Classifications

• • 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
• • 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
• • 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
  • H01M4/621—Binders
  • H01M4/622—Binders being polymers
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F220/00—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 a salt, anhydride ester, amide, imide or nitrile thereof
  • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
  • C08F220/10—Esters
  • C08F220/12—Esters of monohydric alcohols or phenols
  • C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
  • C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
  • C08F220/1804—C4-(meth)acrylate, e.g. butyl (meth)acrylate, isobutyl (meth)acrylate or tert-butyl (meth)acrylate
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F220/00—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 a salt, anhydride ester, amide, imide or nitrile thereof
  • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
  • C08F220/10—Esters
  • C08F220/20—Esters of polyhydric alcohols or phenols, e.g. 2-hydroxyethyl (meth)acrylate or glycerol mono-(meth)acrylate
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • 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
  • C08L33/08—Homopolymers or copolymers of acrylic acid esters
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
  • H01M10/00—Secondary cells; Manufacture thereof
  • H01M10/05—Accumulators with non-aqueous electrolyte
  • H01M10/052—Li-accumulators
  • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
  • H01M10/00—Secondary cells; Manufacture thereof
  • H01M10/05—Accumulators with non-aqueous electrolyte
  • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
  • H01M10/0561—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of inorganic materials only
  • H01M10/0562—Solid materials
• • 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
  • H01M4/139—Processes of manufacture
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
  • H01M10/00—Secondary cells; Manufacture thereof
  • H01M10/05—Accumulators with non-aqueous electrolyte
  • H01M10/052—Li-accumulators
• • 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

Definitions

• the present invention relates to a binder composition for a secondary battery, a slurry composition for a secondary battery, a functional layer for a secondary battery, and a secondary battery.
• non-aqueous electrolyte secondary battery using an organic solvent electrolyte hereinafter, may be abbreviated as "non-aqueous secondary battery" or an all-solid secondary battery using a solid electrolyte instead of the organic solvent electrolyte.
• the secondary batteries illustrated in the above are compact, lightweight, have high energy density, and have the characteristics of being able to be repeatedly charged and discharged, and are used in a wide range of applications. Therefore, in recent years, improvement of battery members such as electrodes has been studied for the purpose of further improving the performance of secondary batteries.
• a binder composition for a secondary battery containing a polymer as a binder and a solvent is used.
• the binder composition is mixed with, for example, particles (hereinafter, referred to as “functional particles”) that are blended in order for the battery member to exhibit a desired function to form a slurry composition for a secondary battery.
• the functional layer for the secondary battery is formed by removing the solvent from the slurry composition for the secondary battery, and the functional layer for the secondary battery is used as a battery member or a battery member thereof. Can be used as part.
• a slurry composition for a secondary battery having excellent storage stability can be prepared, and a binder composition for a secondary battery capable of exhibiting excellent adhesiveness to the functional layer for the secondary battery.
• Another object of the present invention is to provide a slurry composition for a secondary battery capable of forming a functional layer for a secondary battery having excellent storage stability and adhesiveness.
• a further object of the present invention is to provide a functional layer for a secondary battery having excellent adhesiveness and a secondary battery including the functional layer for the secondary battery.
• the present inventor conducted a diligent study for the purpose of solving the above problems. Then, by using a polymer having a predetermined composition as a binder contained in the binder composition for a secondary battery, the present inventor can use the slurry composition as a functional layer while sufficiently ensuring the storage stability of the slurry composition.
• the present invention has been completed by newly discovering that excellent adhesiveness can be exhibited.
• the present invention aims to advantageously solve the above problems, and the binder composition for a secondary battery of the present invention is a binder composition for a secondary battery containing a polymer and a solvent.
• R 1 there are a plurality in formula (I) a plurality of R 1 may be different may be the same.
• a binder composition containing a polymer and a solvent a slurry composition having excellent storage stability can be prepared, and a functional layer having excellent adhesiveness from the slurry composition for a secondary battery. Can be formed.
• containing a monomer unit means "a structural unit derived from a monomer is contained in a polymer obtained by using the monomer”.
• the content ratio (mass% and mol%) of the "structural unit" (including the "monomer unit") in the polymer is determined by 1 H-NMR or other nuclear magnetic resonance (NMR) method. Can be measured using.
• (meth) acrylic means acrylic and / or methacrylic.
• the binder composition for a secondary battery of the present invention is a (meth) acrylic acid ester monomer unit having the aromatic hydrocarbon ring with respect to the structural unit represented by the formula (I) in the polymer.
• the molar ratio is preferably 0.08 or more and 0.80 or less. Molar ratio of (meth) acrylic acid ester monomer unit having an aromatic hydrocarbon ring to structural unit (I) (content ratio of (meth) acrylic acid ester monomer unit having an aromatic hydrocarbon ring (mol%) ) / Content ratio (mol%) of the structural unit (I)) is within the above range, the storage stability of the slurry composition can be further improved.
• the polymer is selected from at least a group consisting of a vinyl cyanide monomer unit, a diene-based monomer unit, and an aromatic vinyl monomer unit. It is preferable to further include one. If the polymer contains at least one of the above-mentioned monomer units, the adhesiveness of the functional layer and the storage stability of the slurry composition can be further improved.
• the present invention also aims to advantageously solve the above problems, and the slurry composition for a secondary battery of the present invention comprises functional particles and a binder composition for any of the above-mentioned secondary batteries. It is characterized by including things.
• the slurry composition containing the functional particles and any of the above-mentioned binder compositions is excellent in storage stability, and when the slurry composition for a secondary battery is used, a functional layer having excellent adhesiveness can be formed. it can.
• the functional particles are at least one selected from the group consisting of, for example, electrode active material particles, solid electrolyte particles, and conductive material particles.
• the present invention is intended to advantageously solve the above problems, and the functional layer for a secondary battery of the present invention is formed by using any of the above-mentioned slurry compositions for a secondary battery. It is characterized by that.
• the functional layer formed by using any of the above-mentioned slurry compositions has excellent adhesiveness.
• the present invention is intended to solve the above problems advantageously, and the secondary battery of the present invention is characterized by including the above-mentioned functional layer for a secondary battery.
• the secondary battery provided with the above-mentioned functional layer is excellent in cell characteristics such as output characteristics and cycle characteristics.
• a slurry composition for a secondary battery having excellent storage stability and a binder composition for a secondary battery capable of exhibiting excellent adhesiveness to the functional layer for the secondary battery.
• a slurry composition for a secondary battery which is excellent in storage stability and can form a functional layer for a secondary battery excellent in adhesiveness.
• a functional layer for a secondary battery having excellent adhesiveness and a secondary battery including the functional layer for the secondary battery it is possible to provide a slurry composition for a secondary battery having excellent storage stability and a binder composition for a secondary battery capable of exhibiting excellent adhesiveness to the functional layer for the secondary battery.
• the binder composition for a secondary battery of the present invention is used for producing a secondary battery such as a non-aqueous secondary battery or an all-solid-state secondary battery.
• the binder composition for a secondary battery of the present invention includes a functional layer for a secondary battery (for example, a solid electrolyte layer containing solid electrolyte particles, electrode active material particles, and optionally a solid) constituting the battery member of the secondary battery. It can be used to form an electrode mixture layer containing electrolyte particles and / or conductive material particles).
• the slurry composition for a secondary battery of the present invention comprises the binder composition for a secondary battery of the present invention, and can be used for forming a functional layer for a secondary battery.
• the functional layer for a secondary battery of the present invention is formed by using the slurry composition for a secondary battery of the present invention.
• the secondary battery of the present invention includes the functional layer for the secondary battery of the present invention.
• the binder composition of the present invention contains a polymer and a solvent, and may optionally further contain other components.
• the binder composition of the present invention contains a polymer containing a (meth) acrylic acid ester monomer unit having an aromatic hydrocarbon ring and a structural unit (I) in the above-mentioned ratios, and a solvent. Therefore, by using the binder composition, it is possible to provide a slurry composition for a secondary battery having excellent storage stability and a functional layer for a secondary battery having excellent adhesiveness.
• the polymer contains at least a (meth) acrylic acid ester monomer unit having an aromatic hydrocarbon ring and a structural unit (I), and optionally contains other structural units.
• ⁇ Composition [(Meta) acrylic acid ester monomer unit having an aromatic hydrocarbon ring]
• the polymer is particularly well adsorbed on the electrode active material particles and the conductive material particles having a high affinity with the aromatic hydrocarbon ring. Presumably because of this, a good dispersed state in these slurry compositions can be realized, and the storage stability of the slurry composition can be improved.
• the (meth) acrylic acid ester monomer unit having an aromatic hydrocarbon ring has a (meth) acrylic acid ester skeleton, it can contribute to the improvement of the adhesive ability and flexibility of the polymer. Therefore, when the polymer has a (meth) acrylic acid ester monomer unit having an aromatic hydrocarbon ring, the adhesiveness of the functional layer can be improved.
• the aromatic hydrocarbon ring contained in the (meth) acrylic acid ester monomer unit having an aromatic hydrocarbon ring is not particularly limited, and examples thereof include a benzene ring, a naphthalene ring, and an anthracene ring. Of these, a benzene ring is preferable.
