parts by mass of the inorganic filler. When the content ratio of the composition for an electric storage device is within the above range, the balance between the toughness of the formed protective film and the permeability of lithium ions becomes good, and as a result, the rate of increase in resistance of the electric storage device to be obtained can be further reduced.
2.1.2. Liquid medium
The protective film-forming slurry of the present embodiment may use the materials described in "1.2. liquid medium (B)" of the above-described composition for an electrical storage device, as needed. The amount of the liquid medium to be added may be adjusted as necessary so that the viscosity of the slurry can be optimized according to the coating method and the like.
2.1.3. Other ingredients
The protective film-forming slurry of the present embodiment may be prepared by using an appropriate amount of the material described in "1.3. other additives" of the composition for an electric storage device.
2.2. Slurry for electric storage device electrode
The "slurry for an electric storage device electrode" in the present specification means a dispersion liquid for forming an active material layer on the surface of a current collector by applying the slurry to the surface of the current collector and then drying the applied slurry. The slurry for an electric storage device electrode of the present embodiment contains the above-described composition for an electric storage device and an active material.
Generally, in order to improve the adhesion, a slurry for an electrode of an electric storage device contains a binder component such as an SBR copolymer and a thickener such as carboxymethyl cellulose in many cases. On the other hand, the slurry for an electric storage device electrode of the present embodiment can improve flexibility and adhesion only with the polymer (a). Needless to say, the slurry for an electric storage device electrode according to the present embodiment may contain a polymer other than the polymer (a) and a thickener in order to further improve the adhesion.
The components contained in the slurry for an electric storage device electrode of the present embodiment will be described below.
2.2.1. Polymer (A)
The composition, properties, and production method of the polymer (a) are as described above, and therefore, the description thereof is omitted.
The content of the polymer (a) in the slurry for an electrode of an electricity storage device of the present embodiment is preferably 1 to 8 parts by mass, more preferably 1 to 7 parts by mass, and particularly preferably 1.5 to 6 parts by mass, based on 100 parts by mass of the active material. When the content ratio of the polymer (a) is within the above range, the dispersibility of the active material in the slurry is good, and the coatability of the slurry is also excellent. The same applies to the case where the slurry for an electric storage device electrode of the present embodiment contains a polymer other than the polymer (a) and a thickener.
2.2.2. Active substance
Examples of the active material used in the slurry for an electric storage device electrode of the present embodiment include a carbon material, a silicon material, an oxide containing a lithium atom, a lead compound, a tin compound, an arsenic compound, an antimony compound, an aluminum compound, and the like. Specific examples thereof include compounds described in japanese patent No. 5999399 and the like.
The active material layer may contain an active material exemplified below. For example, a conductive polymer such as polyacene; a. theXBYOZ(wherein A represents an alkali metal or a transition metal, B represents at least 1 kind of transition metal selected from cobalt, nickel, aluminum, tin, manganese and the like, O represents an oxygen atom, and X, Y and Z are numbers in the ranges of 1.10 > X > 0.05, 4.00 > Y > 0.85, 5.00 > Z > 1.5, respectively), and other metal oxides.
The slurry for an electric storage device electrode of the present embodiment can be used for producing any one of the positive and negative electric storage device electrodes, and is preferably used for both the positive and negative electrodes.
When lithium iron phosphate is used as the positive electrode active material, there is a problem that the charge-discharge characteristics are insufficient and the adhesion is poor. One of the main causes is considered to be that lithium iron phosphate has a fine primary particle size, and is known as a secondary aggregate thereof, and when charge and discharge are repeated, the lithium iron phosphate is aggregated and collapsed in the active material layer to cause separation of the active materials, and the active materials are separated from the current collector, so that the conductive network inside the active material layer is easily broken.
However, in the electric storage device electrode manufactured using the slurry for an electric storage device electrode according to the present embodiment, the above-described problem does not occur even when lithium iron phosphate is used, and favorable electric characteristics can be exhibited. This is considered to be because the polymer (a) can strongly bind lithium iron phosphate and can maintain a state in which lithium iron phosphate is strongly bound even during charging and discharging.
On the other hand, in the case of producing a negative electrode, the above-exemplified active material preferably contains a silicon material. Since the silicon material has a larger amount of lithium absorbed per unit weight than other active materials, the storage capacity of the resulting power storage device can be increased by including the silicon material as a negative electrode active material, and as a result, the output and energy density of the power storage device can be increased.
In addition, as the negative electrode active material, a mixture of a silicon material and a carbon material is more preferable. Since the carbon material has a small volume change accompanying charge and discharge, the use of a mixture of a silicon material and a carbon material as the negative electrode active material can alleviate the influence of the volume change of the silicon material, and can further improve the adhesion between the active material layer and the current collector.
When silicon (Si) is used as an active material, silicon has a high capacity, and a large volume change occurs when lithium is stored. Therefore, the silicon material is easily pulverized by repeated expansion and contraction, and is separated from the current collector, causing separation of the active materials, and the conductive network inside the active material layer is easily broken. Thus, the cycle characteristics are extremely deteriorated in a short time.
However, in the power storage device electrode manufactured using the slurry for power storage device electrodes of the present embodiment, the above-described problems do not occur even when a silicon material is used, and favorable electrical characteristics can be exhibited. This is considered to be because the polymer (a) can firmly bond the silicon material, and even if the silicon material expands in volume due to lithium occlusion, the polymer (a) expands and contracts to maintain the state where the silicon material is firmly bonded.
The content ratio of the silicon material to 100% by mass of the active material is preferably 1% by mass or more, more preferably 1 to 50% by mass, even more preferably 5 to 45% by mass, and particularly preferably 10 to 40% by mass. If the content of the silicon material in 100% by mass of the active material is within the above range, an electric storage device having an excellent balance between improvement in output and energy density of the electric storage device and charge-discharge durability characteristics can be obtained.
The shape of the active material is preferably granular. The average particle diameter of the active material is preferably 0.1 to 100 μm, more preferably 1 to 20 μm. Here, the average particle size of the active material is a volume average particle size calculated from a particle size distribution obtained by measuring the particle size distribution using a particle size distribution measuring apparatus based on a laser diffraction method. Examples of such a laser diffraction particle size distribution measuring apparatus include HORIBA LA-300 series and HORIBA LA-920 series (manufactured by HORIBA, Ltd.).
2.2.3. Other ingredients
In the slurry for an electric storage device electrode of the present embodiment, other components may be added as necessary in addition to the above components. Examples of such components include polymers other than the polymer (a), thickeners, conductivity imparting agents, liquid media (excluding components derived from the composition for electric storage devices), pH adjusting agents, and anticorrosive agents. The polymer and the thickener other than the polymer (A) may be selected from the compounds exemplified in the above-mentioned "1.3. other additives" and used for the same purpose and content ratio. Examples of the conductivity-imparting agent include compounds described in japanese patent No. 5999399 and the like.
< liquid Medium >
The liquid medium that can be added to the slurry for an electric storage device electrode according to the present embodiment may be the same as or different from the liquid medium (B) contained in the composition for an electric storage device, and is preferably selected from the liquid media exemplified in the above-mentioned "1.2. liquid medium (B)".
The ratio of the liquid medium (including components derived from the power storage device composition) in the slurry for the power storage device electrode of the present embodiment is preferably a ratio such that the solid content concentration in the slurry (the ratio of the total mass of components other than the liquid medium in the slurry to the total mass of the slurry, the same applies hereinafter) is 30 to 70 mass%, and more preferably 40 to 60 mass%.
< pH regulator, anticorrosive agent >
The slurry for an electric storage device electrode of the present embodiment may contain a pH adjuster or an anticorrosive agent depending on the kind of the active material for the purpose of suppressing corrosion of the current collector.
Examples of the pH adjuster include hydrochloric acid, phosphoric acid, sulfuric acid, acetic acid, formic acid, ammonium phosphate, ammonium sulfate, ammonium acetate, ammonium formate, ammonium chloride, sodium hydroxide, and potassium hydroxide, and among these, sulfuric acid, ammonium sulfate, sodium hydroxide, and potassium hydroxide are preferable. Further, it may be selected from the compounds described in the method for producing the polymer (a).