• the monomer unit may have one kind of aromatic hydrocarbon ring, or may have two or more kinds of aromatic hydrocarbon rings. Further, in the aromatic hydrocarbon ring, at least one of the hydrogen atoms on the ring may be substituted with another group (halogen atom or the like), but the aromatic hydrocarbon ring does not have a substituent (unsubstituted). Is preferable.
• An example of the (meth) acrylic acid ester monomer having an aromatic hydrocarbon ring which can form a (meth) acrylic acid ester monomer unit having an aromatic hydrocarbon ring, is phenoxyethyl (meth).
• examples thereof include acrylate, phenyl (meth) acrylate, ethoxylated o-phenylphenol (meth) acrylate, and phenoxypolyethylene glycol (meth) acrylate.
• One of these may be used alone, or two or more of them may be used in combination.
• phenoxyethyl (meth) acrylate and ethoxylated o-phenylphenol (meth) acrylate are preferable from the viewpoint of further improving the adhesiveness of the functional layer and enhancing the cell characteristics of the secondary battery.
• "(meth) acrylate” means acrylate and / or methacrylate.
• the ratio of the (meth) acrylic acid ester monomer unit having an aromatic hydrocarbon ring to the total structural units contained in the polymer is 5% by mass as described above, assuming that the total structural units are 100% by mass. % Or more and 45% by mass or less, preferably 7% by mass or more, more preferably 10% by mass or more, preferably 43% by mass or less, and 40% by mass or less. It is more preferably 30% by mass or less, and particularly preferably 25% by mass or less.
• the ratio of the (meth) acrylic acid ester monomer unit having an aromatic hydrocarbon ring to all the structural units is less than 5% by mass, the adhesiveness of the functional layer is lowered.
• the electrode active material particles and the conductive material particles can be satisfactorily dispersed. , The dispersibility of solid electrolyte particles is reduced. Therefore, the storage stability of the slurry composition containing the solid electrolyte particles cannot be ensured.
• the polymer having the structural unit (I) is due to the contribution of the hydrocarbon group having 4 or more carbon atoms which does not have the aromatic hydrocarbon ring of R 1, but in the slurry composition. A good dispersed state of the solid electrolyte particles can be realized, and the storage stability of the slurry composition can be further improved.
• the structural unit (I) does not contain an aromatic hydrocarbon ring, it does not excessively increase the glass transition temperature of the polymer, and can contribute to the improvement of the adhesive ability and flexibility of the polymer. Therefore, when the polymer has the structural unit (I), the adhesiveness of the functional layer can be improved.
• the polymer may contain only one type of structural unit (I), or may contain two or more types of structural unit (I).
• R 1 is not particularly limited as long as it is a hydrocarbon group having no aromatic hydrocarbon ring in its structure and having a total number of carbon atoms of 4 or more, but the number of carbon atoms is 4.
• the above alkyl groups are preferable, and the alkyl groups having 4 or more and 12 or less carbon atoms are more preferable.
• Preferred examples of the alkyl group having 4 or more and 12 or less carbon atoms include a butyl group (n-butyl group, sec-butyl group, isobutyl group, tert-butyl group), 2-ethylhexyl group and dodecyl group (lauryl group). ..
• R 1 contained in R 2 include those similar to the hydrocarbon group in R 1 described above. Among these, R 2 is preferably a hydrogen atom or a methyl group.
• the structural unit (I) can be introduced into the polymer by preparing a polymer using a monomer having a corresponding structure.
• R 1 is an alkyl group having 4 or more and 12 or less carbon atoms
• the structural unit (I) has 4 or more and 12 or less carbon atoms of the alkyl group bonded to the non-carbonyl oxygen atom as a monomer.
• the structural unit (I) can be introduced into the polymer by using the ethylenically unsaturated carboxylic acid alkyl ester monomer.
• Examples of the ethylenically unsaturated carboxylic acid alkyl ester monomer having 4 or more and 12 or less carbon atoms of the alkyl group bonded to the non-carbonyl oxygen atom include butyl (meth) acrylate (n-butyl (meth) acrylate, sec. -Butyl (meth) acrylate, isobutyl (meth) acrylate, tert-butyl (meth) acrylate), 2-ethylhexyl (meth) acrylate, lauryl (meth) acrylate, and dibutylitaconate are preferable.
• One of these may be used alone, or two or more of them may be used in combination.
• the ratio of the structural unit (I) to the total structural units contained in the polymer needs to be 50% by mass or more and 90% by mass or less as described above, assuming that the total structural units are 100% by mass. It is preferably 55% by mass or more, more preferably 60% by mass or more, preferably 85% by mass or less, more preferably 80% by mass or less, and 70% by mass or less. Is even more preferable. If the ratio of the structural unit (I) to all the structural units is less than 50% by mass, the adhesiveness of the functional layer is lowered.
• the solid electrolyte particles can be dispersed well, but the dispersibility of the electrode active material particles and the conductive material particles is lowered. Therefore, the storage stability of the slurry composition containing the electrode active material particles and / or the conductive material particles cannot be ensured.
• the molar ratio of the (meth) acrylic acid ester monomer unit having an aromatic hydrocarbon ring to the structural unit (I) is preferably 0.08 or more, and more preferably 0.09 or more. , 0.10 or more, more preferably 0.18 or more, preferably 0.80 or less, more preferably 0.65 or less, and 0.50 or less. Is even more preferable.
• the molar ratio is 0.08 or more, the dispersibility of the electrode active material particles and the conductive material particles in the slurry composition can be improved, and when it is 0.80 or less, the solid in the slurry composition.
• the dispersibility of the electrolyte particles can be improved. Therefore, if the molar ratio is within the above range, the storage stability of the slurry composition can be further improved.
• Other structural units include, but are not limited to, vinyl cyanide monomer units, diene-based monomer units, aromatic vinyl monomer units, and crosslinkable monomer units.
• the polymer may contain only one type of other structural unit, or may contain two or more types of the polymer.
• the polymer is composed of a vinyl cyanide monomer unit, a diene-based monomer unit, and an aromatic vinyl monomer unit from the viewpoint of further improving the storage stability of the slurry composition and the adhesiveness of the functional layer. It preferably comprises at least one selected from the group.
• vinyl cyanide monomer capable of forming the vinyl cyanide monomer unit examples include acrylonitrile, methacrylonitrile, ⁇ -chloroacrylonitrile, and ⁇ -ethylacrylonitrile. One of these may be used alone, or two or more of them may be used in combination. And among these, acrylonitrile is preferable.
• the ratio of the vinyl cyanide monomer unit to the total structural units contained in the polymer is preferably 3% by mass or more, preferably 4% by mass or more, with the total structural units as 100% by mass. It is more preferably 5% by mass or more, more preferably 40% by mass or less, further preferably 38% by mass or less, and further preferably 35% by mass or less.
• the ratio of the vinyl cyanide monomer unit to the total structural unit is 3% by mass or more, the adhesiveness of the functional layer can be improved, and when it is 40% by mass or less, the solvent of the polymer (particularly, Sufficient solubility in (organic solvent) is ensured, and the storage stability of the slurry composition can be further improved.
• the ratio of the vinyl cyanide monomer unit to the total structural units contained in the polymer is the total structural units. Is 100% by mass, 5% by mass or more, more preferably 6% by mass or more, further preferably 7% by mass or more, preferably 40% by mass or less, and 38% by mass. It is more preferably% or less, and further preferably 35% by mass or less.
• the ratio of the vinyl cyanide monomer unit to the total structural unit is 5% by mass or more, a good dispersed state of the solid electrolyte particles is realized in the slurry composition, and the storage stability of the slurry composition is further improved.
• the binder composition for a secondary battery is a binder composition for a non-aqueous secondary battery such as a lithium ion secondary battery
• the vinyl cyanide monomer unit among all the structural units contained in the polymer is The proportion is preferably 3% by mass or more, more preferably 4% by mass or more, further preferably 5% by mass or more, and 40% by mass or less, assuming that the total structural unit is 100% by mass. It is preferably 38% by mass or less, more preferably 35% by mass or less.
• the leveling property of the slurry composition can be improved, and when it is 40% by mass or less, the solvent of the polymer (particularly, Sufficient solubility in (organic solvent) is ensured, and the storage stability of the slurry composition can be further improved.
• the diene-based monomer capable of forming a diene-based monomer unit include aliphatic conjugates such as 1,3-butadiene, isoprene, 2,3-dimethyl-1,3-butadiene, and 1,3-pentadiene. Diene monomer is mentioned. One of these may be used alone, or two or more of them may be used in combination.
• the "diene-based monomer unit” is a structural unit obtained by further hydrogenating the monomer unit contained in the polymer obtained by using the diene-based monomer (diene-based monomer unit). Hydride unit) shall also be included.
• 1,3-butadiene and isoprene are preferable.
• 1,3-butadiene unit, isoprene unit, 1,3-butadiene hydride unit, and isoprene hydride unit are preferable.
• the ratio of the diene-based monomer unit to the total structural units contained in the polymer is 5% by mass, assuming that all the structural units are 100% by mass.
• the above is preferable, 6% by mass or more is more preferable, 7% by mass or more is further preferable, 40% by mass or less is preferable, and 38% by mass or less is more preferable. It is more preferably 35% by mass or less.
• the ratio of the diene-based monomer unit to the total structural unit is 5% by mass or more, a better dispersed state of the electrode active material particles and the conductive material particles is realized in the slurry composition, and the electrode active material particles and the electrode active material particles and the conductive material particles are realized. / Or the storage stability of the slurry composition containing the conductive material particles can be further improved.
• the ratio of the diene-based monomer unit to the total structural unit is 40% by mass or less, the adhesiveness of the functional layer can be sufficiently ensured.
• aromatic vinyl monomer capable of forming an aromatic vinyl monomer unit examples include styrene, styrene sulfonic acid and salts thereof, ⁇ -methylstyrene, pt-butylstyrene, butoxystyrene, vinyltoluene, and chloro.
• aromatic vinyl monomer capable of forming an aromatic vinyl monomer unit examples include styrene, styrene sulfonic acid and salts thereof, ⁇ -methylstyrene, pt-butylstyrene, butoxystyrene, vinyltoluene, and chloro.
• examples include styrene and vinylnaphthalene. One of these may be used alone, or two or more of them may be used in combination. And among these, styrene is preferable.
• the aromatic vinyl monomer does not contain a monomer corresponding to the (meth) acrylic acid ester monomer having an aromatic hydrocarbon ring (in other words, a single amount of aromatic vinyl).
• the body unit does not include the (meth) acrylic acid ester monomer unit having an aromatic hydrocarbon ring).
• the ratio of the aromatic vinyl monomer unit to the total structural units contained in the polymer is 5 with the total structural unit as 100% by mass. It is preferably 5% by mass or more, more preferably 6% by mass or more, further preferably 7% by mass or more, preferably 40% by mass or less, and more preferably 38% by mass or less. It is preferably 35% by mass or less, and more preferably 35% by mass or less.
• the ratio of the aromatic vinyl monomer unit to the total structural unit is 5% by mass or more, a good dispersed state of the electrode active material particles and the conductive material particles is realized in the slurry composition, and the electrode active material particles and the electrode active material particles and the conductive material particles are realized.
• the storage stability of the slurry composition containing the conductive material particles can be further improved.
• the ratio of the aromatic vinyl monomer unit to the total structural unit is 40% by mass or less, the adhesiveness of the functional layer can be sufficiently ensured.
• the crosslinkable monomer capable of forming a crosslinkable monomer unit is a monomer having two or more polymerizable structures (olefinic double bond, epoxy group, etc.) per molecule.
• Examples of the crosslinkable monomer include allyl (meth) acrylate, allyl glycidyl ether, and ethylene glycol di (meth) acrylate. One of these may be used alone, or two or more of them may be used in combination.
• the ratio of the crosslinkable monomer unit to the total structural units contained in the polymer is 0.1, assuming that the total structural units are 100% by mass. It can be 5% by mass or more, preferably 5% by mass or less, more preferably 4% by mass or less, and further preferably 3% by mass or less.
• the polymer may be either easily soluble or poorly soluble in the solvent contained in the binder composition and the slurry composition. That is, the polymer may be in a state of being dissolved in a solvent in the binder composition and the slurry composition, or may be in a state of being dispersed in a solvent in the form of particles.
• the fact that the polymer is "easily soluble in a solvent” means that the amount of insoluble in the solvent is less than 50% by mass, and the polymer is "poorly soluble in a solvent”. "" Means that the amount of insoluble matter in the solvent is 50% by mass or more.
• the "amount of insoluble matter in the solvent” can be measured by using the method described in Examples.
• the "insoluble amount in the solvent” of the polymer can be adjusted by changing the type of the monomer used for preparing the polymer, the weight average molecular weight of the polymer, and the like. For example, by reducing the amount of vinyl cyanide monomer and / or crosslinkable monomer used in the preparation of the polymer, the amount of insoluble matter in the solvent can be reduced.
• the binder composition is a binder composition for an all-solid-state secondary battery
• the polymer is preferably easily soluble in the solvent contained in the binder composition and the slurry composition.
• the polymer is easily soluble in a solvent, a good dispersed state of solid electrolyte particles and the like can be realized in the slurry composition, and the storage stability of the slurry composition can be further improved.
• the adhesiveness of the functional layer can be further enhanced, and the cell characteristics of the secondary battery can be improved.
• the method for preparing the polymer is not particularly limited, but for example, the polymer can be prepared by polymerizing the above-mentioned monomer composition containing the monomer and optionally hydrogenating it.
• the content ratio of each monomer in the monomer composition can be determined according to the content ratio of each monomer unit and the structural unit in the polymer.
• the polymerization mode is not particularly limited, and any method such as a solution polymerization method, a suspension polymerization method, a massive polymerization method, and an emulsion polymerization method can be used. In each polymerization method, known emulsifiers and polymerization initiators can be used, if necessary.
• the method of hydrogenation is not particularly limited, and a general method using a catalyst (see, for example, International Publication No. 2012/165120, International Publication No. 2013/080989, and JP-A-2013-8485) can be used. it can.
• the solvent is not particularly limited and can be appropriately selected depending on the intended use of the binder composition, and either water or an organic solvent can be used.
• organic solvent chain aliphatic hydrocarbons such as hexane; cyclic aliphatic hydrocarbons such as cyclopentane and cyclohexane; aromatic hydrocarbons such as toluene and xylene; ethylmethyl ketone and cyclohexanone.
• Ketones such as diisobutyl ketone; esters such as ethyl acetate, butyl acetate, butyl butyrate, hexyl butyrate, ⁇ -butyrolactone, ⁇ -caprolactone; acylonitriles such as acetonitrile and propionitrile; tetrahydrofuran, ethylene glycol diethyl ether, Ethers such as n-butyl ether: Alcohols such as methanol, ethanol, isopropanol, ethylene glycol, ethylene glycol monomethyl ether; amides such as N-methylpyrrolidone, N, N-dimethylformamide. As the solvent, one type may be used alone, or two or more types may be used in combination.
• the solvent suppresses deterioration due to a side reaction while increasing the dispersibility of the solid electrolyte particles, and the slurry for the all-solid-state secondary battery.
• xylene, butyl butyrate, hexyl butyrate, n-butyl ether, and diisobutylketone are preferable, and xylene and diisobutylketone are more preferable.
• the solvent is preferably N-methylpyrrolidone.
• the binder composition is used to prepare a slurry composition for a negative electrode mixture layer of a non-aqueous secondary battery, the solvent is preferably water.
• binder composition for a secondary battery examples include, but are not limited to, binders other than the above-mentioned polymers, dispersants, leveling agents, defoaming agents, reinforcing materials, and the like. .. These other components are not particularly limited as long as they do not affect the battery reaction. In addition, one of these components may be used alone, or two or more of these components may be used in combination at any ratio.
• the method for preparing the binder composition of the present invention is not particularly limited.
• the binder composition can be obtained by subjecting the aqueous dispersion of the polymer as the binder obtained as described above to a solvent, if necessary, and further adding other components. Can be prepared.
• the slurry composition for a secondary battery of the present invention contains functional particles and the binder composition for a secondary battery of the present invention described above.
• the slurry composition for a secondary battery of the present invention contains functional particles, the above-mentioned predetermined polymer, and a solvent, and optionally contains other components. Since the slurry composition for a secondary battery of the present invention contains the binder composition of the present invention, it has excellent storage stability, and if the slurry composition for a secondary battery is used, it has an excellent adhesiveness. Layers can be formed.
• the functional particles contained in the slurry composition for a secondary battery can be appropriately selected depending on the use of the slurry composition (type of functional layer prepared using the slurry composition) and the like.
• the functional particles electrode active material particles, solid electrolyte particles, and conductive material particles are preferably mentioned.
• Electrode active material particles are particles that transfer electrons at the electrodes of a secondary battery.
• the slurry composition for a secondary battery is a slurry composition for an all-solid-state lithium ion secondary battery electrode mixture layer
• the slurry composition for a secondary battery is a non-aqueous lithium ion secondary battery electrode combination.
• the case where the slurry composition for a material layer is used will be described, but the present invention is not limited to the following examples.
• the positive electrode active material particles for the all-solid-state lithium ion secondary battery are not particularly limited, and examples thereof include positive electrode active material particles made of an inorganic compound and positive electrode active material particles made of an organic compound.
• Examples of the positive electrode active material particles made of an inorganic compound include particles made of a transition metal oxide, a composite oxide of lithium and a transition metal (lithium-containing composite metal oxide), and a transition metal sulfide.
• a transition metal oxide a composite oxide of lithium and a transition metal (lithium-containing composite metal oxide), and a transition metal sulfide.
• Fe, Co, Ni, Mn and the like are used.
• the inorganic compound used for the positive electrode active material include lithium-containing composite metal oxides such as LiCoO 2 (lithium cobalt oxide), LiNiO 2 , LiMnO 2 , LiMn 2 O 4 , LiFePO 4 , and LiFeVO 4 ; TiS 2 , TiS 3 , transition metal sulfides such as amorphous MoS 2 , transition metals such as Cu 2 V 2 O 3 , amorphous V 2 O-P 2 O 5 , MoO 3 , V 2 O 5 , V 6 O 13 etc. Metal oxides; and the like. These compounds may be partially elementally substituted.
• LiCoO 2 lithium cobalt oxide
• LiNiO 2 LiMnO 2
• LiMn 2 O 4 LiFePO 4
• LiFeVO 4 LiFeVO 4
• TiS 2 , TiS 3 transition metal sulfides
• amorphous MoS 2 transition metals
• transition metals such as Cu 2 V 2 O 3 ,
• positive electrode active material particles composed of organic compounds include polyaniline, polypyrrole, polyacene, disulfide compounds, polysulfide compounds, and N-fluoropyridinium salts.