Examples of the anticorrosive include ammonium metavanadate, sodium metavanadate, potassium metavanadate, ammonium metatungstate, sodium metatungstate, potassium metatungstate, ammonium paratungstate, sodium paratungstate, potassium paratungstate, ammonium molybdate, sodium molybdate, and potassium molybdate, and among these, ammonium paratungstate, ammonium metavanadate, sodium metavanadate, potassium metavanadate, and ammonium molybdate are preferable.
2.2.4. Preparation method of slurry for electrode of electric storage device
The slurry for an electric storage device electrode of the present embodiment may be any slurry for an electric storage device electrode produced by any method as long as it contains the above-described composition for an electric storage device and an active material, and can be produced by a method described in, for example, japanese patent No. 5999399 and the like.
3. Electrode for electrical storage device
The power storage device electrode of the present embodiment includes a current collector and an active material layer formed by applying the above-described slurry for a power storage device electrode on the surface of the current collector and drying the applied slurry. The above-described electric storage device electrode is manufactured by: the slurry for an electric storage device electrode is applied to the surface of a current collector such as a metal foil to form a coating film, and the coating film is dried to form an active material layer. The thus-produced storage device electrode is obtained by bonding an active material layer containing the polymer (a), an active material and, if necessary, an optional component to a current collector, and therefore has excellent flexibility and adhesion, and exhibits good charge/discharge durability.
The current collector is not particularly limited as long as it is made of a conductive material, and examples thereof include those described in japanese patent No. 5999399 and the like.
The method of applying the slurry for an electrode of an electricity storage device to the current collector is also not particularly limited, and the slurry can be applied by a method described in, for example, japanese patent No. 5999399. The electric storage device electrode thus produced has excellent flexibility and adhesion, and exhibits good charge/discharge durability.
In the electricity storage device electrode of the present embodiment, when a silicon material is used as the active material, the content ratio of the silicon element in 100 parts by mass of the active material layer is preferably 2 to 30 parts by mass, more preferably 2 to 20 parts by mass, and particularly preferably 3 to 10 parts by mass. If the content of silicon element in the active material layer is within the above range, the storage capacity of the electric storage device manufactured using the same is improved, and an active material layer in which silicon element is uniformly distributed can be obtained.
The content of silicon element in the active material layer in the present invention can be measured by, for example, the method described in japanese patent No. 5999399 and the like.
4. Electrical storage device
The electric storage device of the present embodiment can be manufactured by a conventional method using a member such as a separator, which includes the above-described electric storage device electrode and further contains an electrolytic solution. Specific examples of the production method include a method in which the negative electrode and the positive electrode are stacked via a separator, and the stack is wound or folded according to the shape of the battery and stored in a battery container, and an electrolyte solution is injected into the battery container to seal the battery container. The shape of the battery may be a coin shape, a cylinder shape, a square shape, a laminate shape, or other suitable shape.
The electrolyte may be in a liquid state or a gel state, and an electrolyte that effectively exhibits a function as a battery may be selected from known electrolytes used in power storage devices depending on the type of the active material. The electrolyte solution may be a solution in which an electrolyte is dissolved in an appropriate solvent. Examples of the electrolyte and the solvent include compounds described in japanese patent No. 5999399 and the like.
5. Examples of the embodiments
The present invention will be specifically described below with reference to examples, but the present invention is not limited to these examples. In examples and comparative examples, "part(s)" and "%" are based on mass unless otherwise specified.