• the above-mentioned positive electrode active material particles can be used alone or in combination of two or more. Further, the particle size of the above-mentioned positive electrode active material particles is not particularly limited, and can be the same as that of the conventionally used positive electrode active material particles.
• Examples of the negative electrode active material particles for the all-solid-state lithium-ion secondary battery include particles made of carbon allotropes such as graphite and coke.
• the negative electrode active material particles made of carbon allotropes can also be used in the form of a mixture with a metal, a metal salt, an oxide, or the like, or a coating body.
• the negative electrode active material particles include oxides or sulfates such as silicon, tin, zinc, manganese, iron and nickel; metallic lithium; lithium alloys such as Li-Al, Li-Bi-Cd and Li-Sn-Cd. Lithium transition metal nitride; silicone; etc. can also be used.
• the above-mentioned negative electrode active material particles can be used alone or in combination of two or more. Further, the particle size of the above-mentioned negative electrode active material particles is not particularly limited, and can be the same as that of the conventionally used negative electrode active material particles.
• the positive electrode active material particles for a non-aqueous lithium ion secondary battery are not particularly limited, and are limited to lithium-containing cobalt oxide (LiCoO 2 ), lithium manganate (LiMn 2 O 4 ), and lithium-containing nickel oxide (LiNiO).
• Li (Co Mn Ni) O 2 Co—Ni—Mn lithium-containing composite oxide
• Ni—Mn—Al lithium-containing composite oxide Ni—Co—Al lithium-containing composite oxide
• olivine Lithium cobalt oxide LiFePO 4
• lithium olivine-type lithium manganese phosphate Li 1 + x Mn 2-x O 4 (0 ⁇ X ⁇ 2)
• Li [ Examples thereof include particles made of known positive electrode active materials such as Ni 0.17 Li 0.2 Co 0.07 Mn 0.56 ] O 2 and LiNi 0.5 Mn 1.5 O 4.
• the above-mentioned positive electrode active material particles can be used alone or in combination of two or more. Further, the particle size of the above-mentioned positive electrode active material particles is not particularly limited, and can be the same as that of the conventionally used positive electrode active material particles.
• the negative electrode active material particles for a non-aqueous lithium ion secondary battery are not particularly limited, and are known negative electrode active materials such as carbon-based active materials, silicone-based active materials, and single metals and alloys forming a lithium alloy. Examples include particles made of a substance.
• the above-mentioned negative electrode active material particles can be used alone or in combination of two or more. Further, the particle size of the above-mentioned negative electrode active material particles is not particularly limited, and can be the same as that of the conventionally used negative electrode active material particles.
• the solid electrolyte particles are particles that conduct ions in the electrodes and the solid electrolyte layer of the all-solid-state secondary battery.
• the solid electrolyte particles used in the all-solid-state lithium ion secondary battery are not particularly limited as long as they are particles made of a solid having ionic conductivity, but particles made of an inorganic solid electrolyte (inorganic solid electrolyte particles) are preferably used. be able to.
• the inorganic solid electrolyte is not particularly limited, and a crystalline inorganic lithium ion conductor, an amorphous inorganic lithium ion conductor, or a mixture thereof can be used.
• Crystalline inorganic lithium ion conductors include Li 3 N, LISION (Li 14 Zn (GeO 4 ) 4 ), perovskite type (eg Li 0.5 La 0.5 TiO 3 ), garnet type (eg Li 7 La 3 Zr). 2 O 12 ), LIPON (Li 3 + y PO 4-x N x ), Thio-LISION (Li 3.25 Ge 0.25 P 0.75 S 4 ) and the like.
• the above-mentioned crystalline inorganic lithium ion conductor can be used alone or in combination of two or more.
• Examples of the amorphous inorganic lithium ion conductor include substances containing a sulfur atom and having ionic conductivity, and more specifically, glass Li—Si—SO, Li—P. -S and those using a raw material composition containing Li 2 S and sulfides of the elements of Groups 13 to 15 of the periodic table, and the like.
• examples of the elements of Groups 13 to 15 include Al, Si, Ge, P, As, Sb and the like.
• Specific examples of the sulfides of the elements of Groups 13 to 15 include Al 2 S 3 , Si S 2 , GeS 2 , P 2 S 3 , P 2 S 5 , As 2 S 3 , and Sb 2. S 3 etc. can be mentioned.
• an amorphization method such as a mechanical milling method or a melt quenching method can be mentioned.
• an amorphous inorganic lithium ion conductor using a raw material composition containing Li 2 S and sulfides of elements of Groups 13 to 15 of the periodic table Li 2 SP 2 S 5 , Li 2 S—SiS 2 , Li 2 S—GeS 2 or Li 2 S—Al 2 S 3 is preferable, and Li 2 SP 2 S 5 is more preferable.
• the above-mentioned amorphous inorganic lithium ion conductor can be used alone or in combination of two or more.
• an amorphous sulfide containing Li and P, Li 7 La 3 Zr 2 O 12 is preferred.
• Amorphous sulfides containing Li and P, and Li 7 La 3 Zr 2 O 12 have high lithium ion conductivity, so when used as an inorganic solid electrolyte, the internal resistance of the battery can be reduced and the internal resistance of the battery can be reduced. The output characteristics can be improved.
• the amorphous sulfide containing Li and P is more preferably a sulfide glass composed of Li 2 S and P 2 S 5 from the viewpoint of reducing the internal resistance of the battery and improving the output characteristics. It is particularly preferable that the sulfide glass is produced from a mixed raw material of Li 2 S and P 2 S 5 having a molar ratio of 2 S: P 2 S 5 of 65:35 to 85:15.
• Amorphous sulfides containing Li and P are made from a mixed raw material of Li 2 S and P 2 S 5 having a molar ratio of Li 2 S: P 2 S 5 of 65:35 to 85:15. It is preferably a sulfide glass-ceramic obtained by reacting by a method. From the viewpoint of maintaining the lithium ion conductivity in a high state, the mixed raw material preferably has a molar ratio of Li 2 S: P 2 S 5 of 68:32 to 80:20.
• an inorganic solid electrolyte to the extent not to lower the ionic conductivity of at least selected from the group consisting of the Li 2 S, Al 2 S 3 as another starting material of P 2 S 5, B 2 S 3 and SiS 2 It may contain one kind of sulfide. By adding such a sulfide, the glass component in the inorganic solid electrolyte can be stabilized.
• the inorganic solid electrolyte is at least selected from the group consisting of Li 2 S and P 2 S 5 , as well as Li 3 PO 4 , Li 4 SiO 4 , Li 4 GeO 4 , Li 3 BO 3 and Li 3 AlO 3. It may contain one type of lithium orthooxoate. When such lithium orthooxoate is contained, the glass component in the inorganic solid electrolyte can be stabilized.
• the above-mentioned solid electrolyte particles can be used alone or in combination of two or more. Further, the particle size of the above-mentioned solid electrolyte particles is not particularly limited, and can be the same as that of the conventionally used solid electrolyte particles.
• the conductive material particles are for ensuring electrical contact between the electrode active materials in the electrode mixture layer.
• the conductive material particles are not particularly limited, and particles made of a known conductive substance can be used.
• the shape of the conductive material particles is not particularly limited, and any shape such as a substantially spherical shape, a fibrous shape, or a plate shape can be taken.
• the conductive material particles include carbon black (for example, acetylene black, Ketjen black (registered trademark), graphene black, etc.), single-walled or multi-walled carbon nanotubes (multi-walled carbon nanotubes include cup-stack type), and carbon.
• Conductive carbon materials such as nanohorns, vapor-grown carbon fibers, milled carbon fibers obtained by crushing polymer fibers after firing, single-walled or multi-walled graphene, carbon non-woven sheets obtained by firing non-woven fabrics made of polymer fibers, and Various metal fibers or foils can be used.
• the above-mentioned conductive material particles can be used alone or in combination of two or more. Further, the size of the above-mentioned conductive material particles (particle diameter, fiber diameter, fiber length, etc.) is not particularly limited and can be the same as that of the conventionally used conductive material particles.
• Binder composition As the binder composition used for preparing the slurry composition, the above-mentioned binder composition for a secondary battery of the present invention containing a polymer and a solvent and optionally containing other components is used.
• the mixing amount ratio of the functional particles and the binder composition for a secondary battery containing the polymer and the solvent is not particularly limited, and can be appropriately adjusted depending on the use of the slurry composition and the type of the functional particles.
• the amount of the polymer contained in the slurry composition for an all-solid secondary battery is based on 100 parts by mass of the solid electrolyte particles as functional particles. It is preferably 0.1 part by mass or more, more preferably 0.2 part by mass or more, further preferably 0.3 part by mass or more, preferably 10 parts by mass or less, and 8 mass by mass. It is more preferably parts or less, and even more preferably 5 parts by mass or less.
• the content of the polymer in the slurry composition for an all-solid secondary battery is 0.1 part by mass or more per 100 parts by mass of the solid electrolyte particles, the polymer sufficiently exerts its function as a binder. , Solid electrolyte particles can be dispersed well. Therefore, the storage stability of the slurry composition can be further improved, and the ionic conductivity of the functional layer (solid electrolyte layer, electrode mixture layer) can be further improved to enhance the cell characteristics of the all-solid secondary battery.