5.1. Example 1
5.1.1. Preparation and evaluation of composition for electric storage device
(1) Preparation of composition for electricity storage device
900 parts by mass of water, 0.1 part by mass of sodium persulfate, 0.5 part by mass of dodecylbenzenesulfonic acid, 20 parts by mass of 1, 3-butadiene, 20 parts by mass of acrylic acid and 60 parts by mass of acrylamide were charged in a 100-L autoclave and reacted at 70 ℃ for 18 hours. Thereafter, the reaction mixture was cooled and divided into 2 portions, and one portion was adjusted to pH3.0 and the other portion was adjusted to pH9.0 using a5 wt% aqueous solution of sodium hydroxide. Thereafter, residual monomers were removed by steam distillation and concentrated under reduced pressure, thereby obtaining a composition for an electricity storage device having a ph of 3.0 containing 20 mass% of the polymer (a1) and a composition for an electricity storage device having a ph of 9.0 containing 20 mass% of the polymer (a1), respectively. The pH was adjusted by adding a5 wt% aqueous solution of sodium hydroxide dropwise while measuring the pH at 25 ℃ using a pH meter (manufactured by horiba, Ltd.).
(2) Measurement of viscosity
The 2 types of compositions for power storage devices obtained above were adjusted to pH3.0 or 9.0 by adding water so that the polymer (a1) became 5 mass%, and dropping a5 wt% aqueous solution of sodium hydroxide. The viscosity at 25 ℃ of the 2 types of compositions for electricity storage devices thus obtained was measured with a B-type viscometer, and as a result, the viscosity of the composition for electricity storage devices having a ph of 3.0 was 100mPa · s, and the viscosity of the composition for electricity storage devices having a ph of 9.0 was 10000mPa · s. The results are shown in table 1.
(3) Determination of swelling degree of electrolyte
A composition for an electricity storage device having a pH of 9.0 and containing 20 mass% of the polymer (A1) obtained above was poured into a petri dish having a diameter of 8cm in terms of solid content, and dried at 40 ℃ for 1 day to obtain a dried film. Thereafter, the dried membrane was taken out of the petri dish and further dried at 160 ℃ for 0.5 hour to obtain a membrane for test. Then, a plurality of the test membranes obtained were cut into pieces of 2cm × 2cm, and the initial mass was measured (W0 (g)). Thereafter, the test membrane was immersed in a screw bottle with a standard electrolyte added thereto at 70 ℃ for 24 hours. Thereafter, the test film was taken out of the standard electrolyte solution, and the mass after immersion after the test was measured after wiping off the electrolyte solution adhering to the film surface (W1 (g)). From the initial mass (W0(g)) and the mass after immersion (W1(g)) thus obtained, the swelling degree of the electrolyte solution was calculated according to the following formula.
Degree of swelling (%) of electrolyte solution (W1/W0) × 100
(4) Evaluation of Water solubility
The composition for an electricity storage device having ph9.0 obtained above was diluted with water so that the polymer (a1) became 1 mass%. The transparency of the thus obtained composition for an electrical storage device was confirmed by visual observation under 1 atmosphere at 23 ℃. The results are shown in table 1. The composition for an electric storage device is judged to be "water-soluble" and is described as "a" when it is transparent, and is judged to be "water-insoluble" and is described as "B" when it is translucent or white-turbid.
5.1.2. Preparation and evaluation of slurry for electric storage device electrode
(1) Synthesis of silicon materials (active substances)
Heating a mixture of pulverized silicon dioxide powder (average particle diameter of 10 μm) and carbon powder (average particle diameter of 35 μm) in an electric furnace at 1100-1600 ℃ for 10 hours under nitrogen gas flow (0.5 NL/min) to obtain SiOxAnd (x is 0.5 to 1.1) a powder of silicon oxide (average particle diameter 8 μm). 300g of this silicon oxide powder was charged into a batch-type heating furnace, and the temperature was raised from room temperature (25 ℃ C.) to 1100 ℃ at a temperature raising rate of 300 ℃/h while maintaining a reduced pressure of 100Pa in absolute pressure by a vacuum pump. Subsequently, while maintaining the pressure in the heating furnace at 2000Pa, methane was introduced at a flow rate of 0.5 NL/minThe graphite film was heated at 1100 ℃ for 5 hours while the gas was being introduced. After the completion of the graphite coating treatment, the resultant was cooled to room temperature at a cooling rate of 50 ℃/h to obtain about 330g of graphite coated silica powder. The graphite-coated silica is a conductive powder (active material) in which the surface of silica is coated with graphite, and has an average particle diameter of 10.5 μm, and the proportion of the graphite coating is 2 mass% assuming that the whole of the obtained graphite-coated silica is 100 mass%.
(2) Preparation of slurry for electric storage device electrode
4 parts by mass of a polymer (A1) (solid content equivalent, added as a composition for an electricity storage device having a pH of 9.0 containing 20% by mass of the obtained polymer (A1)), 76 parts by mass of an artificial graphite (MAG) which is highly crystalline graphite (manufactured by Hitachi chemical Co., Ltd.) (solid content equivalent), 19 parts by mass of a powder of the graphite-coated silicon oxide (solid content equivalent) obtained above, and 1 part by mass of carbon (acetylene black, manufactured by Denka Co., Ltd.) as a conductivity-imparting agent were put into a biaxial planetary mixer (manufactured by Primex corporation, trade name "TKHIVIS MIX 2P-03"), and stirred at 60rpm for 1 hour to obtain a paste. The obtained paste was charged with water to adjust the solid content concentration to 48% by mass, and then stirred and mixed at 200rpm for 2 minutes, 1800rpm for 5 minutes using a stirring and defoaming machine (product name "Awatori Rentaro" manufactured by THINKY Co., Ltd.), and further under reduced pressure (about 2.5X 10)4Pa) was stirred and mixed at 1800rpm for 1.5 minutes, thereby preparing a slurry for an electrode of an electric storage device (C/Si (20%)) containing 20 mass% of Si in the negative electrode active material.
5.1.3. Production and evaluation of Electrical storage device
(1) Production of electrode (negative electrode) for electricity storage device
The slurry for an electric storage device electrode (C/Si (20%)) obtained as described above was uniformly applied to the surface of a current collector made of a copper foil having a thickness of 20 μm by a doctor blade method so that the dried film thickness became 80 μm, and was dried at 60 ℃ for 10 minutes and then dried at 120 ℃ for 10 minutes. Thereafter, the active material layer was rolled using a roll press so that the density of the active material layer became 1.5g/cm3The electric storage device electrode (negative electrode) was obtained by performing press working.
(2) Evaluation of adhesion strength of negative coating layer
On the surface of the electrode sheet obtained above, 10 cuts each having a length and a width of from the active material layer to the depth reaching the current collector were cut at 2mm intervals using a knife to prepare cuts of the base grid. An adhesive tape (product name "Cellotape" (registered trademark) JIS Z1522, manufactured by Nichiban corporation) having a width of 18mm was attached to the cut, and immediately peeled off, and the degree of peeling of the active material was evaluated by visual observation and determination. The evaluation criteria are as follows. The evaluation results are shown in table 1.
(evaluation criteria)
5 min: the number of active material layers dropped was 0.
4 min: the number of active material layers dropped is 1 to 5.
3 min: the number of the active material layers falling off is 6 to 20.
2 min: the number of active material layers dropped is 21 to 40.
1 part: the number of the active material layers dropped was 41 or more.
(3) Manufacture of counter electrode (positive electrode)
A biaxial planetary mixer (manufactured by Primex corporation, trade name "TKHIVIS MIX 2P-03") was charged with 4.0 parts by mass (solid content converted value) of a binder for electrochemical device electrodes (manufactured by KUREHA, trade name "KF Polymer # 1120", hereinafter abbreviated as "PVDF"), 3.0 parts by mass of a conductive aid (manufactured by Denka corporation, trade name "Denka Black 50% compact"), and LiCoO having an average particle diameter of 5 μm as a positive electrode active material2(Lin chemical products Co., Ltd.) 100 parts by mass (solid content) and N-methyl pyrrolidone (NMP)36 parts by mass, 60rpm for 2 time stirring. NMP was added to the resulting paste to adjust the solid content concentration to 65 mass%, and then the mixture was stirred and mixed at 200rpm for 2 minutes, 1800rpm for 5 minutes using a stirring and defoaming machine (product of THINKY, Inc., trade name "Awatorei Rentaro"), and further under reduced pressure (about 2.5X 10)4Pa) was stirred and mixed at 1800rpm for 1.5 minutes, to thereby prepare a positive electrodeA slurry is used. The slurry for a positive electrode was uniformly applied to the surface of a current collector made of aluminum foil by a doctor blade method so that the thickness of the film after the solvent removal became 80 μm, and the solvent was removed by heating at 120 ℃ for 20 minutes. Thereafter, the density of the active material layer was adjusted to 3.0g/cm by a roll press3The counter electrode (positive electrode) was obtained by press working.