• the content of the polymer in the slurry composition for an all-solid secondary battery is 10 parts by mass or less per 100 parts by mass of the solid electrolyte particles, the ion conduction of the functional layer (solid electrolyte layer, electrode mixture layer) Sufficient properties can be ensured, and the cell characteristics of the all-solid-state secondary battery are not excessively impaired.
• the slurry composition is a slurry composition for a non-aqueous secondary battery electrode mixture layer
• the amount of the polymer contained in the non-aqueous secondary battery electrode mixture layer slurry composition is as functional particles.
• the polymer in the slurry composition for the electrode mixture layer of the non-aqueous secondary battery is 0.1 parts by mass or more per 100 parts by mass of the electrode active material particles, the polymer functions as a binder. It is possible to disperse the electrode active material particles satisfactorily while fully exerting the effect.
• the storage stability of the slurry composition can be further enhanced, and an electrode mixture layer in which the electrode active material particles are uniformly distributed can be obtained, and the cell characteristics of the non-aqueous secondary battery can be enhanced.
• the content of the polymer in the slurry composition for the electrode mixture layer of the non-aqueous secondary battery is 10 parts by mass or less per 100 parts by mass of the electrode active material particles, the resistance of the electrode mixture layer increases excessively. It is possible to sufficiently secure the cell characteristics of the non-aqueous secondary battery without doing so.
• a slurry composition can be prepared by mixing the functional particles and the binder composition of the present invention by a known mixing method.
• the slurry composition of the present invention is a slurry composition for an electrode mixture layer
• electrode active material particles and conductive material particles as functional particles are prepared by mixing with the binder composition of the present invention.
• the conductive material particles as functional particles and the binder composition of the present invention may be mixed to prepare a slurry composition (a conductive material paste containing the conductive material particles and the binder composition), and then the conductive material.
• the material paste and the electrode active material particles as functional particles may be mixed and prepared.
• the functional layer of the present invention is a layer containing functional particles and a polymer as a binder.
• the functional layers include, for example, an electrode mixture layer (positive electrode mixture layer, negative electrode mixture layer) that transfers electrons via an electrochemical reaction, and a positive electrode mixture layer that faces each other in an all-solid-state secondary battery. Examples thereof include a solid electrolyte layer provided between the negative electrode mixture layer and the negative electrode mixture layer.
• the functional layer of the present invention is formed by using the above-mentioned slurry composition of the present invention. For example, the above-mentioned slurry composition is applied to the surface of an appropriate base material to form a coating film. After that, it can be produced by drying the formed coating film.
• the functional layer of the present invention comprises a dried product of the above-mentioned slurry composition, usually contains functional particles and a polymer, and may further contain other components as desired.
• Each component contained in the functional layer was contained in the slurry composition, and the content ratio of these components is usually equal to the content ratio in the slurry composition.
• the functional layer of the present invention is formed by using the slurry composition of the present invention, it is excellent in adhesiveness.
• ⁇ Base material> there is no limitation on the base material to which the slurry composition is applied.
• a coating film of the slurry composition is formed on the surface of the release base material, and the coating film is dried to form a functional layer.
• the release base material may be peeled off from the mold.
• the functional layer peeled off from the release base material can be used as a self-supporting film for forming a battery member (for example, an electrode, a solid electrolyte layer, etc.) of a secondary battery.
• a current collector or an electrode it is preferable to use as the base material.
• the slurry composition when preparing the electrode mixture layer, it is preferable to apply the slurry composition on the current collector as the base material. Further, when preparing the solid electrolyte layer, it is preferable to apply the slurry composition on the electrode (positive electrode or negative electrode).
• ⁇ Current collector a material having electrical conductivity and which is electrochemically durable is used.
• a current collector made of iron, copper, aluminum, nickel, stainless steel, titanium, tantalum, gold, platinum or the like can be used.
• copper foil is particularly preferable as the current collector used for the negative electrode.
• an aluminum foil is particularly preferable.
• one kind of the said material may be used alone, or two or more kinds may be used in combination at an arbitrary ratio.
• Electrode The electrodes (positive electrode and negative electrode) are not particularly limited, but an electrode containing at least electrode active material particles and a binder (and solid electrolyte particles in the case of an electrode for an all-solid secondary battery) on the above-mentioned current collector. Examples thereof include electrodes on which a mixture layer is formed.
• the electrode active particles, the binder, and the solid electrolyte particles contained in the electrode mixture layer in the electrode are not particularly limited, and known ones can be used.
• the electrode mixture layer in the electrode may correspond to the functional layer of the present invention.
• Examples of the method for forming the functional layer on the base material such as the current collector and the electrode described above include the following methods. 1) A method in which the slurry composition of the present invention is applied to the surface of a base material (in the case of an electrode, the surface on the electrode mixture layer side, the same applies hereinafter), and then dried; 2) A method of immersing a base material in the slurry composition of the present invention and then drying it; and 3) applying the slurry composition of the present invention on a release base material and drying to produce a functional layer. A method of transferring the obtained functional layer to the surface of an electrode or the like.
• the method 1) above is particularly preferable because it is easy to control the layer thickness of the functional layer.
• the method 1) described above includes a step of applying the slurry composition onto the substrate (coating step) and a step of drying the slurry composition coated on the substrate to form a functional layer (function). Layer formation step) is included.
• the method of coating the slurry composition on the substrate is not particularly limited, and for example, a doctor blade method, a reverse roll method, a direct roll method, a gravure method, an extrusion method, a brush coating method and the like. Method can be mentioned.
• the method for drying the slurry composition on the substrate is not particularly limited, and a known method can be used.
• the drying method include a drying method using warm air, hot air, and low humidity air, a vacuum drying method, and a drying method using irradiation with infrared rays or an electron beam.
• the functional layer is an electrode mixture layer
• the secondary battery of the present invention includes the above-mentioned functional layer for the secondary battery.
• the secondary battery of the present invention is an all-solid secondary battery
• the all-solid secondary battery of the present invention usually has a positive electrode, a negative electrode, and a solid electrolyte layer, and the positive electrode mixture layer of the positive electrode, At least one of the negative electrode mixture layer and the solid electrolyte layer of the negative electrode is the functional layer of the present invention.
• the non-aqueous secondary battery of the present invention when the secondary battery of the present invention is a non-aqueous secondary battery, the non-aqueous secondary battery of the present invention usually has a positive electrode, a negative electrode, an electrolytic solution, and a separator, and is a positive electrode mixture of the positive electrode. At least one of the layer and the negative electrode mixture layer of the negative electrode is the functional layer of the present invention. Since the secondary battery of the present invention has the functional layer of the present invention, it is excellent in cell characteristics such as output characteristics and cycle characteristics.
• an electrode for an all-solid-state secondary battery having an electrode mixture layer that does not correspond to the functional layer of the present invention which can be used for the all-solid-state secondary battery of the present invention
• an electrode combination that does not correspond to the functional layer of the present invention Any electrode for an all-solid-state secondary battery can be used without particular limitation as long as it has a material layer.
• the solid electrolyte layer that can be used in the all-solid-state secondary battery of the present invention and does not correspond to the functional layer of the present invention is not particularly limited, and is, for example, JP-A-2012-243476, JP-A-2013-. Any solid electrolyte layer such as the solid electrolyte layer described in Japanese Patent Application Laid-Open No. 143299 and Japanese Patent Application Laid-Open No. 2016-143614 can be used.
• the positive electrode and the negative electrode are laminated so that the positive electrode mixture layer of the positive electrode and the negative electrode mixture layer of the negative electrode face each other via the solid electrolyte layer, and pressurized arbitrarily.
• the laminated body After obtaining the laminated body, it can be obtained as it is, or by rolling, folding, etc., putting it in a battery container, and sealing it, depending on the shape of the battery.
• an expanded metal, an overcurrent prevention element such as a fuse or a PTC element, a lead plate, or the like can be placed in the battery container to prevent the pressure inside the battery from rising and overcharging / discharging.
• the shape of the battery may be any of a coin type, a button type, a sheet type, a cylindrical type, a square type, a flat type and the like.
• Non-water secondary battery> As an electrode for a non-aqueous secondary battery having an electrode mixture layer that does not correspond to the functional layer of the present invention, which can be used for the non-aqueous secondary battery of the present invention, an electrode combination that does not correspond to the functional layer of the present invention. Any non-aqueous secondary battery electrode can be used without particular limitation as long as it has a material layer.
• an organic electrolytic solution in which a supporting electrolyte is dissolved in an organic solvent is usually used.
• a lithium salt is used as the supporting electrolyte for a non-aqueous lithium ion secondary battery.
• lithium salts include LiPF 6 , LiAsF 6 , LiBF 4 , LiSbF 6 , LiAlCl 4 , LiClO 4 , CF 3 SO 3 Li, C 4 F 9 SO 3 Li, CF 3 COOLi, (CF 3 CO) 2 NLi. , (CF 3 SO 2 ) 2 NLi, (C 2 F 5 SO 2 ) NLi and the like.
• LiPF 6 , LiClO 4 , CF 3 SO 3 Li are preferable, and LiPF 6 is particularly preferable because they are easily dissolved in a solvent and show a high degree of dissociation.