(4) Assembly of lithium ion battery cells
The negative electrode thus produced was punched and molded into a 15.95mm diameter molded article in a glove box in which Ar was replaced with a material having a dew point of-80 ℃ or lower, and the molded article was placed on a 2-pole coin Cell (trade name "HS Flat Cell" manufactured by Baoquan Co., Ltd.). Next, a separator (product name "Celgard # 2400") made of a polypropylene porous membrane punched out to have a diameter of 24mm was placed, 500 μ L of an electrolyte was injected so as not to enter air, the positive electrode thus produced was punched out to have a diameter of 16.16mm, and the outer casing of the 2-pole coin battery was screwed and sealed to assemble a lithium ion battery cell (power storage device). The electrolyte used here was a solution of LiPF dissolved in a solvent of ethylene carbonate/ethyl methyl carbonate 1/1 (mass ratio) at a concentration of 1 mol/L6The solution of (1).
(5) Evaluation of Charge-discharge cycle characteristics
In the electric storage device manufactured as described above, charging was started with a constant current (1.0C) in a thermostatic bath with a temperature controlled at 25 ℃, and continued with a constant voltage (4.2V) at a time when the voltage became 4.2V, and the end of charging (cut off) was set at a time when the current value became 0.01C. Thereafter, discharge was started at a constant current (1.0C), and the discharge capacity in the 1 st cycle was calculated with the time when the voltage became 3.0V set as the discharge end (cut off). This was repeated 100 times. The capacity retention rate was calculated from the following formula and evaluated by the following criteria. The evaluation results are shown in table 1.
Capacity retention (%) - (discharge capacity at 100 th cycle)/(discharge capacity at 1 st cycle)
(evaluation criteria)
5 min: the capacity retention rate is 95% or more.
4 min: the capacity retention rate is 90% or more and less than 95%.
3 min: the capacity retention rate is 85% or more and less than 90%.
2 min: the capacity retention rate is 80% or more and less than 85%.
1 part: the capacity retention rate is 75% or more and less than 80%.
0 min: the capacity retention rate is less than 75%.
In the measurement conditions, "1C" indicates a current value at which the battery cell having a certain constant capacity is discharged at a constant current and reaches the end of discharge within 1 hour. For example, "0.1C" is a current value at which the end of discharge is reached in 10 hours, and "10C" is a current value at which the end of discharge is reached in 0.1 hours.
5.2. Examples 2 to 25 and comparative examples 1 to 8
In the above "preparation and evaluation of composition for electricity storage device of 5.1.1" (1) preparation of composition for electricity storage device ", compositions for electricity storage device containing 20 mass% of polymer component were obtained in the same manner except that the kind and amount of each monomer were as shown in table 1 or table 2 below. In the present specification, the polymer (a) obtained in example 1 is referred to as "polymer (a 1)", the polymer (a) obtained in example 7 is referred to as "polymer (a 7)", and the polymer (a) obtained in example 14 is referred to as "polymer (a 14)", for example. The polymer obtained in comparative example 1 is referred to as "polymer (B1)", and the polymer obtained in comparative example 5 is referred to as "polymer (B5)", for example.
Further, other than using the above-prepared composition for an electric storage device, slurries for electric storage device electrodes were prepared in the same manner as in example 1, and an electric storage device electrode and an electric storage device were prepared and evaluated in the same manner as in example 1.
5.3. Example 31
A composition for an electricity storage device having a ph of 9.0 and containing 20 mass% of the polymer (a7) was obtained in the same manner as in example 7. Then, the mixture was stirred in a biaxial planetary mixer (Primex Co., Ltd.)The material was added under the trade name "TK HIVIS MIX 2P-03") as a preliminary additive, 1 part by mass of a thickener (trade name "CMC 2200", manufactured by Daicel corporation) (solid content equivalent, added as an aqueous solution having a concentration of 2% by mass), 1 part by mass of a polymer (a7) (solid content equivalent, added as a composition for electric storage devices having a ph of 9.0 containing 20% by mass of the obtained polymer (a7), 76 parts by mass of an artificial graphite (MAG, manufactured by hitachi chemical industries, inc.) as a graphite having high crystallinity as a negative electrode active material (solid content equivalent), 19 parts by mass of a powder of the graphite-coated silicon oxide (solid content equivalent), and 1 part by mass of carbon (acetylene black, manufactured by Denka corporation) as a conductivity-imparting agent, and the mixture was stirred at 60rpm for 1 hour. Then, SBR (trade name "TRD 105A", manufactured by JSR corporation) as a post-addition component was added in an amount corresponding to only 2 parts by mass (in terms of solid content), and the mixture was further stirred for 1 hour to obtain a paste. The obtained paste was charged with water to adjust the solid content concentration to 48% by mass, and then stirred and mixed at 200rpm for 2 minutes, 1800rpm for 5 minutes using a stirring and defoaming machine (product of THINKY, inc., trade name "Awatori rentro"), and further subjected to reduced pressure (about 2.5 × 10)4Pa) was stirred and mixed at 1800rpm for 1.5 minutes, thereby preparing a slurry for an electrode of an electric storage device (C/Si (20%)) containing 20 mass% of Si in the negative electrode active material.
An electric storage device electrode and an electric storage device were each produced in the same manner as in example 1, except that the slurry for an electric storage device electrode prepared in the above was used, and evaluated in the same manner as in example 1.
5.4. Examples 26 to 30 and 32 and comparative examples 9 to 15
An electric storage device electrode slurry was prepared in the same manner as in example 31 above, an electric storage device electrode and an electric storage device were prepared, respectively, and evaluated in the same manner as in example 31, except that the composition of the electric storage device electrode slurry was changed as shown in table 3 below.
5.5. Evaluation results
Tables 1 to 3 below summarize the polymer compositions, physical properties, and evaluation results used in examples 1 to 32 and comparative examples 1 to 15.
[ Table 1]
[ Table 2]
[ Table 3]
The abbreviations for the monomers in tables 1 to 3 above represent the following compounds, respectively.
< conjugated diene Compound >
BD: 1, 3-butadiene
< unsaturated carboxylic acid >
TA: itaconic acid
AA: acrylic acid
MAA: methacrylic acid
(meth) acrylamide
AAM: acrylamide
MAM: methacrylamide
< unsaturated carboxylic acid ester having hydroxyl group >
HEMA: 2-Hydroxyethyl methacrylate
HEA: 2-Hydroxyethyl acrylate
GLM: glycerol monomethacrylate
< unsaturated Carboxylic acid ester >
MMA: methacrylic acid methyl ester
CHMA: cyclohexyl methacrylate
2 EHA: 2-ethylhexyl acrylate
BA: acrylic acid n-butyl ester
EA: acrylic acid ethyl ester
< alpha, beta-unsaturated nitrile Compound >
AN: acrylonitrile
< aromatic vinyl Compound >
ST: styrene (meth) acrylic acid ester
< Compound having sulfonic acid group >
NASS: sodium styrene sulfonate
As is clear from table 1 and table 2 above, the slurries for an electrode of an electric storage device, which were prepared using the compositions for an electric storage device of the present invention shown in examples 1 to 25, can appropriately bind active materials having a large volume change accompanying charge and discharge to each other, and can maintain good adhesion between the active material layer and the current collector, as compared with the cases of comparative examples 1 to 8. As a result, an electrode for an electric storage device can be obtained which can suppress the separation of the active material layer and maintain good charge and discharge characteristics continuously, despite repeated charge and discharge and repeated volume expansion and contraction of the active material. Further, it was found that the charge/discharge rate characteristics of the power storage device (lithium ion secondary battery) including these power storage device electrodes were also good. This is presumed to be because the storage battery electrodes of examples 1 to 25 shown in the table can reduce the change in film thickness of the active material layer due to charge and discharge as compared with the cases of comparative examples 1 to 8, and can thereby maintain the conductive network inside the active material layer.