• One type of electrolyte may be used alone, or two or more types may be used in combination at an arbitrary ratio. Normally, the more the supporting electrolyte with a higher degree of dissociation is used, the higher the lithium ion conductivity tends to be. Therefore, the lithium ion conductivity can be adjusted depending on the type of the supporting electrolyte.
• the organic solvent used in the electrolytic solution is not particularly limited as long as it can dissolve the supporting electrolyte.
• examples of the organic solvent used in the electrolytic solution of the non-aqueous lithium ion secondary battery include dimethyl carbonate (DMC), ethylene carbonate (EC), diethyl carbonate (DEC), propylene carbonate (PC), butylene carbonate (BC), and the like.
• Carbonates such as ethyl methyl carbonate (EMC); esters such as ⁇ -butyrolactone and methyl formate; ethers such as 1,2-dimethoxyethane and tetrahydrofuran; sulfur-containing compounds such as sulfolane and dimethyl sulfoxide; are preferable. Used.
• a mixed solution of these solvents may be used. Above all, it is preferable to use carbonates because the dielectric constant is high and the stable potential region is wide.
• concentration of the electrolyte in the electrolytic solution can be adjusted as appropriate.
• known additives can be added to the electrolytic solution.
• the separator is not particularly limited, and for example, the separator described in Japanese Patent Application Laid-Open No. 2012-204303 can be used. Among these, the film thickness of the entire separator can be reduced, and as a result, the ratio of the electrode active material particles in the non-aqueous secondary battery can be increased to increase the capacity per volume.
• a microporous film made of a polyolefin-based (polyethylene, polypropylene, polybutene, polyvinyl chloride) resin is preferable.
• the positive electrode and the negative electrode are overlapped with each other via a separator, and if necessary, the positive electrode and the negative electrode are put into the battery container by winding or folding according to the battery shape, and put into the battery container. It can be manufactured by injecting an electrolytic solution and sealing it. If necessary, an expanded metal, an overcurrent prevention element such as a fuse or a PTC element, a lead plate, or the like can be placed in the battery container to prevent the pressure inside the battery from rising and overcharging / discharging.
• the shape of the battery may be any of a coin type, a button type, a sheet type, a cylindrical type, a square type, a flat type and the like.
• the produced film was cut into 5 mm squares to prepare a film piece.
• About 1 g of these film pieces were precisely weighed, and the weight of the finely weighed film pieces was defined as W0.
• the finely weighed film piece was immersed in 100 g of a solvent (temperature 25 ° C.) of the binder composition for 24 hours. After immersion for 24 hours, the film piece was lifted from the solvent, and the lifted film piece was vacuum dried at 105 ° C. for 3 hours, and the weight (weight of insoluble matter) W1 was precisely weighed. Then, the insoluble content (%) in the solvent was calculated according to the following formula.
• Insoluble content in solvent (%) W1 / W0 ⁇ 100 ⁇ Dispersibility>
• the viscosity of the slurry composition was measured with a Brookfield B-type viscometer at 60 rpm (25 ° C.) and evaluated according to the following criteria. The smaller the viscosity of the slurry composition, the better the dispersion of the functional particles (electrode active material particles, solid electrolyte particles, conductive material particles) contained in the slurry composition.
• the slurry composition was then stored in a hermetically sealed state at 25 ° C.
• the upper part of the stored slurry composition was sampled every day (24 hours) until the lapse of 6 days, and the solid content concentration was measured by the same method as described above.
• the number of storage days which was 1.0% or more lower than the initial solid content concentration, was recorded and evaluated according to the following criteria. The longer the number of days, the more difficult it is for the solid content in the slurry composition to settle, indicating that the slurry composition is excellent in storage stability.
• B Confirmed a decrease in solid content concentration after 4 or 5 days of storage.
• the battery was charged to 4.2 V at 0.1 C and then discharged to 3.0 V at 2 C to determine the 2 C discharge capacity.
• the average value of the 0.1C discharge capacity of the three cells is the discharge capacity a
• the average value of the 2C discharge capacity of the three cells is the discharge capacity b
• the ratio of the discharge capacity b to the discharge capacity a (capacity ratio) discharge capacity b / discharge.
• the capacity a ⁇ 100 (%) was determined and evaluated according to the following criteria. The larger the capacity ratio value, the better the output characteristics of the all-solid-state secondary battery.
• Capacity ratio is 90% or more
• a 3-cell lithium-ion secondary battery was charged to 4.2 V by a constant current method of 0.2 C, and then discharged to 3.0 V at 0.2 C to determine a 0.2 C discharge capacity. Then, the battery was charged to 4.2 V at 0.2 C and then discharged to 3.0 V at 2 C to determine the 2 C discharge capacity.
• the average value of the 0.2C discharge capacity of the three cells is the discharge capacity c
• the average value of the 2C discharge capacity of the three cells is the discharge capacity d
• the ratio of the discharge capacity d to the discharge capacity c (capacity ratio) discharge capacity d / discharge.
• the capacity c ⁇ 100 (%) was determined and evaluated according to the following criteria. The larger the capacity ratio value, the better the output characteristics of the lithium ion secondary battery.
• Capacity ratio is 90% or more
• the value obtained by calculating the ratio of the 0.1C discharge capacity in the 50th cycle to the 0.1C discharge capacity in the first cycle as a percentage was defined as the capacity retention rate A and evaluated according to the following criteria.
• Capacity retention rate A is 90% or more
• B Capacity retention rate A is 80% or more and less than 90%
• C Capacity retention rate A is 50% or more and less than 80%
• D Capacity retention rate A is less than 50% ⁇ Cycle characteristics- Lithium-ion secondary battery (non-aqueous secondary battery)-> The lithium ion secondary battery was charged at 1.0 C from 3 V to 4.2 V under an environment of 25 ° C., and then charged / discharged at 1.0 C from 4.2 V to 3 V, which was repeatedly charged and discharged for 100 cycles.
• the value obtained by calculating the ratio of the 1.0C discharge capacity in the 100th cycle to the 1.0C discharge capacity in the first cycle as a percentage was defined as the capacity retention rate B, and was evaluated according to the following criteria.
• Capacity retention rate B is 90% or more
• Capacity retention rate B is 80% or more and less than 90%
• Capacity retention rate B is 50% or more and less than 80%
• D Capacity retention rate B is less than 50% ⁇ Cycle characteristics (cycle characteristics ( After storing the slurry) -All-solid-state secondary battery->
• the slurry composition was stored in a glove box (water content: 10 ppm or less) in a closed state for 48 hours. After storage, the slurry composition was used to prepare electrodes and a solid electrolyte layer in a dry room (moisture content 127 ppm, dew point -40 ° C. equivalent) in the same manner as in each Example and Comparative Example, and all-solid secondary A battery was manufactured.
• the capacity retention rate was A'and evaluated according to the following criteria. The larger the value of the capacity retention rate A', the smaller the decrease in discharge capacity, which means that the all-solid-state secondary battery provided with the electrodes formed from the slurry composition after storage has excellent cycle characteristics.
• the slurry composition was used to prepare electrodes in a dry room (moisture content 127 ppm, equivalent to dew point ⁇ 40 ° C.) in the same manner as in each Example and Comparative Example to prepare a lithium ion secondary battery. .. Then, the same operation as the above-mentioned "cycle characteristics-lithium ion secondary battery (non-aqueous secondary battery)-" is performed, and the ratio of the 1.0C discharge capacity in the 100th cycle to the 1.0C discharge capacity in the first cycle is performed. The value calculated as a percentage was defined as the capacity retention rate B', and was evaluated according to the following criteria.
• Capacity retention rate B' is 90% or more
• B Capacity retention rate B'is 80% or more and less than 90%
• C Capacity retention rate B'is 50% or more and less than 80%
• D Capacity retention rate B'is less than 50%
• Example 1 Preparation of binder composition for secondary batteries> Add 100 parts of ion-exchanged water and 0.2 part of sodium dodecylbenzenesulfonate as an emulsifier to a 1 L flask with a septum equipped with a stirrer, replace the gas phase part with nitrogen gas, heat the temperature to 60 ° C, and then start polymerization. As an agent, 0.25 part of potassium persulfate was dissolved in 20.0 parts of ion-exchanged water and added.
• the amount of the polymer insoluble in the diisobutyl ketone (solvent) was measured, and whether the polymer was easily soluble or sparingly soluble in the diisobutyl ketone was determined. Identified. The results are shown in Table 1. Subsequently, an appropriate amount of diisobutyl ketone as a solvent was added to the aqueous dispersion of the obtained polymer to obtain a mixture. Then, vacuum distillation was carried out at 80 ° C. to remove water and excess diisobutyl ketone from the mixture to obtain a binder composition (solid content concentration: 8%). The composition of the polymer was measured using the obtained binder composition.
• Lithium sulfide glass Li 2 S / P 2 S
• Li 2 S and P 2 S 5 Li 2 S and P 2 S 5 as solid electrolyte particles.
• a diisobutyl ketone was further added to adjust the solid content concentration to 60%, and then the mixture was mixed with a planetary mixer to prepare a slurry composition for a negative electrode mixture layer.
• a sulfide glass Li 2 S /
• Li 2 S and P 2 S 5 as solid electrolyte particles in a glove box (moisture concentration 0.6 mass ppm, oxygen concentration 1.8 mass ppm) under an argon gas atmosphere.