Further, as is clear from the results in table 3 above, it is found that the slurries for an electric storage device electrode, which are prepared using the compositions for an electric storage device of the present invention shown in examples 26 to 32, can appropriately bind active materials having a large volume change accompanying charge and discharge to each other and can maintain the adhesion between the active material layer and the current collector well, even when the slurries are used in combination with a thickener or other polymer, as compared with the cases of comparative examples 9 to 15.
The present invention is not limited to the above-described embodiments, and various modifications can be made. The present invention includes substantially the same configurations (for example, configurations having the same functions, methods, and results, or configurations having the same objects and effects) as those described in the embodiments. The present invention includes a configuration in which the non-essential part of the configuration described in the above embodiment is replaced with another configuration. The present invention also includes a configuration that achieves the same operational effects or the same objects as those of the configuration described in the above embodiment. The present invention also includes a configuration in which a known technique is added to the configuration described in the above embodiment.
Claims (12)
1. A composition for an electric storage device comprising a polymer (A) and a liquid medium (B),
the polymer (A) contains 5 to 50 parts by mass of a repeating unit (a1) derived from a conjugated diene compound, 5 to 90 parts by mass of a repeating unit (a2) derived from an unsaturated carboxylic acid, and 5 to 90 parts by mass of a repeating unit (a3) derived from a (meth) acrylamide, wherein the total of the repeating units contained in the polymer (A) is 100 parts by mass,
the total amount of the repeating unit (a2) and the repeating unit (a3) is 50 parts by mass or more.
2. The composition for a power storage device according to claim 1, wherein the polymer (A) is a water-soluble polymer having a solubility in water of 1g or more relative to 100g of water at 25 ℃ under 1 atmosphere.
3. The composition for power storage devices according to claim 1 or 2, wherein the pH is 6 to 11.
4. The composition for power storage devices according to any one of claims 1 to 3, wherein a ratio V9/V3 of a viscosity V9 at pH9 and a viscosity V3 at pH3 of 5 mass% water of the polymer (A) is 10 or more, and a unit of the viscosity is mPas.
5. The composition for power storage devices according to any one of claims 1 to 4, wherein the viscosity of 5% by mass water in the polymer (A) at pH9 is 500 to 150000 mPas.
6. The composition for a power storage device according to any one of claims 1 to 5, wherein the liquid medium (B) is water.
7. A slurry for an electrode of an electric storage device, comprising the composition for an electric storage device according to any one of claims 1 to 6 and an active material.
8. The slurry for an electrode of a power storage device according to claim 7, wherein a silicon material is contained as the active material.
9. The slurry for an electrode of an electric storage device according to claim 7 or 8, further comprising at least 1 polymer selected from a styrene-butadiene copolymer, an acrylic polymer, and a fluorine-based polymer.
10. The slurry for an electrode of an electric storage device according to any one of claims 7 to 9, further comprising a thickener.
11. An electricity storage device electrode comprising a current collector and an active material layer formed by applying the slurry for an electricity storage device electrode according to any one of claims 7 to 10 on the surface of the current collector and drying the slurry.
12. An electric storage device comprising the electric storage device electrode according to claim 11.
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| JP2018130442 | 2018-07-10 | ||
| JP2018-130442 | 2018-07-10 | ||
| PCT/JP2019/024998 WO2020012940A1 (en) | 2018-07-10 | 2019-06-24 | Power storage device composition, power storage device electrode slurry, power storage device electrode, and power storage device |
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| JPWO2020012940A1 (en) | 2021-08-02 |
| JP7220215B2 (en) | 2023-02-09 |
| WO2020012940A1 (en) | 2020-01-16 |
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