• P 2 S 5 70 mol% / 30 mol%, number average particle size: 0.9 ⁇ m) 100 parts and 2 parts (solid content equivalent amount) of the binder composition obtained as described above are mixed, and further.
• Diisobutylketone as a solvent was added to adjust the solid content concentration to 60% by mass, and then the mixture was mixed with a planetary mixer for 60 minutes. Then, a diisobutyl ketone was further added to adjust the solid content concentration to 45%, and then the mixture was mixed with a planetary mixer to prepare a slurry composition for a solid electrolyte layer.
• the slurry composition for the positive electrode mixture layer is applied to the surface of the current collector (aluminum foil, thickness: 20 ⁇ m) and dried (120 ° C., 60 minutes) to form a positive electrode mixture layer having a thickness of 50 ⁇ m. A positive electrode was obtained.
• the adhesiveness of the positive electrode mixture layer was evaluated. The results are shown in Table 1. Further, the slurry composition for the negative electrode mixture layer is applied to the surface of another current collector (copper foil, thickness: 15 ⁇ m) and dried (120 ° C., 60 minutes) to have a negative electrode mixture layer having a thickness of 60 ⁇ m. Was formed to obtain a negative electrode. Next, the slurry composition for the solid electrolyte layer is applied to the surface of the positive electrode mixture layer of the positive electrode and dried (120 ° C., 60 minutes) to form a solid electrolyte layer having a thickness of 150 ⁇ m, and the solid electrolyte layer is attached. A positive electrode was obtained.
• the positive electrode and the negative electrode with the solid electrolyte layer were bonded together so that the solid electrolyte layer of the positive electrode with the solid electrolyte layer and the negative electrode mixture layer of the negative electrode were in contact with each other, and pressed to obtain an all-solid secondary battery.
• the thickness of the solid electrolyte layer of the all-solid-state secondary battery after pressing was 100 ⁇ m.
• the cycle characteristics and rate characteristics of this all-solid-state secondary battery were evaluated. The results are shown in Table 1. Except that the above-mentioned slurry compositions (slurry composition for positive electrode mixture layer, slurry composition for negative electrode mixture layer, and slurry composition for solid electrolyte layer) were separately stored and the stored slurry composition was used. A positive electrode, a negative electrode, a solid electrolyte layer, and an all-solid secondary battery were prepared in the same manner as in the above procedure, and the cycle characteristics (after storage of the slurry) were evaluated. The results are shown in Table 1.
• Example 2 A binder for a secondary battery was prepared in the same manner as in Example 1 except that 67 parts of 2-ethylhexyl acrylate, 25 parts of phenoxyethyl acrylate, and 8 parts of acrylonitrile were used as monomers in the preparation of the binder composition for a secondary battery.
• a composition, a slurry composition for a positive electrode mixture layer, a slurry composition for a negative electrode mixture layer, a slurry composition for a solid electrolyte layer, and an all-solid secondary battery were prepared and evaluated in various ways. The results are shown in Table 1.
• Example 3 In the preparation of the binder composition for a secondary battery, the same as in Example 1 except that 30 parts of n-butyl acrylate, 40 parts of lauryl acrylate, 20 parts of phenoxyethyl acrylate and 10 parts of acrylonitrile were used as monomers.
• a binder composition for a secondary battery, a slurry composition for a positive electrode mixture layer, a slurry composition for a negative electrode mixture layer, a slurry composition for a solid electrolyte layer, and an all-solid secondary battery were prepared and evaluated in various ways. The results are shown in Table 1.
• Example 4 When preparing the binder composition for a secondary battery, the binder for a secondary battery was prepared in the same manner as in Example 1 except that 50 parts of n-butyl acrylate, 40 parts of phenoxyethyl acrylate, and 10 parts of acrylonitrile were used as monomers. A composition, a slurry composition for a positive electrode mixture layer, a slurry composition for a negative electrode mixture layer, a slurry composition for a solid electrolyte layer, and an all-solid secondary battery were prepared and evaluated in various ways. The results are shown in Table 1.
• Example 5 Batteries for secondary batteries Binders for secondary batteries were prepared in the same manner as in Example 1 except that 85 parts of n-butyl acrylate, 7 parts of phenoxyethyl acrylate and 8 parts of acrylonitrile were used as monomers.
• a composition, a slurry composition for a positive electrode mixture layer, a slurry composition for a negative electrode mixture layer, a slurry composition for a solid electrolyte layer, and an all-solid secondary battery were prepared and evaluated in various ways. The results are shown in Table 1.
• Example 6 In the preparation of the binder composition for a secondary battery and various slurry compositions, Except that xylene (Example 6) and butyl butyrate (Example 7) were used instead of diisobutylketone as a solvent, the same as in Example 1. Similarly, a binder composition for a secondary battery, a slurry composition for a positive electrode mixture layer, a slurry composition for a negative electrode mixture layer, a slurry composition for a solid electrolyte layer, and an all-solid secondary battery are prepared and evaluated in various ways. went. The results are shown in Table 1.
• Example 8 When preparing the binder composition for a secondary battery, the binder composition for a secondary battery was the same as in Example 1 except that 67 parts of n-butyl acrylate, 25 parts of phenyl acrylate, and 8 parts of acrylonitrile were used as monomers.
• a product, a slurry composition for a positive electrode mixture layer, a slurry composition for a negative electrode mixture layer, a slurry composition for a solid electrolyte layer, and an all-solid secondary battery were prepared and evaluated in various ways. The results are shown in Table 1.
• Example 9 In the preparation of the binder composition for a secondary battery, 67 parts of n-butyl acrylate, 25 parts of ethoxylated o-phenylphenol acrylate, and 8 parts of acrylonitrile were used as monomers in the same manner as in Example 1.
• a binder composition for a secondary battery, a slurry composition for a positive electrode mixture layer, a slurry composition for a negative electrode mixture layer, a slurry composition for a solid electrolyte layer, and an all-solid secondary battery were prepared and evaluated in various ways. The results are shown in Table 2.
• Example 10 When preparing the binder composition for a secondary battery, the same as in Example 1 except that 67 parts of n-butyl acrylate, 25 parts of phenoxypolyethylene glycol acrylate, and 8 parts of acrylonitrile were used as monomers for the secondary battery.
• a binder composition, a slurry composition for a positive electrode mixture layer, a slurry composition for a negative electrode mixture layer, a slurry composition for a solid electrolyte layer, and an all-solid secondary battery were prepared and evaluated in various ways. The results are shown in Table 2.
• Example 11 Example 1 except that 60 parts of n-butyl acrylate, 29.8 parts of phenoxyethyl acrylate, 10 parts of acrylonitrile, and 0.2 part of allyl methacrylate were used as monomers in the preparation of the binder composition for a secondary battery.
• a binder composition for a secondary battery, a slurry composition for a positive electrode mixture layer, a slurry composition for a negative electrode mixture layer, a slurry composition for a solid electrolyte layer, and an all-solid secondary battery are prepared and evaluated in various ways. Was done. The results are shown in Table 2.
• Example 12 A slurry composition for a positive electrode mixture layer, a slurry composition for a negative electrode mixture layer, and a solid electrolyte layer are used in the same manner as in Example 1 except that the binder composition for a secondary battery prepared as follows is used. A slurry composition and an all-solid-state secondary battery were prepared and evaluated in various ways. The results are shown in Table 2. ⁇ Preparation of binder composition for secondary batteries> The reactor was charged with 2 parts of potassium oleate as an emulsifier, 0.1 part of potassium phosphate and 150 parts of water as a stabilizer, and 5 parts of acrylonitrile, 35 parts of 1,3-butadiene and n-butyl as monomers.
• Example 13 When preparing the binder composition for a secondary battery, the same as in Example 1 except that 58 parts of n-butyl acrylate, 20 parts of phenoxyethyl acrylate, 7 parts of acrylonitrile, and 15 parts of styrene were used as monomers.
• a binder composition for a secondary battery, a slurry composition for a positive electrode mixture layer, a slurry composition for a negative electrode mixture layer, a slurry composition for a solid electrolyte layer, and an all-solid secondary battery were prepared and evaluated in various ways. The results are shown in Table 2.
• Example 14 ⁇ Preparation of Binder Composition for Non-Aqueous Secondary Battery Positive Electrode Mixture Layer (Example 14)> An aqueous dispersion of a polymer (hydrogenated nitrile rubber) was obtained in the same manner as in Example 12. Using the obtained aqueous dispersion of the polymer, the amount of the polymer insoluble in N-methylpyrrolidone (solvent) was calculated, and the polymer was either easily soluble or sparingly soluble in N-methylpyrrolidone. Identified whether it is applicable. The results are shown in Table 2.
• Example 15 ⁇ Preparation of Binder Composition for Non-Aqueous Secondary Battery Negative Electrode Mixture Layer (Example 15)> Add 100 parts of ion-exchanged water and 0.2 part of sodium dodecylbenzenesulfonate as an emulsifier to a 1 L flask with a septum equipped with a stirrer, replace the gas phase part with nitrogen gas, heat the temperature to 60 ° C, and then start polymerization. As an agent, 0.25 part of potassium persulfate was dissolved in 20.0 parts of ion-exchanged water and added.
• the solid content concentration was adjusted to 30% to obtain an aqueous dispersion of the polymer (binder composition for the negative electrode mixture layer).
• the amount of the polymer insoluble in water (solvent) was calculated, and the polymer was easily soluble or difficult to dissolve in water. It was identified which of the solubility was applicable.
• Table 2 Further, the composition of the polymer was measured using the obtained aqueous dispersion of the polymer (binder composition for the negative electrode mixture layer). The results are shown in Table 2.
• N-methylpyrrolidone as a solvent is gradually added, and the mixture is stirred and mixed at a temperature of 25 ⁇ 3 ° C. and a rotation speed of 40 rpm to obtain a viscosity (using a B-type viscometer. Temperature: 25 ⁇ 3 ° C., Rotor: M4. , Rotor rotation speed: 60 rpm) was 3600 mPa ⁇ s to obtain a slurry composition for a positive mixture layer. The dispersibility and storage stability of the obtained slurry composition for the positive electrode mixture layer were evaluated. The results are shown in Table 2.
• Example 15 ⁇ Preparation of Slurry Composition for Non-Aqueous Secondary Battery Negative Electrode Mixture Layer (Example 15)> 97 parts of natural graphite (theoretical capacity: 360 mAh / g) as negative electrode active material particles and 1 part (solid content equivalent amount) of carboxymethyl cellulose (CMC) as a thickener were put into a planetary mixer. Further, it was diluted with ion-exchanged water so that the solid content concentration became 65%, and then kneaded at a rotation speed of 45 rpm for 60 minutes.
• natural graphite theoretical capacity: 360 mAh / g
• CMC carboxymethyl cellulose
• slurry composition for a positive electrode mixture layer was applied to an aluminum foil having a thickness of 20 ⁇ m, which is a current collector, with a comma coater so that the coating amount was 18 ⁇ 0.5 mg / cm 2 . Further, the slurry composition on the aluminum foil is dried and collected by transporting the slurry composition on the aluminum foil at a speed of 200 mm / min in an oven having a temperature of 120 ° C. for 2 minutes and further in an oven having a temperature of 130 ° C. for 2 minutes. A positive electrode original fabric having a positive electrode mixture layer formed on it was obtained.
• the copper foil coated with the slurry composition for the negative electrode mixture layer is conveyed at a rate of 400 mm / min in an oven at a temperature of 120 ° C. for 2 minutes and further in an oven at a temperature of 130 ° C. for 2 minutes.
• the slurry composition on the copper foil was dried to obtain a negative electrode raw fabric in which a negative electrode mixture layer was formed on the current collector.
• the negative electrode mixture layer side of the prepared negative electrode raw material was roll-pressed in an environment of a temperature of 25 ⁇ 3 ° C. to obtain a negative electrode having a negative electrode mixture layer density of 1.65 g / cm 3.
• the adhesiveness of the negative electrode mixture layer was evaluated. The results are shown in Table 2.
• ⁇ Preparation of Separator As a separator, a single-layer polypropylene separator (manufactured by Cellguard, product name "Cellguard 2500") was prepared. ⁇ Preparation of Lithium Ion Secondary Battery (Examples 14 and 15)> A single-layer laminated cell (equivalent to an initial design discharge capacity of 30 mAh) was prepared using the above negative electrode, positive electrode, and separator, placed in an aluminum packaging material, and vacuum dried under the conditions of 60 ° C. and 10 hours. ..
• the positive electrode, the negative electrode, the separator, and lithium were obtained in the same manner as in the above procedure except that the above-mentioned slurry composition for the positive electrode mixture layer and the slurry composition for the negative electrode mixture layer were separately stored and the stored slurry composition was used.
• An ion secondary battery was prepared or prepared, and the cycle characteristics (after storage of the slurry) were evaluated. The results are shown in Table 2.
• Example 16 In the preparation of the binder composition for a secondary battery, the binder composition for a secondary battery and the positive electrode were the same as in Example 1 except that 70 parts of n-butyl acrylate and 30 parts of phenoxyethyl acrylate were used as the monomers.
• a slurry composition for a mixture layer, a slurry composition for a negative electrode mixture layer, a slurry composition for a solid electrolyte layer, and an all-solid secondary battery were prepared and evaluated in various ways. The results are shown in Table 2.
• Comparative Example 1 When preparing the binder composition for a secondary battery, the same as in Example 1 except that 40 parts of n-butyl acrylate, 30 parts of phenoxyethyl acrylate, 15 parts of acrylonitrile, and 15 parts of styrene were used as monomers.
• a binder composition for a secondary battery, a slurry composition for a positive electrode mixture layer, a slurry composition for a negative electrode mixture layer, a slurry composition for a solid electrolyte layer, and an all-solid secondary battery were prepared and evaluated in various ways. The results are shown in Table 3.
• Comparative Example 2 In the preparation of the binder composition for a secondary battery, the same as in Example 1 except that 52 parts of n-butyl acrylate, 4 parts of phenoxyethyl acrylate, 18 parts of acrylonitrile and 26 parts of styrene were used as monomers.
• a binder composition for a secondary battery, a slurry composition for a positive electrode mixture layer, a slurry composition for a negative electrode mixture layer, a slurry composition for a solid electrolyte layer, and an all-solid secondary battery were prepared and evaluated in various ways. The results are shown in Table 3.
• Example 3 In the preparation of the binder composition for a secondary battery, the binder composition for a secondary battery and the positive electrode were the same as in Example 1 except that 40 parts of n-butyl acrylate and 60 parts of phenoxyethyl acrylate were used as the monomers.
• a slurry composition for a mixture layer, a slurry composition for a negative electrode mixture layer, a slurry composition for a solid electrolyte layer, and an all-solid secondary battery were prepared and evaluated in various ways. The results are shown in Table 3.
• the binder for a secondary battery was prepared in the same manner as in Example 1 except that 91 parts of n-butyl acrylate, 4 parts of phenoxyethyl acrylate, and 5 parts of acrylonitrile were used as monomers.
• a composition, a slurry composition for a positive electrode mixture layer, a slurry composition for a negative electrode mixture layer, a slurry composition for a solid electrolyte layer, and an all-solid secondary battery were prepared and evaluated in various ways. The results are shown in Table 3.
• the binder composition for a secondary battery was prepared in the same manner as in Example 1 except that 67 parts of n-butyl acrylate, 8 parts of acrylonitrile, and 25 parts of styrene were used as monomers.
• a slurry composition for a positive electrode mixture layer, a slurry composition for a negative electrode mixture layer, a slurry composition for a solid electrolyte layer, and an all-solid secondary battery were prepared and evaluated in various ways. The results are shown in Table 3.
• the binder composition for a secondary battery was prepared in the same manner as in Example 1 except that 70 parts of ethyl acrylate, 25 parts of phenoxyethyl acrylate, and 5 parts of acrylonitrile were used as monomers.
• a slurry composition for a positive electrode mixture layer, a slurry composition for a negative electrode mixture layer, a slurry composition for a solid electrolyte layer, and an all-solid secondary battery were prepared and evaluated in various ways. The results are shown in Table 3.
• Example 7 In the preparation of the binder composition for a secondary battery, the secondary was the same as in Example 1 except that 50 parts of methyl acrylate, 40 parts of methyl methacrylate, 5 parts of phenoxyethyl acrylate and 5 parts of acrylonitrile were used as monomers.
• a binder composition for a battery, a slurry composition for a positive electrode mixture layer, a slurry composition for a negative electrode mixture layer, a slurry composition for a solid electrolyte layer, and an all-solid secondary battery were prepared and evaluated in various ways. The results are shown in Table 3.
• PEA indicates a phenoxyethyl acrylate unit
• PA indicates a phenyl acrylate unit
• EPA represents an ethoxylated o-phenylphenol acrylate unit
• PPA represents a phenoxypolyethylene glycol acrylate unit
• BA represents an n-butyl acrylate unit and represents
• LA represents a lauryl acrylate unit
• EHA represents a 2-ethylhexyl acrylate unit
• EA indicates an ethyl acrylate unit and represents "MA” indicates a methyl acrylate unit
• MAA represents a methyl methacrylate unit
• AN indicates an acrylonitrile unit
• H-BD represents a 1,3-butadiene hydride unit
• ST indicates a styrene unit
• AMA indicates an allyl methacrylate unit
• EDM represents ethylene glycol dimethacrylate units
• DIK indicates ethylene glycol dimethacrylate units
• a slurry composition having excellent storage stability can be prepared, and a functional layer having excellent adhesiveness (positive electrode mixture layer or It can be seen that the negative electrode mixture layer) can be formed. Further, in Examples 1 to 16, it can be seen that the secondary batteries having good dispersibility of the slurry composition and excellent cell characteristics can be produced.
• Comparative Examples 1 to 7 using the material it can be seen that the dispersibility and storage stability of the slurry composition, the adhesiveness of the functional layer, and the cell characteristics of the secondary battery are deteriorated.
• a slurry composition for a secondary battery having excellent storage stability and a binder composition for a secondary battery capable of exhibiting excellent adhesiveness to the functional layer for the secondary battery.
• a slurry composition for a secondary battery which is excellent in storage stability and can form a functional layer for a secondary battery excellent in adhesiveness.
• a functional layer for a secondary battery having excellent adhesiveness and a secondary battery including the functional layer for the secondary battery it is possible to provide a slurry composition for a secondary battery having excellent storage stability and a binder composition for a secondary battery capable of exhibiting excellent adhesiveness to the functional layer for the secondary battery.

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